Systematic Survey on Petrochemical Technology

2

Keizo Tajima
 Abstract
The petrochemical industry involves the production of basic petrochemicals, industrialorganic chemicals and polymers using petroleum or natural gas as the raw material. The industry
took hold in Japan in the 1950s and almost immediately dominated the chemical industry; to thisday, the petrochemical industry still remains a key industry, providing raw materials to a wide
range of sectors in the Japanese chemical industry, including pharmaceuticals, cosmetics,
synthetic detergents, paints, plastic molding and rubber molding. By the 1960s, a mass supply ofplastic products had dramatically impacted society, triggering a polymer revolution andundergirding Japan’s rapid economic growth. New chemical factory conglomerates sprang up
along the coastlines, known as petrochemical industrial complexes or kombinats.
The petrochemical industry originated in the 1920s in the United States. However, up until
the early 1940s, it was little more than a chemical industry that existed only in the United States,
supplying a few industrial organic chemicals. Wood chemistry, oleochemistry, fermentation
chemistry and coal chemistry had all long flourished to the point of mass production prior to theadvent of petrochemistry, in Europe, the United States and Japan alike. Petrochemistryco-existed with these in the United States as yet another type of chemical industry. The
development of naphtha steam-cracking technology in the 1940s and the European migration of
the petrochemical industry in the 1950s had a major impact on petrochemical technology.
Innovations in petrochemical technology suddenly began to proliferate as the technology began
to be combined with conventional European chemical technology. The petrochemical industry
swallowed up many of the existing mass-producing chemical industries and quickly assumed a
key role among the other chemical industries.
It was at this time that Japan entered the petrochemicals arena. Since it already had
mass-producing chemical industries in place, it was in a position to do more than simply adopt
the new petrochemical technology being introduced; it took an active role in new technologicalinnovations. Japan’s prior experience meant that by the late 1960s it was absorbing
petrochemical technologies and successively developing its own. By the late 1970s, theintensive developments in petrochemical technology had eased, and petrochemistry began tospread across the developing nations. It was during this time that the negative aspects ofpetrochemistry began to emerge, such as environmental issues and chemical pollution issues. On
top of this, the two oil crises in the 1970s escalated the cost of petrochemical products, resulting
in a demand for low-emission technology and energy-conserving technology. By this time theJapanese petrochemical industry was no longer simply relying on technology imports and wasdeveloping its own technology. From the 1980s, the challenge was to develop olefins-based
products with at least three carbon atoms, rather than ethylene products with two carbon atoms.
The Japanese petrochemical industry was very active in this field. Petrochemistry became asubstantial chemical industry with a wide range of products in its arsenal.
Meanwhile, significant changes started taking place on the petrochemical industrial world
map with the emergence of the Middle Eastern petrochemical industry in the 1980s. This trend
has accelerated since the 2000s with China entering the industry and huge increases in
production. In the 2010s, the core of the petrochemical industry is taking a dramatic shift awayfrom the West and towards Asia and the Middle East. Accordingly, Western companies havebeen successively dropping out of the industry since the 1990s. However, unlike theircounterparts in the West, Japanese petrochemical companies took a different path. Japan is now
not only planning for greater functionalization within the petrochemical industry, but also
developing fields of functional chemistry outside of the conventional scope of petrochemistry,even incorporating polymer molding technology.

There have also been changes within the conventional scope of petrochemistry, such as
significant growth in the demand for propylene in contrast to ethylene. In response to thesechanges in business environment, new trends have been observed in petrochemical technology
since the 1990s. Petrochemistry may change significantly in the next decade or two.

 Profile
Keizo Tajima
Chief Survey Officer, Center of the History ofJapanese Industrial Technology, National Museum of
Nature and Science
1967:

Graduated from Tokyo Metropolitan Ueno
High School
1972:
Graduated from the Department ofSynthetic Chemistry, Faculty ofEngineering, The University of Tokyo
1974:
Completed Master’s degree at the Graduate
School of Engineering, The University ofTokyo
Joined the Ministry of International Tradeand Industry (administrative post)
1987:
Joined Mitsui Toatsu Chemicals Co., Ltd.
1997:
Transferred to Mitsui Chemicals, Inc. bymerger
2008:
Retired from Mitsui Chemicals, Inc.
Subsequently involved in writing, editing, translating
and lecturing
2015:
Chief Survey Officer, Center of the Historyof Japanese Industrial Technology, National
Museum of Nature and ScienceContents
Introduction..........................................................3
1
Overview of petrochemistry.................................62
Petrochemical product categories.....................22
3
Industrial organic chemicals and polymers
4
predating petrochemistry....................................56
History of the petrochemical industry................94
5
Technological system and systematization of
6
petrochemistry..................................................134
Conclusion......................................................194
7
Location Confirmation of Historical Technology
Resource Items from the Petrochemical Industry..........................................................................196
A list of abbreviations for the product names usedin this document ...............................................199

1 Introduction
Let us begin by defining petrochemistry
and clarifying the scope of what is covered inthis survey report.

1.1 Definition of petrochemistry
The petrochemical industry is often
defined as “a chemical industry withpetroleum as its raw material.” Certainly,
petroleum is the main raw material used intheJapanesepetrochemicalindustry.
However, globally speaking, there are vast
petrochemical industries in the United Statesand Middle East that use natural gas andassociated petroleum gas as raw materials; itis therefore inaccurate to use a definition that
only applies to the Japanese petrochemicalindustry. Furthermore, the above definition
only qualifies the raw material used in anindustry without determining to what extent
the products produced in that industry can beproducts of the petrochemical industry.
Current chemical industries are structured
as shown in Fig. 1.1. The petrochemicalindustry forms a core industry providing raw
materials to low-molecular organic chemical
end-product industries (pharmaceuticals,pesticides etc.) and high-molecular chemical
end-product industries (plastic molding,chemical fibers, coatings, etc.).
As shown in Table 1.1, the chemicalindustries here are the chemical and allied
product industries as defined by the Japan
Standard Industrial Classifications, as well as
plastic products, rubber products andchemical fibers (rayon, acetate, synthetic
fibers). Although the chemical fiber industry
was classified as a chemical industry up until
the 2002 revision of the Japan Standard
Industrial Classification, since then it has
been classified as a textile industry. Out ofconsideration for continuity of statistics,
production history and technical details, it has
been included as a chemical industry for the
purposes of this report.
In light of the current structure of thechemical industries, the petrochemicalindustry is defined in this report as “achemicalindustry
producingbasic
petrochemical products, industrial organic
chemicals and polymers using petroleum or
natural gas as the raw material.” Thepetrochemical industry spans a number ofindustries in the Japan Standard Industrial
Classifications, namely: basic petrochemicals,
aliphatic intermediates, cyclic intermediates,
plastics, synthetic rubber and surface-active
agents (surfactants). This definition is slightly
broader than what is generally termed as
petrochemistry, and includes industrialorganic chemicals made from methane,engineering plastics and functional polymers,
which have recently been developed into a
number of different products.
However, since the petrochemicalindustry often refers to products withsignificantly high production and demand
volumes, this report focuses on products
within this broader definition that have highproduction and demand volumes.

1.2 Focus of the survey report
Present-day petrochemical
products
include vinyl chloride, polyvinyl chloride(PVC), synthetic surfactants, coating resins
and adhesive resins. Some of these have been
touched on in other technology systemization
survey reports, such as the reports on vinyl
chloride (March 2001, March 2002), soaps
and synthetic detergents (March 2007),
coating (March 2010) and adhesives (August2012). The petrochemical industry has
produced a great number of products andproduct groups with an equally impressive
production scale, history and technology
system, including methanol and its
derivatives, olefins (including dienes),aromatics, alcohols, organic solvents,
plasticizers, acetic acid, polyvinyl acetate andits derivatives, ethylene oxide and its
derivatives, acrylonitrile and its derivatives,
acrylic acid and its derivatives, methyl
methacrylate and polymethyl methacrylate,polyethylene, polypropylene, styrene andstyrenic polymers, phenol and its derivatives,
Systematic Survey on Petrochemical Technology

3phenol resin and amino resin, polyurethane
and its raw materials, epoxy resin,
unsaturated polyester resin, polyethylene
terephthalate (PET) resin and its raw
materials, polyamide resin (nylon resin) and

its raw materials, engineering plastics,
generic synthetic rubbers, special synthetic
rubbers, thermoplastic elastomers, siliconresin and fluorine-based industrial organic
chemicals and resins.

Fig. 1.1 Chemical industry and petrochemical industry.
Table 1.1 Definition of chemical industry

Supposing that olefins, vinyl chloride or
the like were single trees, then petrochemistry
would be an entire forest. Accordingly,
surveying petrochemistry to the same depth
as vinyl chloride or other technology

4systematization reports that have already been
done would be impossible, not only in termsof the sheer number of hours and pages
required, but also in terms of the capabilities
of a single survey officer. It would also not be

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

enough to simply focus on some of the as yet
unreported areas of petrochemistry, such as
olefins, phenol and its derivatives, or
polyethylene, as then the overall picture of
petrochemistry would be lost. Consequently,
this survey report does not focus in on any
particular area, instead providing awide-angle view of the overall field of
petrochemistry and discussing the wider
trends of the entire forest. Readers should be
advised that this report will not go into thesame level of detail on the individual trees, so
to speak, as has been done in other survey
reports.
As a lead-up to the history of
petrochemistry, this report does provide a
relatively detailed outline of the industrialorganic chemical and polymer industries thatexisted prior to the establishment of thepetrochemical industry, using raw materials
other than petroleum or natural gas, such as
the coal chemical industry. These industries
have now come under pressure from thepetrochemistry industry and have diminishedsignificantly. However, they are essential toany consideration of the history of
petrochemical industry technology. They

have been included in this report because
there would be few other opportunities toinclude
them
in
other
technology
systematization survey reports.
The petrochemical industry was foundedin the United States of America in the 1920sand developed from there. Industries were
established in Europe and Japan following aworldwide increase in Middle Eastern oil
exports from the 1950s onwards. Since the1970s, petrochemical industries havecontinued to expand all around the world.
The raw materials, products and technologiesof the petrochemical industry have been
traded the world over since the 1950s.
Accordingly, the development of thepetrochemical industry in Japan must be
viewed in the context of global trends; thissurvey report focuses the worldwide
petrochemical industry as much as possible,
rather than just Japan.
Please note that since this report isintended for the general public, the use ofchemical structural formulas has been
provided only for reference and the use ofchemical reaction formulas has been avoided
as much as possible.

Systematic Survey on Petrochemical Technology

5

2 Overview of petrochemistryThis chapter provides an overview ofpetrochemistry. What are petrochemical
products? What are they used for? How does
the petrochemical industry relate to society
and to other industries? What are thedistinguishing
characteristics
oftheproduction
technology?
What
other
technologies
have
been
based
on
petrochemical technology and what related
technologies
undergird
petrochemistry?
These are the points that shall be addressed.

2.1 Uses of petrochemical products
Petrochemical products can be divided
into three major categories, as shown in
Fig. 2.1. These are basic petrochemicals,
industrial organic chemicals and polymers.
Figure 2.1 also shows some of the main
products in each of these categories.
However, there are actually far moreproducts than those given here.

hydrocarbons. Aromatic hydrocarbons arehydrocarbons with a relatively stable carbon
ring (aromatic ring) [Footnote 2]. Typical
products include benzene (C6), toluene (C7)and xylene (C8). Olefins are hydrocarbons
with double bonds and no aromatic ring.
Typical products include ethylene (C2, one
double bond), propylene (C3, one doublebond), butylene (C4, one double bond),
butadiene (C4, two double bonds), isoprene(C5, two double bonds) and cyclopentadiene(C5, cyclic structure, two double bonds)[Footnote 3]. The molecular structures ofsome typical basic petrochemical products areshown in Fig. 2.2 for reference.

Fig. 2.1 Current raw materials and principal
products of the petrochemical industry.
2.1.1 Uses of basic petrochemicals
The main use for basic petrochemicals
with a one carbon atom (C1) (syngas, carbon
monoxide, phosgene, hydrogen cyanide,chloromethane) is as the raw materials forindustrial organic chemicals. A small amountis used as organic solvents and also as a raw
material for industrial inorganic chemicals.
Basic petrochemicals with two or morecarbon atoms can be divided into two broad
categories: olefins [Footnote 1] and aromatic[Footnote 1] A compound comprising only carbon and hydrogen iscalled a hydrocarbon. As the number of carbon bonds and bonding
methods can vary greatly, there are an almost unlimited number of6

different hydrocarbons. Hydrocarbons with one or more double
bonds are called olefins. Hydrocarbons with only one double bondare also called alkenes. Double bonds are more reactive than single
bonds[Footnote 2] Typical examples are benzene rings, with six carbons
joined in a ring, and naphthalene rings. Aromatic rings themselves
are very stable and do not break easily. Atoms or functional groups
attached to the edge of an aromatic ring are more susceptible than to
substitution reactions or oxidation reactions than the carbon-carbon
bonds forming the aromatic ring.
[Footnote 3] Other than cyclopentadiene, the typical olefins-based
products mentioned have a linear carbon structure (and are capableof branching). Cyclopentadiene has five carbon atoms in a cyclic
structure. See Fig. 2.2 for the chemical structural formula.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

provide the raw material for industrialorganic chemicals. Other than industrialorganic chemicals, another major application
for these is in solvents. Benzene, toluene andmixed xylene (xylene isomer mixture) areused in solvents.
Fig. 2.2 Molecular structures of typical basic
petrochemicals.
In principle, there are many otherhydrocarbons besides these with eight or lesscarbon atoms. This also includes some
substances produced by steam cracking of
naphtha, as shall be mentioned later.
However, these are seldom used as basic
petrochemical products as they do not have
any widespread applications and theseparation and purification process is adifficult one.
Thus,
even
includingisomers[Footnote 4], there are no more than around adozen basic petrochemical products at mostthat are being put to use in large quantities.
The only use for basic petrochemical
products is to provide the raw materials forindustrial organic chemicals and polymers.
Olefins are often consumed as raw materials(monomers) for polymers without being madeinto industrial organic chemicals. Of all of thepetrochemical products produced worldwide,around 60% of ethylene is estimated to be
consumed as polyethylene, 60% of propylene
goes into polypropylene (PP) and synthetic
ethylene-propylene rubber (EPR), at least
90% of butadiene goes into styrene-butadiene
rubber (SBR), butadiene rubber (BR),acrylonitrile-butadiene rubber (NBR) andother synthetic rubbers, as well as
acrylonitrile-butadiene-styrene resin (ABSresin) [Footnote 5]. The remaining 40% of
ethylene and propylene goes into a very wide
variety of industrial organic chemicals.
Meanwhile, aromatic hydrocarbons arealmost never used in polymers directly; they

2.1.2 Uses of industrial organic chemicals
Industrial organic chemicals are made byreacting basic petrochemical products
together, or by reacting them with inorganic
chemicals, such as air, oxygen, hydrogen,water, ammonia, chlorine, sulfuric acid or
nitric acid. Unlike basic petrochemical
products, there is an extremely diverse range
of industrial organic chemicals with various
chemical and physical properties. The
products shown in Table 2.1 are just a very
few examples of industrial organic chemical
products with particularly high production
volumes.
To a certain extent, industrial organic
chemicals can be broadly categorized byfunctional group [Footnote 6]. Table 2.1
shows examples of types and products oftypicalindustrialorganic
chemicals
categorized by functional group. Fig. 2.3 also
shows examples of typical functional groups
along with chemical structural formulas oftypical products. Since the chemical
properties of industrial organic chemicals
largely depend on the functional group, thesecategorizations can provide a general idea of
their application and method of production.
For example, many alcohols are used directly
as solvents and have esters or ethers as theirfeedstock. As epoxides have very reactive
three-membered rings containing oxygen,they are used to produce other industrialorganic chemicals or in polymerization
reactions. In many cases, a single industrialorganic chemical has multiple applications,being used as an organic solvent as well as anorganic intermediate.

[Footnote 4] Some substances have different chemical and physicalproperties despite having the same molecular formula, due to having
different chemical structures. The substances are called isomers. For
example, there are four isomers of butylene with four carbon atoms
and three isomers of xylene with eight carbon atoms, as shown in
Fig. 2.2. Including the similarly-structured ehtylbenzene, there are
four such isomers.
[Footnote 5] Since the Japanese petrochemical industry supplies adiverse range of products, around 40% of ethylene and propylene isconsumed only as polyethylene and PP.

[Footnote 6] An atom or group of atoms that determines theproperties of an organic compound is called a functional group. For
example, the alkyl group, which is composed of only carbon andhydrogen, carries the properties of being hydrophobic and having
relatively low reactivity. The hydroxyl group, composed of oxygenand hydrogen, carries the property of being hydrophilic. The chlorogroup carries the property of being flame retardant.
Systematic Survey on Petrochemical Technology

7

Table 2.1 Typical industrial organic chemical types and products

Fig. 2.3 Examples of typical functional groups and molecular structures ofindustrial organic chemicals.
As shown in Table 2.2, the main uses forindustrial organic chemicals are monomers(feedstocks for polymers), organic solvents,
refrigerants,
heattransfer
medium,plasticizers, surfactants, organic intermediates
and other uses.

8(1) Monomers (feedstocks for polymers)
Quantitatively, the most common
application by far for industrial organic
chemicals is monomers. There are four typesof monomers, as shown in Table 2.2.
Carbon-carbon double-bonded monomers
form polymers through a reaction whereby

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

the double bond becomes a single bond, andthe monomers join together. Cyclic
monomers form polymers through the
opening of the ring. Monomers with multiple
functional groups within one molecule form
polymers through a reaction between
functional groups that creates new bonds. For
example, ethylene glycol (EG) is a type ofalcohol and has two hydroxyl groups.
High-purity terephthalic acid (PTA) is acarboxylic acid and has two carboxyl groups.
The hydroxyl groups and carboxyl groups
react, releasing water and forming an ester
linkage. When EG and PTA form an ester

linkage on a molecule, a hydroxyl group anda carboxyl group form at the ends of themolecule, and the EG and PTA can react
further. The same thing happens even whenlarger molecules produced react together.
Thus, the molecule grows and forms apolymer. Monomers with multiple reactive
sites act the same way as monomers withmultiple functional groups, with reactive sites
reacting to form new bonds and creating a
polymer. For example, phenol has threereactive sites, and formaldehyde has tworeactive sites.

Table 2.2 Typical industrial organic chemical applications and example products(2) Organic solvents, refrigerants, heattransfer mediums, plasticizers
Not only are organic solvents used in thechemicalindustry (reaction
solvents,
synthetic fiber spinning solvents, extraction
solvents, etc.), they are also used in large
quantities in the machinery industry(degreasing agents for machine parts
processing, and cleaners for semiconductor
manufacturing, refrigerants and heat transfer
mediums, etc.) and the laundry industry (drycleaning) as well. They are also used ascomponents in chemical products, such as
coatings, adhesives, printing inks, aromas,
cosmetics and pesticides. Furthermore, they
have also recently started being used as acomponent(electrolyte
solution)inlithium-ion secondary batteries. Plasticizers
are liquid organic chemical products withhigh boiling points; these are used to soften
polymers and to improve moldability.
(3) Surfactants
A large amount of surfactants are used insynthetic detergents. They also have a wide
range of other applications, such as fabricsofteners, concrete water-reducing agents,
disinfectants, foaming and antifoaming agentsand solubilizers and emulsifiers for cosmetics
and pesticides.
(4) Organic intermediates
Organic intermediates are solely used as
feedstocks for other industrial organic
Systematic Survey on Petrochemical Technology

9chemicals, such as ethylbenzene, feedstock
for styrenes, cyclohexane, feedstock forcaprolactam and adipic acid and ethylene
dichloride, feedstock for vinyl chloride andchlorinated solvents. These form asubstantially high volume of products. Some
organic intermediates are also used as
feedstocks in chemical industries outside of
the petrochemical industry, pharmaceuticals,pesticides and dyes. There are numerous
different types of these organic intermediates,
although the individual types are not very
substantial in volume.
(5) Other uses
Other applications that use high volumesof industrial organic chemicals are gasoline
feedstocks and petroleum additives, such asalkylates [Footnote 7] and methyl tertiary
butyl ether (MTBE). Alkylates are producedby oil refineries and are often self-consumed.
2.1.3 Uses of polymers
Substances with a molecular weight ofaround 1,000 or higher are called polymers.
Since polymers are formed by monomers,
substances with a low molecular weight,
going through a very large number ofreactions, their molecular structure is madeup of a very long series of repeated units. The
reaction that produces polymers is calledpolymerization.
There are a very high number of different
types of polymers, although they are not as
numerous as industrial organic chemicals.
Polymers can be classified in various ways,
such as by molecular structure, bypolymerization method or by application. For
reference, Fig. 2.4 shows the molecular
structures of some typical polymers. Table
2.3 shows a classification of polymers byapplication. Polymer applications can be
categorized into molding products, coatings,
adhesives and binders and high performance
products. In this report we shall only covermolding products, since these account for thehighest volume by far.
Molding products can be divided into
three broad categories: plastic molding
products, synthetic fibers and rubber molding

products.
(1) Plastic molding products
While the term plastic can refer to any
material that can be molded into a desired
shape (any material with plasticity),
nowadays it is generally only used to describe
polymers. Plastics can be grouped into
thermoplastics and thermoset plastics.
Thermoplastics are polymers that soften or
fluidize when heated. These are molded while
hot and form the finished product once cooled.
If the finished product is heated again, it
softens or melts. Conversely, thermoset
plastic finished products no longer soften or
melt, even when heated again. Thermoset
plastics are molded at the raw material stage
while the molecular weight is low and thematerial has some fluidity, or at asemi-polymer stage when the molecularweight has increased to a certain extent. After
molding, the product is then heated tocomplete the reaction further, resulting in thefinished product. The reaction that takes placethrough heating after molding links thepolymers together in three dimensions(crosslinking).

[Footnote 7] Gasoline base materials that are multi-branch chain
saturated hydrocarbon mixtures made by reacting isobutene withpropylene, butylene or other olefins.

10

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 2.4 Typical polymer chemical structures.
Table 2.3 Polymer applications and example products

Since the molding stage generally allows
thermoplastics to have a far greater
productivity
thanthermoset
plastics,
thermoplastics have far higher production
volumes. These categorizations are notabsolute, as the same polymer can be madeinto a thermoplastic or a thermoset plastic,
depending on the molecular design of thepolymer structure and on how thepolymerization and molding are achieved.
For example, polyethylene is very commonlyused as a thermoplastic; however, in somecases it is used as a thermoset plastic, being
crosslinked to form a three-dimensional
structure after molding, such as forhigh-voltage cables and for water supply andhot water piping. Polyurethane is also often
used as a thermoset plastic, and thepolyurethane foam used in cushions is athermoset
plastic
product.
However,thermoplastics
with
one-dimensional
molecular structures are used for synthetic
Systematic Survey on Petrochemical Technology

11fibers.

history of the petrochemical industry in Japanas an example.

(2) Synthetic fibers
Synthetic fibers are made from polymers
with one-dimensional structures that areeasily crystallized. After forming the fiber
shape, they are stretched to increase thedegree of crystallinity, which significantly
increases the tensile strength of the fiber.
Synthetic fibers can be treated as a type ofthermoplastic molding product.
(3) Synthetic rubber molding products
Synthetic rubbers are materials with
so-called rubber elasticity. Rubber molecules
have a far looser molecular structure at room
temperature than plastic molecules. Therefore,
when stretched, their tensile strength
decreases considerably and they expand
significantly. Since the rubber molecules arecrosslinked to each other and the molecular
chain does not shift, when the stretching force
is released, the rubber immediately returns to
its former shape. Thus, rubbers differ
significantly from plastics in terms of their
physical properties. Synthetic rubbers are
molded in a softened state. At that stage,
sulfur and crosslinking agents are kneaded in.
After molding, a vulcanization reaction
occurs upon heating. This is the same as the
crosslinking reaction in thermoset plastics.
The sulfur and crosslinking agents link therubber molecules together and the elastic
properties emerge.
Bycontrast,
likethermoplastics,
thermoplastic elastomers melt when heatedand can be molded. Once cooled, this forms amolding product with elastic properties.
There is also no need to add sulfur andcrosslinking agents or to induce avulcanization reaction by heating. These
synthetic rubbers are high in productivity due
to the molding process.

2.2 Interaction

betweenthepetrochemical industry and otherindustries and society

The petrochemical industry has hadvarious interactions with other chemicalindustries, other industries and also wider
society. The following is a brief outline of the12

2.2.1 The polymer revolution
The petrochemical industry became
industrialized in Japan in the late 1950s,
mainly through introduced technology fromthe West. By the end of 1960s, the industry
was supplying large volumes of new products,
suchaspolyethylene,
polystyrene,
polypropylene (PP), polyester fiber, acrylic
fiber and SBR.
On top of this, changes in raw materials
and manufacturing methods in the 1960s saw
the petrochemical industry take up andsignificantly develop new product categories
that had been previously supplied by otherchemical industries, such as nylon fiber,
polyvinyl chloride, vinylon fiber, acetates andplasticizers. The petrochemical industry
expanded by thus supplying large quantitiesof polymers to society, having a significant
impact both on society and on other industries.
Polymers had steadily spread across theUnited States throughout the 1930s–1950s
and took Japan by storm in the late 1950s
with the introduction of the petrochemicalindustry, sparking a polymer revolution in
Japanese society. In addition, petrochemicalindustry production volumes skyrocketedfrom the late 1950s to the 1960s; this requiredlarge-scale capital investments to fund it, andplayed a hand in spurring Japan’s rapid
economic growth. From the 1970s onwards,
this pattern repeated again and again with theestablishment of petrochemical industries in
Korea, Taiwan, the ASEAN nations and even
China.
Polymers advanced into new territories
that had previously been the domains of wood,
paper, natural fiber, natural rubber, glass,ceramics and metals. Polymers had theadvantages of being lightweight, moldable,
water resistant and corrosion resistant. They
were initially used in a number ofapplications,
includingfibers,packaging/containers,
daily necessaries,
agricultural film, tires and wire coating. Later,
they also came to be used in applications
requiring higher strength and durability, suchas construction, civil engineering, machineparts, fishing vessels, large-scale tanks andNational Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

optical fibers. Currently, they are even being
used in aircraft fuselages. Thus, polymers
have made a significant contribution toenergy conservation, product longevity andcost reduction in many industries, including
manufacturing, distribution, transport andcommunications
andthe informationindustry.
2.2.2

Structural changes in the chemicalindustry
While the Japanese petrochemicalindustry was achieving considerable growthwithin the first two decades of its
establishment,
the
wider
Japanesepetrochemical industry was also undergoingsignificant structural changes, in which thepetrochemical industry came to take a leadingrole. The coal chemical industry (theacetylene chemical industry and coal tar
chemical industry) and the fermentation
chemical industry (ethanol fermentationindustry and acetone-butanol fermentationindustry), suddenly went into decline at theend of the 1960s, despite both having
predatedtheestablishmentofthepetrochemical industry. The celluloid
industry, which had been one of Japan’s
leading chemical industries since the 1910s,
using cellulose (natural polymer) fromwood/pulp as a raw material, and therayon/acetate industry went into decline in
the 1960s under pressure from the newplastics and synthetic fibers that were being
produced by the petrochemical industry.
By contrast, polymer molding industries,
such as plastic molding, rubber molding andsynthetic fibers, were expanding dramatically
due to the high-volume supply of low-cost
plastics, synthetic rubbers and synthetic
fibers.
Even the soap industry, which usednatural fat as a raw material, went into
decline due to pressure from the synthetic
detergent industry, which used synthetic
surfactants supplied by the petrochemicalindustry as its main raw material. The paintindustry, which had similarly used natural
fats and oils as raw materials, alsotransitioned to synthetic polymers as raw
materials.
Synthetic
dyes,
synthetic
pharmaceuticals, cosmetics, pesticides andother chemical industries that had used coalchemical products and natural products as
raw materials likewise transitioned to using
petrochemical products as raw materials.
2.2.3

Location changes in the chemicalindustry
The Japanese petrochemical industry wasestablished using naphtha (a petroleum
distillate with a boiling point between 30–
200°C) as a feedstock; the naphtha was
supplied by oil refineries refining andseparating crude oil imported mainly from theMiddle East. The steam cracking of naphtha
produced a number of liquid and gas basic
petrochemical co-products. Costs werereduced by piping these products to adjacentindustrial organic chemical plants andpolymer plants. At that time, it was importantthat all of the basic petrochemical
co-products were used up. Accordingly, theJapanese petrochemical industry took theform of a coastal industrial complex or
kombinat, incorporating multiple chemicalplants on an expansive site, right from theoutset.
Until then, the chemical industries inJapan had used coal, electricity (mainlyhydroelectric) and agricultural produce as raw
materials, and had developed separately in
different inland areas where those raw
materials could be obtained [Footnote 8].
These existing chemical industries wereforced to move to coastal industrial
complexes by the petrochemical industry at
the point where the raw materials wereconverted into petrochemistry. Many
high-producing inorganic chemical industries,
such as ammonia, industrial gas (oxygen,nitrogen, etc.) and salt electrolysis (chlorine,
sodium hydroxide), have a far longer history
than the petrochemical industry. Since thepetrochemical industry requires large
amounts of ammonia, oxygen, nitrogen andchlorine, as well as the carbon source, manyof these inorganic chemical industries also
started relocating to coastal industrial
complexes as the petrochemical industry
began to grow in scale. Thus, the[Footnote 8] Some of the coal chemical industries andelectrochemical industries also had factories in the form of industrial
complexes to maintain their product chains.
Systematic Survey on Petrochemical Technology

13petrochemical industry effected significant
structural changes in the geographic mappingof Japan’s chemical industries, withindustries centering on the petrochemicalindustrial complexes.
2.2.4

Pollution/environmental issues andresponses
Meanwhile, as the petrochemical industry
developed, expanded in scale and centralized,
its negative impacts on society also began toemerge. These included industrial pollution
issues, plastic waste issues, chemical
pollution issues and global environmental
issues. To manage these, Japan carried out
intensive emergency-response anti-pollution
measures within a short period in the 1970s.
From the 1980s onwards, these were followedby technology developments to revolutionize
the chemical reaction processes from theground up and to develop substitute products.
The problem of plastic waste has beendifficult to resolve, but the cooperation ofsociety (such segregated collection and waste
power generation) and other industries (suchas the cement and steel industries) has now
finally led to some progress towards a
resolution, mainly through thermal recycling
and material recycling.
Contribution to energy
conservation
The two oil crises of the 1970ssignificantly impacted the petrochemicalindustry, not only in Japan, but all over theworld. This prompted the development ofenergy-conserving technologies within the
petrochemical industry, such as gas phaselinear low-density polyethylene (L-LDPE)
production
technology.
Meanwhile,lightweightplastics
werebecoming
widespread throughout the automotive andaircraft industries, thereby improving theenergy efficiency of cars and airplanes.
Plastics with superior thermal insulation
performance were being promoted as
insulation in refrigerators, buildings andresidential facilities. Thus, the petrochemicalindustry made a major contribution to social
and industrial energy conservation through its
products.

2.3 Undergirding technologies for the
petrochemical industry
Petrochemistry is said to have had theUnited States as a mother, and Germany as afather. This refers to the fact that petroleum
refining technology was developed in the
UnitedStates,andthat
industrialorganic/industrial inorganic chemicals andlarge-scale synthesis technology for synthetic
oil were developed in Germany, as well as
referring to polymer synthesis technology,
such as the industrialization of synthetic
rubber, which also started in Germany. These
technologies laid the foundation for theestablishment of the petrochemical industry.
The technologies that formed the basis for theestablishment
anddevelopmentof
petrochemistry can be broadly grouped into
four main areas, as shown in Fig. 2.5.
Essentially, petrochemistry is an organic
chemical industry; accordingly, organic
chemistry technology plays the mostsignificant role in undergirding it. However,this goes without saying and can beoverlooked here.

2.2.5

14

Fig. 2.5 Undergirding technologies for the
petrochemical industry.
2.3.1

Petroleum cracking technology andpetroleum reforming technology
Petroleum cracking technology andpetroleum reforming technology weredeveloped in the United States as a means ofobtaining as much good-quality gasoline aspossible from crude oil. These are related to
steam cracking technology and aromatichydrocarbon production technology, and form
the core technologies for producing basic
petrochemical products.
2.3.2

Cryogenic distillation technology

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

German company Linde AG completed
an industrial air liquefaction equipment in
1895. This was followed by initiatives todevelop cryogenic distillation technology,
with devices developed for pure oxygen in
1902, pure nitrogen in 1903 and a
two-column device for both pure oxygen andpure nitrogen in 1910. At the time, pureoxygen was used for welding and cutting; inthe middle part of the 20th century, it started
being used in large quantities in converter
furnaces. Pure nitrogen was used to produce
nitrolime, and also in ammonia synthesis.
Cryogenic distillation technology was later
used to separate hydrogen from syngas andwater gas; the hydrogen was used in thehydrogenation of fats and oils and as a raw
material in ammonia synthesis.
This kind of cryogenic distillation
technology was essential in petrochemistry.
In particular, accurate separation of different
gases was very important in the steam
cracking of naphtha. Distillative separation of
ethane from natural gas, as well as precise
distillation separation of ethane and ethylene,
and propane and propylene, is the mostprominent example of how cryogenic
distillation
technology
underpins
petrochemistry.
2.3.3

Industrial catalyst technology,
high-pressure technology andcontinuous operation technology
Industrial catalyst technology andhigh-pressure technology, starting withammonia synthesis in the 1910s, have comeincreasingly into play in petrochemical
technology.
Acrossthehistoryofpetrochemistry, nearly all new products andprocesses have come about due to thedevelopment of new industrial catalysts. At
the same time, high-pressure technology laida significant milestone in petrochemistry withhigh-pressure
low-density
polyethylene
production technology in the 1930s.
Reactions under high pressure have been
established as one of the fundamental
petrochemical technologies, although not tosuch a high pressure as this. Petrochemical
equipment often used in high-pressurechemistry is extremely compact and highly
productive.

Meanwhile,
continuous
operationtechnology for successively reacting and also
separating and purifying large volumes ofgases and liquids can be traced back to 1867,
with the Solvay process (ammonia-soda
process). However, it was technologies
developed for ammonia synthesis, methanol
synthesis and synthetic oil that laid theimmediate foundation for the continuous
processes widely used in petrochemistry.
2.3.4 Polymer synthesis technology
For the first couple of decades of its
establishment in the United States,
petrochemistry was mainly used for products
such as solvents, petroleum additives andantifreeze. However, a push for the
production of synthetic rubber in the UnitedStates in the 1940s formed the first links ofthe polymer industry with petrochemistry,and significant development began on the
petrochemical industry in the United States.
Even today, as mentioned previously,
polymers make up for an overwhelmingly
high proportion of basic petrochemical
product consumption and industrial organic
chemical consumption. By linking withpolymers, petrochemistry has transformed
into a materials-supply industry, and alarge-scale industry at that. Most of thepolymer synthesis technology alreadyachieved by the 1940s involved monomers
produced by the coal chemical industry or thefermentation chemical industry. These
technologies
wereincorporated
into
petrochemistry and became fundamental
technologies of the petrochemical industry. In
the 1950s, Europe also entered thepetrochemical era, with large quantities ofolefin being supplied. Ziegler-Natta catalysts
were discovered in Europe at that same time,
and this new polymer synthesis technology
became the first polymer technology inpetrochemistry. This technology later resulted
in a great leap forward in petrochemistry.

2.4 Related technologies that support
petrochemistry
As mentioned several times previously,
petrochemical technology was introduced toJapan in the late 1950s. A lot of related
Systematic Survey on Petrochemical Technology

15supporting technology was also introduced toJapan at the same time. There were four maintechnologies, as shown in Fig. 2.6. This was
also a time of breakthrough in thesetechnologies that were essential topetrochemistry. In that sense, petrochemistrybecame industrialized in Japan with very
good timing.

Fig. 2.6 Related technologies that support
petrochemistry.
However, not all chemical companies
adopted these related technologies. If we lookat the history of various chemical companies,
we see that in the early 1950s many of theminvestigated the American petrochemicalindustry and petrochemical technology andconsidered whether or not to enter the market.
At that time, there was often a strong sense ofresistance to petrochemical technology andalso related technologies among chemicalcompanies experienced in batch reactions,such as synthetic dyes. This was due todifferences between science-type chemical
corporate culture and engineering-type
chemical corporate culture. In many cases,
these differences in corporate culture resulted
in companies failing or lagging behind in
introducing petrochemistry.
2.4.1 Chemical engineering
Chemical engineering was developed in
the 1910s by the American oil refining
industry. It developed as an academic
discipline focused on physical operations thatare utilized across the oil refining andchemical industries, such as flow (fluid
transport, filtration), thermal conductivity andmass transfer (gas absorption, distillation,
extraction, drying, adsorption). Arthur D
Little from the United States advocated theidea of unit operation; chemical engineering
was established once it was incorporated into

16

the education curriculum. By the end of the
1920s, unit operation had a greater amount of
substance, such as the completion of
distillation theory, and it began to be utilized
by the American oil refining industry and also
the petrochemical industry as well. Further
developments were also taking place inprocess engineering, which examines the oil
refining process and chemical processes
overall, and reaction engineering, which
focuses on the core reaction part of theprocess. Chemical engineering became an
essential technology, not only in terms ofdesigning,procurement,
managing
construction and operation of individual
petrochemical facilities, but also for planningand designing complete factories and overall
industrial complexes.
German-style industrial chemistry andapplied chemistry had also been taught inJapan since the start. However, this was
fundamentallydifferent
fromthesystems-engineering nature of chemicalengineering. Although organizations such as
Kanazawa Higher School of Technology(now
Kanazawa
University),
Kyoto
University and Tokyo Institute of Technology
had established chemical machinery andchemical engineering departments by around
1940, chemical engineering was not yet
widely known about in the Japanese chemicalindustry. In the 1950s, petrochemical
technology and chemical engineering wereboth adopted by the Japanese chemicalindustry, and the idea of chemicalengineering was welcomed with new wonder.
Today, chemical engineering has taken holdin many fields of the chemical industry
besides petrochemistry and is becoming a key
technology right across the chemical industry.
2.4.2

Instrumentation and control
technology
Instrumentation and control is technology
to operate a plant using three factors:
measurements by measuring instrumentation,
automated feedback control and automatic
valves. When petrochemistry was introduced
to Japan, instrumentation and control
technology was transitioning from pneumatic
control to electronic control, and thetechnology was becoming more compact andmore long-range. Accordingly, Japan’s new

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

petrochemical plants built central control
rooms for monitoring and control. Thismethod of operation, called process
automation, had not been available to theexisting chemical industries in Japan. The
petrochemical industry and the oil refining
industry were the first to implement
automated production processes.
2.4.3 Instrumental analysis
The late 1950s, when petrochemistry was
introduced to Japan, was the time in which
technologies to support petrochemistry were
just coming into full swing; instrumental
analysis technology was no exception. Gas
chromatography and infrared spectroscopy
are often used in petrochemistry. In gas
chromatography, analysis is made byseparating out gaseous components andeasily-vaporized liquid components; ininfrared spectroscopy, organic compounds areanalyzed by functional group. The world’s
first gas chromatograph was introduced in
1955; by 1957, Japan had developed its own
mass-produced gas chromatograph equipment.
By 1958, the process gas chromatograph was
being developed. By 1957, a high-resolution
infrared spectrophotometer had also beendeveloped.
While these analysis devices were
initially expensive, prices eventually dropped
significantly and they came to be widely usedin the petrochemical industry, not only for
research and development and quality control,
but also for process management.
2.4.4 Polymer molding technology
Natural rubber molding technology as apolymer molding technology developed fromthe mid-19th century onwards. Vulcanization
was discovered in 1839. The development ofrubberprocessing
machineryandvulcanization techniques (1849) by Thomas
Hancock in the United Kingdom significantly
advanced rubber molding technology.
Although natural rubber is a difficult material
to process, molding was achieved withcalender molding technology using rollers,
and through press molding technology. In the20th century, rubber molding technology had
become a large-scale industry before theSecond World War, with many rubber
molding products being used in theautomotive industry, such as for car tires.
Natural rubber molding in Japan started in
1886, when Tsuchiya Rubber Factorycommenced operations using vulcanization
methods. The tire industry became
established in Japan in the 1920s, and by1931 Bridgestone had commenced productionof a purely Japanese-produced tire.
Meanwhile, celluloid, a thermoplastic
polymer, was industrialized in the late 19th
century and was being used in molding
products. Natural rubber molding technology
was applied to celluloid molding. In the
1910s, phenol resin, a thermosetting resin,
was industrialized. The molding method wascompression molding, an extension of press
molding. By the 1930s, polyvinyl chloride,
polystyrene, polyethylene and other polymers
had been industrialized in Europe. While themolding of these polymers did not extend
beyond applying rubber molding technology,
the screw extruder soon emerged as what
could be called an archetype for modern
extruders. By 1939, hard PVC pipes werebeing manufactured in Europe.
Highly productive molding technologies
for thermoplastics include extrusion molding,blow molding and injection molding.
Injection molding had been developed in theWest before the Second World War, but only
for very small products at very slow speeds.
In the 1950s, Japan made significant
advances in PVC, polyvinyl acetate (PVA)
and urea resins through coal chemistry. Japan
was also importing polyethylene andpolystyrene. Molding fabricators and molding
machine companies started out by importing
molding machines from the West and starting
to produce molding products. Right aroundthis time there were some rapid developments
in extrusion molding and injection molding,making it possible to produce larger products
faster. Accordingly, in the late 1950s, just as
the petrochemical industry was being
established in Japan, a foundation was beinglaid for new plastic molding. After that,
petrochemistryandplastic
moldingtechnology started developing through mutualinteraction, a trend that has continued to thepresent day.
A similar thing occurred with synthetic
fibers. The rayon industry, which had seen
Systematic Survey on Petrochemical Technology

17major developments in Japan since the 1920s,
used a wet spinning method in which thepolymers were dissolved in a solvent and thenspun. This was because cellulose, thefeedstock for rayon, is not a thermoplastic
polymer. By contrast, nylon, industrialized in
the United States at the end of the 1930s,
used a process called melt spinning, since it isa thermoplastic polymer. Even Japan started
small-scale production of nylon during theSecond World War using domestic
technology, and was able to produce it using
melt spinning. Melt spinning was applied topolyester fiber as well in the late 1950s,
leading to a series of technologicalinnovations from the 1970s onwards, such ascontinuous polymerization and spinning, andintegration of high-speed spinning, drawing
and false-twist texturing.

2.5 Petrochemical

technology

characteristics
While there are of course many
exceptions,acomparison
withmass-producing chemical industries that
predated petrochemistry and present-day
non-petrochemistrychemicalindustries
reveals the five major distinguishing
characteristics of petrochemical technology
shown in Fig. 2.7.
2.5.1 Part of energy revolution
In the 1950s, oil from the Middle East
started being supplied in large volumes toJapan and Europe, and the main source ofenergy switched to petroleum from coal,
which had been in constant use since theIndustrial Revolution of the 18th century.
This era was known as energy revolution.
Chemical industries that used coal andagricultural produce for feedstocks also
started switching to petroleum as a feedstock.
This was part of energy revolution.

Fig. 2.7 Petrochemical technology
characteristics.
Onesignificant
characteristicofpetrochemistry is not only using petroleum asa feedstock, but also using it in fluid form as
much as possible at each stage of
petrochemical product production. Basic
petrochemicals and many industrial organic
chemicals exist in gas or liquid form at
normal temperatures. Therefore, they areoften transported within factories by pumps
and pipes, and often stored in tanks. One of
the biggest reasons for amalgamating
petrochemical factories together and forming
petrochemical industrial complexes is that
this makes it easier to handle fluid substances.
Long-haul transportation between factories isalso often done on a large scale by tank trucks,
railroad tank cars or tankers, thereby making
best use of the fluid properties.
By contrast, polymers are often solid
products, although some are liquids, such as
solvents and emulsions. However, thesesolids are often handled in grain form, such as
powders or pellets.
2.5.2 Kombinats or industrial complexesIn
petrochemistry,
severalbasic
petrochemical products are co-produced, andthen used to produce industrial organic
chemicals and polymer products. As
mentioned above, basic petrochemical
products and many industrial organic
chemicals are fluids. Therefore, the factories
are converged together and connected withpipes for transporting products or raw
materials, thus forming kombinats orindustrial complexes [Footnote 9].
In many cases in Japan, industrial[Footnote 9] As mentioned in Footnote 8, there were instances ofindustrial complexes forming in coal chemistry and electrochemistry.
However, it is standard practice in petrochemistry to form industrial
complexes; petrochemical industrial complexes are also far larger inscale.

18

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

complexes have formed as industrial organic
chemical plants and polymer plants havegathered around naphtha steam-cracking
plants. Most industrial complexes are notconnected to each other and instances ofversatility between basic petrochemical
products such as ethylene or propylene
through pipes are rare. Although the situationin Europe is essentially similar to Japan, there
are long-distance ethylene pipelines acrossthe continent, and some industrial complexes
even link to other industrial organic chemicalplants and polymer plants. The United States
has a long-distance pipeline network for
ethylene and other products; many ethane or
naphtha steam-cracking plants are connected
into this network. Many industrial organic
chemical plants and polymer plants are also
connected into this network. This situation isreferred to as a “spaghetti bowl.”
2.5.3

Continuous, high-pressure,catalytic
Factory layout and operational methods
in the chemical industries vary significantly
depending on whether a chemical reaction
takes places continuously or in batches. Manyreactions in petrochemistry are continuous,with distillation and other processes also
carried out continuously. Operations are also
carried out continuously. Under theprovisions of the old High Pressure Gas
Control Act and other such laws, naphthasteam-cracking plants in Japan would close
once a year for maintenance, but operatecontinuously at all other times. At the present
time, the regulations have eased up, andplants can now operate continuously forseveral years at a time. Many industrialorganic chemical plants and polymer plants
also operate continuously and carry out
continuous reactions.
Many petrochemical reactions are also
carried out under high pressure, unlike someof the other chemical industries that predate
petrochemistry, such as coal tar chemistry,
acetylene chemistry and fermentation
chemistry. The use of high pressure has often
come under criticism from the perspective ofenergy conservation and been deemed as toomuch of a contrast from natural conditions, inwhich reactions are carried out at room

temperature and atmospheric pressure.
However, the use of moderately high pressure
has made a significant contribution toequipment productivity, and is also a meansof achieving optimal reaction conditions.
Reactions at room temperature andatmospheric pressure are not necessarily
categorically superior.
Petrochemical technology can also be
categorized by heavy catalyst use,
particularly solid catalysts. Advances andimprovements in catalysts have been crucial
tocompetition
among
petrochemicalcompanies. Ironically, ethane and naphthasteam-cracking have the largest plants inpetrochemistry and also serve as thefoundation for the supply of basic
petrochemical products, but are non-catalytic
reactions.
2.5.4 Large-scale
Even in the late 1950s, whenpetrochemical technology was only justintroduced to Japan from the West,petrochemical facilities and factories were farlarger in scale than those found in coalchemistry and other mass-producing chemicalindustries. The amount of capital needed tobuild these large-scale facilities and factories
was far more than made sense to any of theother chemical industries. Also, since manyof the products were unknown to the Japanesemarket, there were huge risks for companies
aspiring to get into petrochemistry. This was
one reason for promoting the formation of
corporate groups.
Up-scaling rapidly progressed from the
1950s to the 1960s. With the price of oil
dropping, the petrochemical industry proved
to have good economy of scale. Naphthasteam-cracking plants that had been built inthe late 1950s with 20,000-ton annual
ethylene production capabilities rapidly
expanded to 50,000-ton capabilities in theearly 1960s, to 100,000-ton capabilities in the
mid-1960s, and to 300,000-ton capabilities by
the end of the 1960s. The speed of expansion
slowed after the oil crises; currently, four
decades since the 1970s, new ethylene plants
are built with annual production capabilities
of around 0.6–1.2 million tons (or 1–1.5
million tons for ethane steam-cracking plants,
Systematic Survey on Petrochemical Technology

19which require less investment expenditure).
Industrial organic chemical plants andpolymer plants are also increasing in scale.
Thus, one of the major distinguishing
characteristics of petrochemistry is being far
greater in scale than other chemicalindustries.
2.5.5 Internationality
Since expanding to Europe and Japan
from the United States in the 1950s,
petrochemistry has been international in its
technology, feedstocks and product trading.
Neither the synthetic dye industry, whichdeveloped in the late 19th century, nor thecoal chemical industry, which developed in
the 20th century, has had this level ofinternationality; they have shown strong
cartel-like tendencies, rejecting newcomers
and trying to hold a monopoly. Technology
was an effective means to that end. By
contrast, since petrochemistry came after theSecond World War amidst a world-wide
proliferation of antitrust policies, it has beendifficult for anybody to gain a worldwide
production monopoly by concealing new
petrochemical technologies. The patentagreement between DuPont in the UnitedStates and ICI in the United Kingdom wasabolished in 1952 due to violation of antitrust
laws. In the 1950s, concerned that thedominant American petrochemical companies
would expand into Japan and Europe, theJapanese government and various European
governments placed strict regulations on
capital expansion. This is thought to beanother
reasonthatfacilitatedtheinternationalization of the technology. Insteadof being unable to be leveraged, newtechnology was licensed to start recovering
the expenses of development as soon as
possible. British company ICI sent an enquiry
commission to Japan in the 1950s specificallyto promote the high-pressure polyethylene
technology it had developed in the 1930s.
From such beginnings, petrochemical
technology continued to become even moreinternationalized from the 1970s onwards asplant engineering companies expanded.
Bibliography[1] Y. Hayashi, “Chemical industries of20

Japan,” Iwanami Shoten, 1st edition
1957, 2nd edition 1961; Y. Hayashi andT. Watanabe, “Chemical industries ofJapan,” Iwanami Shoten, 3rd edition
1968, 4th edition 1974.
[2] T. Watanabe, “The petrochemicalindustry,” Iwanami Shoten, 1st edition
1966, 2nd edition 1972; “Thepetrochemical industry at a turning
point,” Iwanami Shoten, 1984.
[3] “Ten-year history of the petrochemicalindustry,” Japan Petrochemical Industry
Association, ed., Japan Petrochemical
Industry Association, 1971.
[4] “A technical survey of process control
systems,” Survey Report on the
Systematization of Technologies, no. 11,
National Museum of Nature andScience, March 2008.
[5] “Analytical
instruments/scientificequipment heritage catalog (2014),”
Japan
Analytical
Instruments
Manufacturers’ Association and Japan
Scientific Instruments Association, eds.,
September 2014.
[6] Y. Yasuda, “Plastic centenary special:history of molding methods andmachines,” Plastics, Japan Plastics
Industry Federation, 2007.
[7] H. Koyama, “The history of Japan’s
plastic industry,” Kogyo Chosakai,
1967.
[8] “A 10-year history of injection moldingin Japan,” Japan Injection Molding
Industry Association, 1963.
[9] “Injection molding,” Japan Patent
Office, ed., Patent Map by TechnicalField, 1997.
[10] “Plastic extrusion,” Japan Patent Office,ed., Patent Map by Technical Field,
1998.
[11] “An outline of the development of polyvinyl chloride technology in Japan,
inclusing a description of historicalmaterials (2),” Survey Report on the
Systematization of Technologies, no. 2,
National Museum of Nature andScience, March 2002.
[12] “Systematic review of tyre technology,”
Survey Report on the Systematization ofTechnologies, no. 16, National Museumof Nature and Science, March 2011.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

[13] “History of polyester fiber technologies
used for making textiles,” Survey
Report on the Systematization ofTechnologies, no. 7, National Museumof Nature and Science, March 2007.

Systematic Survey on Petrochemical Technology

21

3 Petrochemical product categories

The previous chapter provided abird’s-eye view of the forest that is
petrochemistry. Since this does little to reveal
any detail, let us now enter that forest. In
other words, this chapter discusses
petrochemical product categories and how
these products are made.
While petrochemical products can bebroadly grouped into three categories: basic
petrochemical products, industrial organic
chemicals and polymers, they are notnecessarily always produced in this order. In
many cases, polymers are made from basic
petrochemical products without first being
made into industrial organic chemicals. Since
industrial organic chemical products andpolymer products are generally madeseparately according to the number of carbon
atoms in the basic petrochemical product,
here we shall discuss industrial organic
chemicals and polymers together in order ofthe number of carbon atoms in the basic
petrochemical product.
For those who are unfamiliar to chemistry,
this chapter may seem to be complicated andconfusing. It should suffice to look at only the
figures and tables, and to note themagnificence and intricacy of modern
petrochemical industries.

3.1 Global petrochemical industries byproduct categories
Since petrochemical product categories
are complex and there is every chance that wewould lose sight of the overall forest if werelooked too closely at the individual trees, let
us first examine the patterns in major
petrochemical product categories around theworld, thereby revealing the broader
categories in the forest that is petrochemistry.
Basic petrochemical product categories
largely depend on the raw material used. If
the raw material is methane, with C1, then
only basic petrochemical products with C1
can be produced. If the raw material is ethane,with C2, then the only basic petrochemical
product that can be produced is ethylene, with
C2. If the raw material is propane or butane,with C3 or C4, then the main basic

22

petrochemical products produced will beolefins with C2 to C4. If the raw material isnaphtha, gas oil or other petroleum product(hydrocarbon mixtures with five or morecarbon atoms), then the basic petrochemical
products produced will be olefins andaromatic hydrocarbons.
The size and complexity of petrochemical
products are determined by the number ofcarbon atoms in the raw material. The main
petrochemical product line patterns aroundthe world can be broadly categorized into fivegroups, as shown in Table 3.1.
Pattern (1) is the petrochemistry to
produce methanol from syngas using natural
methane gas as a raw material. At the present
time, over 1 million tons of methanol is
produced annually at large-scale plants.
Although there are several derivative
products made from methanol, as shall bementioned later, very few derivative products
are produced on a large scale at methanol
production sites. In many cases, methanol isexported in its manufactured form.
Accordingly, it is no overstatement to say that
Pattern (1) is methanol-plant petrochemistry.
Pattern (2) is the petrochemistry to
produce ethylene products from ethylene
using ethane from natural gas and associatedpetroleum gas as raw materials. At present,
plants have been built with annual ethylene
production capabilities of over 1 million tons;
these are in the form of industrial complexes
that produce several different types of
ethylene-based products using ethylene as araw material. Pattern (3) is the petrochemistry
to produce a lot of different industrial organic
chemicals and polymers from a wide varietyof olefins and aromatic hydrocarbons using
naphtha, gas oil and other liquid petroleum
products as raw materials. Since plants arepresently being built with ethylene production
capabilities of over 500,000 tons (over 1.5
million tons of basic petrochemical products
in total), these are taking the form ofindustrial complexes surrounded by a numberof derivative product plants. While Patterns(2) and (3) are in competition on the global
ethylene-based
products
market,National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

non-ethylene-based products are mainly
provided through Pattern (3), as Pattern (2)generally produces no non-ethylene-based
products.

Table 3.1 Global petrochemical industries by products

Pattern (4) is the petrochemistry to
produce propylene-based and butylene-based
products from propylene and butylene frombyproduct waste gas emitted when producing
the gasoline fraction using heavy oil as a raw
material. Pattern (5) is the petrochemistry to
producearomatic-based
products
byextracting aromatic hydrocarbons fromreformate. Patterns (4) and (5) only take placein countries and regions where gasoline isproduced from heavy oil, or where
high-octane gasoline is produced in large
volumes. Since the main aim is to produce
gasoline, and basic petrochemical products
are byproducts, these complement Patterns(2) and (3). In the United States, Pattern (2) iscommon while Pattern (3) is rare; meanwhile,
since there is a high supply from Patterns (4)and (5), these are the main source of supply
for non-ethylene-based products.

3.2 Raw materials for petrochemistry
Different petrochemical industries indifferent countries around the world produce
different product categories, due to thedifferent raw materials available. Since raw
materials are the greatest determining factor
for the petrochemical industry, let us first

discuss the raw materials in petrochemistry.
3.2.1

Oil/natural gas producing areas
and location of petrochemicalindustries
The raw materials for petrochemistry are
petroleum and natural gas, as previously
mentioned. Both are made up ofhydrocarbons, and both are extremely useful
as sources of fuel (energy). In terms of theoverall consumption of petroleum and naturalgas, only a very small amount is used as raw
materials for petrochemistry. Where natural
gas is used as a fuel (energy) source, it istransported long distances in its natural statethrough pipelines, or converted into liquefied
natural gas (LNG) and transported by LNG
tankers. Long-distance transportation can beadequately covered by a fixed cost, since far
higher quantities of gas are used for fuel thanfor petrochemical raw materials. However,where natural gas is used as a petrochemical
raw material, it is consumed near the
production site rather than being transported
long distances. By contrast, petroleum isoften transported near to the area ofconsumption, since crude oil and evennaphtha, the main petrochemical raw material,can be transported long distances in large
Systematic Survey on Petrochemical Technology

23

tankers.
Consequently, in areas with natural gas,petrochemical industries tend to be locatednear production sites. In areas without naturalgas, imported crude oil, naphtha and otherpetroleum products are used as raw materials,
and petrochemical industries have developed
near areas of consumption.
3.2.2 Natural gas
Most of the natural gas mined in the
North Sea, Russia, Asia and the Pacific,
including the small amount mined in Japan, ismade up of only methane. Methane is thesimplest saturated hydrocarbon with C1[Footnote 1]. In Japan, methane is imported
long-haul in large quantities in LNG form; itis solely used as fuel for thermal power
generation and city gas supplies. Since it canbe expensive, it is rarely used as apetrochemical raw material. Petrochemical
and ammonia/fertilizer industries that use
methane as a raw material are often locatednear methane production sites. Many of theworld’s natural gas fields are in remotelocations that are of little use, as the methanecannot be transported anywhere.
While natural gas mined in the UnitedStates, Canada and the Middle East is mainly
made up of methane, it can also contain apercentage of ethane, a saturated hydrocarbon
with C2, as well as a small proportion of
propane and butane, saturated hydrocarbons
with C3 or C4. The same is true of shale gas
mined in the United States, a recent topic ofdiscussion. Ethane, propane and butane canbe cracked and used as raw materials forolefins. As propane and butane are easilyliquefied, they are often made into liquefied
petroleum gas (LPG) and transported long
distances to be sold for fuel. Since ethane is
not as easily liquefied as propane and butane,
it is used almost solely as a petrochemical
raw material near production sites, likemethane. If there are no nearby petrochemical
facilities, ethane can also be used in fuelwithout being separated from methane.

[Footnote 1] Hydrocarbons made up of carbon chains with only
single bonds are called saturated hydrocarbons. They are also known
as paraffins or alkanes. Their molecular formula can be represented
as CnH2n+2. Methane CH4 has the lowest number of carbon atoms ofany saturated hydrocarbon. Saturated hydrocarbons are the least
reactive of the hydrocarbons.

24

3.2.3 Associated petroleum gas
Gaseous hydrocarbons dissolve into
crude oil at high pressure underground, butthey naturally separate out again atatmospheric pressure when the crude oil ismined. This is called associated petroleum
gas. Associated petroleum gas often contains
ethane, propane and butane, as well as
methane. Once the ethane is separated andrecovered, it is used as a raw material for
ethylene. The petrochemical industries thathave developed in the Middle East on a large
scale since the 1980s used associatedpetroleum gas as a raw material, wherepreviously it had not been used for anything.
Associated petroleum gas also containshydrocarbons that liquefy at atmosphericpressure, corresponding to the naphtha
fraction. This is called gas condensate, or
natural gasoline. With simple distillation, gascondensate makes an extremely good
petrochemical raw material, which ismarketed as naphtha, like that distilled fromcrude oil.
3.2.4 Crude oil and petroleum products
Hydrocarbons with five or more carbon
atoms exist in liquid form at atmosphericpressure. Crude oil comes in various forms,
depending on where it is produced; someforms are mainly made up of saturatedhydrocarbons, while some forms contain highamountsofalicyclichydrocarbons[Footnote 2] or aromatic hydrocarbons. Crude
oil also contains sulfur, nitrogen or otherorganic compounds. Oil refining industries
distill and refine crude oil, separating out
different products according to their boilingpoints:thenaphtha/gasoline
fraction[Footnote 3], the kerosene/jet fuel fraction,
the diesel oil fraction and the heavy oil
fraction. Oil refineries also produce various
types of complementary petroleum productsin the required quantities through various
physical treatments and chemical processes,
such as vacuum distillation, hydrocracking,[Footnote 2] Hydrocarbons that are made up of only single bonds
and have a cyclic structure are called alicyclic hydrocarbons. Also
called naphthenes or cycloparaffins.
[Footnote 3] The oil fraction with a boiling point between 30–180˚C(or 200˚C) is called naphtha. Naphtha, also called crude gasoline, ismainly made up of hydrocarbons with C5–C12. Gasoline is a type of
naphtha used as automotive fuel, with its octane number, sulfur
content and benzene content adjusted to particular standards.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

thermal cracking, catalytic cracking, catalytic
reforming,
alkylation,
dehydrogenation,hydrotreating, isomerization and caulking
processes.
In Japan and other parts of Asia, only
naphtha is used as a petrochemical raw
material. In Europe, both naphtha and gas oil[Footnote 4] are used as petrochemical raw
materials.
Oil refineries produce large amounts ofpetroleum waste gas during catalytic cracking
and other chemical processing. These waste
gases are made up of propylene, butylene andother olefins. These olefins can be used as
raw materials for petrochemistry as necessary.
Catalytic reforming is a type of chemical
processing to raise the octane number[Footnote 5] of gasoline. Since catalytic
reformate contains high quantities of aromatichydrocarbons, these can be extracted asnecessary to produce basic petrochemical
products. Thus, oil refineries often produce
and supply basic petrochemicals. Further
details on petroleum refining technology havenot been included in this report.

3.3 Productcategories
petrochemicals

of

basic

Main basic petrochemicals include C1
syngas, C2–C5 olefins and C6–C8 aromatichydrocarbons. The product categories ofbasic petrochemicals are given below foreach raw material and production technique.
3.3.1 C1 basic petrochemicals
Figure 1 shows the product categories of
C1 basic petrochemicals made from methane.
The main C1 basic petrochemical is syngas.
Carbon monoxide (CO), phosgene (COCl2),hydrogencyanide(HCN)
andchroromethanes
are
also
C1
basic
petrochemicals.

[Footnote 4] Gas oil is generally the same thing as diesel oil.
However, in some cases, gas oil refers to both kerosene and diesel
oil.
[Footnote 5] Octane number is an index that indicates theanti-knocking capacity of gasoline engine fuels. The reference
criteria range from 0 to 100, with iso-octane having an octane
number of 100, and n-heptane having an octane number of 0.

Fig. 3.1 Basic petrochemicals from methane.
Syngas is a mixture of carbon monoxideand hydrogen. It can be made from coal,natural gas and petroleum and also fromcarbohydrates, though in small quantities. In
the petrochemical industry, it is entirely madefrom natural gas (methane). Syngas thus
obtained is further chemically treated tochange the carbon monoxide/hydrogen ratio
depending on the expected use and is used forsynthesis of methanol and production ofcarbon monoxide. As a raw material for oxo
process (hydroformylation), syngas is also
used for production of oxoaldehyde andoxoalcohol. In industries other thanpetrochemistry, it is used for production ofhydrogen and synthesis of ammonia andartificial petroleum.
Syngas is manufactured from methane bysteam reforming. Methane is reacted withwater to give syngas composed of carbon
monoxide and hydrogen that is 3 times thevolume of carbon monoxide.
C1 basic petrochemicals other thansyngas are described below. Carbon
monoxide is produced from syngas. Phosgene(COCl2) is made by the reaction of carbon
monoxide and chlorine. According to theAndrussow process, hydrogen cyanide issynthesized from methane, ammonia and air
at 1,000°C. Water is obtained as a byproduct.
According to a modification of theAndrussow process, hydrogen cyanide andhydrogen are only made from ammonia andmethane at 1,400°C in the absence of air.
Because hydrogen cyanide is produced inlarge quantities as a byproduct whenacrylonitrile is made by ammoxidation of
propylene, this process has been used tosupply of hydrogen cyanide at a low pricesince the 1960s. However, owing to
improvement of catalysts for ammoxidation
Systematic Survey on Petrochemical Technology

25

in recent years, the production of hydrogencyanide as a byproduct has been markedly
decreasing.
Chloromethane is made by direct
chlorination of methane. It is classified into
four types, which are methyl chloride,
dichloromethane(methylene
chloride),chloroformandcarbontetrachloride,
depending on the number of chlorine atoms.
If another manufacturing process is used,methyl chloride is made from methanol andhydrogen chloride by dehydration, and is thenchlorinated to produce chloromethanes withmore chlorine atoms. If this process is used,
the necessary products can easily be obtainedwith a higher yield.
The commercial value of carbon
tetrachloride was lost in the 1990s when it
was specified as an ozone layer depleting
substance and its production and consumption
were regulated by the Montreal Protocol. The
commercial values of fluorocarbons (such ashydrogen-free chlorofluoromethanes) andhalons(suchashydrogen-freebromofluoromethanes)
made
from
chloromethanes have also been lost, because
these substances were also classified as ozone
layer depleting substances. Fluorocarbon
substitutes made from chloroform, etc. arealso being regulated one by one to prevent
global warming.
3.3.2

Basic petrochemicals from steam
cracking of gaseous hydrocarbons
Ethylene and hydrogen are only produced
by steam cracking of ethane that is separated
from natural gas, crude oil associated gas, etc.
Other olefins or aromatic hydrocarbons are
rarely produced. In the United States, steam
cracking of a mixture of ethane and propane
or a mixture of propane and butane is also
performed, though on a small scale. In thiscase, not only ethylene but also olefins suchas propylene and butylene are obtained. The
production of aromatic hydrocarbons is low.
As the steam cracking technique for gaseoushydrocarbons is the same as that for naphtha
and gas oil, it is described in the following
section.
3.3.3

Basic petrochemicals from steam
cracking of liquid hydrocarbons
As shown in Fig. 3.2, liquid

26hydrocarbons are steam-cracked to give
mixturesofolefinsandaromatichydrocarbons as co-products.
(1) Steam cracking techniqueHydrocarbon is cracked when naphtha or
gas oil is mixed with superheated steam andis then passed for a few milliseconds througha pipe that is heated above 1,000°C from theoutside. The cracked gas is quenched toapproximately 300°C in a heat exchanger(quench cooler). As the reaction temperatureof steam cracking is 800–900°C, heat can berecovered as high-pressure steam using thequench cooler. The cracked gas is thensprayed with oil (mainly cracked gasoline,
mentioned below) in the quench tower andthen with water in the next quench tower. As
a result, the steam mixed at the time ofreaction changes to water, and the C5–C9
fractions of the cracked products arecondensed/separated and collected as a liquid(cracked gasoline). Further separation andpurification of the cracked product aredescribed in the next section.
Steam cracking described here is not areaction of hydrocarbons with steam as was
mentioned in the preceding section on
manufacture of syngas (steam reforming).
Steam only lowers the partial pressure ofgaseous hydrocarbons. Steam cracking
achieved by thermal cracking in the absenceof a catalyst is markedly endothermic.
Cutting of carbon chains, isomerization,
cyclization
anddehydrogenationofhydrocarbons occur during the reaction. If theretention time of hydrocarbons is too long,thermal cracking will progress further,ultimately resulting in cracking into carbon
and hydrogen. Therefore, the retention time isshortened to avoid this problem, but carbon
as a byproduct of hydrocarbon thermal
cracking still accumulates in the pipes during
operation. Since steam cracking devices arecomposed of up to a dozen furnaces, thefurnace in which the carbon accumulates in
the pipes is separated after the supply of raw
materials is stopped, and then air is supplied
to remove the carbon by combustion. After
this decoking operation, the furnace is put
into operation again.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 3.2 Major basic petrochemicals obtained from steam cracking of naphtha or gas oil.
The production of olefins is higher when
the cracking temperature is higher, retention
time is shorter, and partial pressure ofhydrocarbons is lower (mixed with moresteam). Recently, because the main suppliersof aromatic hydrocarbons as a basic
petrochemical have also transitioned to oil
refiners (catalytic reformate) in Japan, steam
cracking devices for naphtha tend to be
operated in such a way to obtain more olefins.
The yields of basic petrochemicals
produced by steam cracking differ greatly
depending on the raw material and conditions
for cracking. If the raw material is ethane asmentioned in the preceding section, the yieldsof ethylene and hydrogen/methane areapproximately 80% and 14%, respectively. If
the raw material is butane as mentioned in thepreceding section, the yields of ethylene,
propylene,
butylene/butadieneandhydrogen/methane are approximately 38%,
15%, 10% and 25%, respectively. In contrast,
if the raw material is naphtha, the yields ofethylene, propylene, butylene/butadiene,
basic petrochemicals with five or morecarbonatoms(including
aromatichydrocarbons) and hydrogen/methane areapproximately 30–35%, 15–17%, 9–12%,
25% and 14–16%, respectively.

(2) Separation and purification of olefins
and aromatic hydrocarbons
Since many olefins and hydrocarbons areproduced simultaneously during steam
cracking of naphtha and gas oil, thetechniques for separating and purifying themhave
progressed.
Severalseparation/purification processes have beendeveloped depending on the order of productseparation. Detailed description of eachprocess is avoided here, and how to separate
and purify co-products is described below byshowing an example.
At first, the cracked product cooled toroom temperature in the water quench tower
is divided three ways, namely, water, a gas
component and a component that occurs as aliquid at room temperature (cracked
gasoline).
The gas component is washed with asolution of sodium hydroxide to remove
carbon dioxide and traces of sulfur
compounds. After drying, the gas is cooled
under compression. Hydrogen, the C1
fraction and the C2, C3 and C4 fractions are
separated one by one while the gas is being
passed sequentially through the distillation
columns for demethanization, deethanization,
depropanization, debutanization, etc. The C2
fraction is further separated into ethylene andSystematic Survey on Petrochemical Technology

27ethane in the ethylene column to give
ethylene. Ethane is charged again as a raw
material into the cracking furnace. The C3
fraction is separated into propane andpropylene in the propylene column to give
propylene. As it is very difficult to separate
propane and propylene by distillation, adistillation column with a large number ofplates is needed. To synthesize industrialorganic chemicals, propylene is often purified
to a chemical grade of approximately 94%.
To produce PP, its purity must be further
increased to a polymer grade of 99.5% or
more.
Separation of the C4 fraction istime-consuming, because it contains many
components. As shown in Fig. 3.3, butadiene
is separated first by extractive distillation
using a polar solvent. Because three kinds ofn-butylene [Footnote 6] and isobutylene arecontained in raffinate I from which butadiene
has been removed, isobutylene with thehighest reactivity is changed to tert-butyl
alcohol by hydration in the presence of asolid acid catalyst and separated. Tert-butyl
alcohol is returned to isobutylene bydehydration. If it is necessary to separate
1-butylene from the remaining raffinate II, it
can be separated by extractive distillation or
by using a porous solid adsorbent. Raffinate
III from which 1-butylene has been removed
is a mixture of cis- and trans-2-butylene. This
mixture is usually used, without further
separation, for manufacture of alkylate
gasoline or synthesis of sec-butyl alcohol.

Fig. 3.3 Separation of the C4 fractions.

[Footnote 6] Molecules with a straight carbon chain are called linear
molecules, and n is attached. In the case of butylene, 1-butylene,
cis-2-butylene and trans-2-butylene shown in Fig. 2.2 are linear
molecules.

28

On the other hand, the C5 fraction isseparated first from cracked gasoline which
has been separated from the gas component
and water in the water quench tower as
mentioned at the beginning of this section.
Various hydrocarbons are contained in theC5 fraction. However, because it is difficult
to separate all of them, only isoprene andcyclopentadiene are separated due todemand. When the C5 fraction is heated at
150°C under pressure, cyclopentadiene isdimerized to give C10 dicyclopentadiene(DCPD) which can be separated by
distillation. When C10 dicyclopentadiene isheated at 350°C after separation,
cyclopentadiene is reproduced. The C5
fraction from which cyclopentadiene has
been separated is subjected to extractive
distillation with acetonitrile or N-methyl
pyrrolidone to separate isoprene. The
remaining C5 fraction is not separated
further, but is polymerized and used as
petroleum resin.
Aromatic and non-aromatic hydrocarbons
are then separated first from the six or morecarbon atoms fractions. For this purpose,
solvent extraction is often performed using asolvent such as N-methyl pyrrolidone,
N-formylmorpholine
orN,N-dimethylformamide (DMF).
Aromatic hydrocarbons are further
separated by distillation into benzene, toluene
and mixed xylene. Mixed xylene (the C8
aromatic hydrocarbon fraction) is a mixtureof ethylbenzene, o-xylene, m-xylene andp-xylene. Since these chemicals cannot be
separated by distillation due to having similarboiling points, various methods of separatingthem have been developed. As the demandfor p-xylene is much greater, its separation is
the most important. At present, the Parex
process developed by Universal Oil Products(UOP) in 1971 is widely used (see Section
6.1.1 (6)).
3.3.4

Basic petrochemicals from catalytic
cracking and catalytic reforming
In the oil refinery industry, catalytic
cracking of the heavy oil fraction is
performed to obtain more gasoline fraction as
well as the fraction contained in crude oil,resulting in the formation of large quantities

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

of waste gas. Since olefins such as propylene
and butylene are contained in the waste gas, it
is possible to separate/purify and use them asnecessary. However, this process is notefficient, because the concentrations ofpropylene and butylene in waste gas arelower for catalytic cracking of heavy oil thanfor steam cracking of naphtha. In countries
where steam cracking of naphtha is actively
carried out, there is low dependence on
propylene and butylene separated from waste
gas from catalytic cracking, because theproduction of propylene and of butylene fromsteam cracking of naphtha correspond to
approximately one-half and one-third of the
production of ethylene, respectively. On theother hand, in the United States, catalytic
cracking of petroleum is performed on a large
scale (Section 3.1). When the C3 fraction
from catalytic cracked gas is used forsynthesis of alkylate gasoline, etc. in the oil
refinery industry, it is not distilled precisely
but to a refinery grade (approximately 70%
propylene purity) (the main impurity is
propane with low reactivity). When it is used
for production of industrial organic chemicals
and polymers, it must be purified to achemical or polymer grade as mentioned
above.
In the oil refining industry, catalytic
reforming of naphtha/gasoline fractions is
performed to enhance the octane number ofgasoline. It is enhanced because hydrocarbon
molecules are branced, cyclized andaromatized by catalytic reforming. As a result,aromatic hydrocarbons are contained in
catalytic reformates. However, because
concentrations of aromatic hydrocarbons arelower for catalytic reformates than forcracked gasoline, various solvent extraction
methods have been developed. Old
well-known methods are the Udex process(extracting solvent: ethylene glycols/water)developed by UOP-Dow Chemical in 1952
and the sulfolane process developed by
Shell-UOP in 1959. On the other hand, newprocesses using new solvents have also beendeveloped one after another. Catalytic
reformates are the main supply source ofaromatic hydrocarbons in the United States In
places like Europe and Japan, where steam
cracking of naphtha is actively carried out,

aromatic hydrocarbons can be supplied fromcracked gasoline. However, because thedemand for aromatic hydrocarbons has
increased, the main supply source of aromatichydrocarbons in Japan has also changed fromcracked gasoline to catalytic reformates.
3.3.5

Disproportionation andisomerization of aromatichydrocarbons
Production of benzene and xylene bydisproportionation of toluene and productionof mixed xylene by isomerization ofm-xylene are included in the techniques ofmanufacturing basic petrochemicals (seeSection 6.1.1 (6)).

3.4 Product categories of industrialorganic chemicals and polymers
In the petrochemical industry, industrialorganic chemicals and polymers are madefrom basic petrochemicals according to thenumber of carbons, and different industrialorganic chemicals and polymers are madefrom individual industrial organic chemicals.
Therefore, in this section, the productcategories of industrial organic chemicals andpolymers are described for each carbon
number found among basic petrochemicals.
There are usually several competitive
routes and techniques for manufacture ofindustrial organic chemicals. Moreover,historically, they have often shown profoundchanges. In this section, typical routes andtechniques are described to provide further
insight on the product categories of current
petrochemistry. Competitive routes andhistorical changes are explained later.
As there are much more industrialorganic chemicals and polymers than basic
petrochemicals in the petrochemical industry,
it is impossible to describe all of them. Since
the purpose of this report is to take a generalview of petrochemical manufacturing
techniquesandtoconsiderthesystematization of such techniques, only thetypical products manufactured in large
quantities worldwide or in Japan are
described below.
3.4.1

Product categories from the C1
Systematic Survey on Petrochemical Technology

29fraction
C1 basic petrochemicals include syngas,
carbon monoxide, phosgene, hydrogencyanide and chloromethanes. Figure 3.4
shows the categories of main industrialorganic
chemicals
andpolymers
manufactured from each of them.

Fig. 3.4 Major product categories from basic
petrochemicals with C1.
(1) Methanol
The production of methanol from syngas
is greater than that of any other C1
petrochemicals. Methanol is made by thereaction of syngas as a mixture of carbon
monoxide and hydrogen at a gas volume ratioof 1:2. . Methanol is used not only as asolvent but also in large quantities forsynthesizing industrial organic chemicals. It
is used for manufacture of various methyl
esters as well as formaldehyde and acetic acid.
In recent years, methanol has also been usedin large quantities for synthesizing fuels andfuel additives, such as biodiesel oil from fats
and oils [Footnote 7] and dimethyl ether.
Formaldehyde
is
made
by
dehydrogenationoroxidative
dehydrogenationofmethanol.
Many
industrialized processes are available.
Formaldehyde is also used for production ofphenol, urea and melamine resins. It is used
for producing polyacetal as one of theengineering plastics. It is also used as anorganic intermediate for making variousorganic
compounds.
Pentaerythritol(tetrahydric alcohol), trimethylol propane(trihydric alcohol) and neopentyl glycol[Footnote 7] Biodiesel oil is a higher fatty acid methyl ester. Higher
fatty acid methyl esters and glycerin are produced bytransesterification between oils/fats (triglycerides as higher fatty
acids) and methanol. As the oils and fats, palm oil, rape seed oil andsunflower oil are often used. Biodiesel oil can also be made fromused edible oil, though in very small quantities.

30(dihydric alcohol) are made by aldol
condensation and reduction reaction offormaldehyde with various aldehydes. These
alcohols are used as raw materials forunsaturated polyester and alkyd resin and as
raw materials for polyether polyol used inpolyurethane. Formaldehyde is also used forsynthesizing 4,4-diaminodiphenyl methane asa raw material for methylene diphenyl
diisocyanate (MDI).
At present, acetic acid is manufactured
mainly from methanol and carbon monoxide.
This process is explained under (3) in thissection.
(2) Oxoaldehyde and oxoalcohol
Aldehydes are synthesized by the oxo
process (hydroformylation) in which olefins,etc. are reacted with carbon monoxide andhydrogen. Aldehydes thus obtained have one
more carbon atom than the original olefins.
Synthesis of n-butyraldehyde andisobutyraldehyde from propylene is thegreatest use of the oxo process. This reactionis also used for synthesis of propionaldehyde
from ethylene and for synthesis of
β-hydroxypropionaldehyde from ethyleneoxide.
Propionaldehyde
andβ-hydroxypropionaldehyde are reduced withhydrogen to give n-propylalcohol and1,3-propanediol, respectively. Linear higher
alcohols are made by the oxo process of
α-olefins. Such a series of aldehydes
produced by the oxo process are called
oxoaldehydes, while alcohols formed by
reduction of these oxoaldehydes are called
oxo alcohols.
(3) Industrial organic chemicals fromcarbon monoxide
The most significant industrial organic
chemical from carbon monoxide is acetic acid.
It is produced by the reaction of methanol andcarbon monoxide. The most important use ofacetic acid is vinyl acetate. Acetic acid is also
used as a solvent for manufacture of
terephthalic acid. Acetic acid is also used forother purposes such as the production of
acetate, acetic anhydride and chloroacetic
acid.
Ube Industries has industrialized amethod of co-producing dimethyl carbonate

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)and dimethyl oxalate by the reaction ofcarbon monoxide with methyl nitrite in thepresence of a platinum-group metal catalyst(nitrite process). Methyl nitrite is synthesizedfrom nitrogen monoxide, methanol andoxygen. Oxalic acid is obtained fromdimethyl oxalate. Ethylene glycol (EG) is
obtained by hydrogen reduction of dimethyl
oxalate. Accordingly, C2 industrial organic
chemicals (oxalic acid and EG) can beobtained from C1 petrochemicals such ascarbon monoxide and methanol by the nitrite
process (see Section 6.2.3).
(4) Products from phosgene
Phosgene is a highly reactive gas and isused in large quantities for the manufacture of
diisocyanate as raw materials of polyurethaneand polycarbonate.
Isocyanate is synthesized by the reactionof amine with phosgene. Aromatic
diisocyanates (MDI and toluene diisocyanate[TDI]) are produced on a large scale. Of thealiphatic
diisocyanates,
hexamethylene
diisocyanate, isophorone diisocyanate, etc.
are not produced on such a large scale, but
are essential for the manufacture of
non-yellowing polyurethane foam.
Phosgene is reacted with compounds
having hydroxy groups to give carbonic acid
esters (carbonates). Of these, bisphenol A(BPA) is reacted with phosgene to give large
quantities of polycarbonate as an engineering
plastic.
Phosgene is also reacted with carboxylic
acid
to
give
acid
chlorides.
As
monoisocyanate and acid chlorides are highly
reactive industrial organic chemicals, they areused as organic intermediates for the
manufacture of pesticides, pharmaceuticals
and surfactants.
(5) Industrial organic chemicals fromhydrogen cyanide
Alkali salts (sodium cyanide andpotassium cyanide) of hydrogen cyanide(hydrocyanic acid) are used in the metal
refining, plating and inorganic chemicalindustries. These substances are also used for
introducing a cyano group in organic
synthetic reactions
andasorganic
intermediates for dyes, feed additives,

pharmaceuticals, pesticides, etc.
Hydrogen cyanide used to be obtained inlarge quantities as a byproduct of acrylonitrile.
At that time, it was reacted with acetone andbutadiene to give methyl metacrylate andadiponitrile, respectively. However, in recent
years, because the production of hydrogencyanide as a cheap byproduct has decreased,
its large-scale uses have also decreased.
(6) Products from chloromethanes
As industrial organic chemicals fromchloromethanes have become regulated asozone depleting substances or greenhousegases, the production of these substances has
recently decreased to a large extent. However,some important petrochemicals are still being
manufactured from chloromethanes.
As a solvent/detergent, dichloromethane(methylene chloride) is widely used not onlyin the chemical industry but also in themachine industry. Methyl chloride is reactedwithsilicon to
give chlorosilanes.
Chlorosilanes are important raw materials ofsilicone oil, silicone rubber and silicone resin.
Chlorodifluoromethane(HCFC-22)
obtained by the reaction of chloroform withanhydrous hydrofluoric acid is thermallycracked to give C2 tetrafluoroethylene.
Polytetrafluoroethylene is obtained by radical
polymerizationoftetrafluoroethylene
according to the suspension polymerization
method. Polytetrafluoroethylene (PTFE) is atypical fluororesin (Teflon).
3.4.2

Products from the C2 fraction(ethylene-based products)
The C2 basic petrochemical is ethylene.
Figure 3.5 shows the categories of main
products from ethylene. Of the four major
general-purpose resins which are produced in
exceptionally large quantities compared withother polymers, polyethylene, polystyrene
and vinyl polychloride are made fromethylene. Furthermore, because ethylene isoften used as a comonomer of propylene[Footnote 8], it may be said that the products
from ethylene including PP play the most[Footnote 8] Polymers in which only one type of molecule(monomer) is polymerized are called homopolymers. Polymers inwhich different types of molecule are polymerized (copolymerized)
are called copolymers. Of more than one monomer involved incopolymerization, the monomers other than the main monomer are
called comonomers.
Systematic Survey on Petrochemical Technology

31

important role in the petrochemical industry.
The reaction of ethylene is mostly addition

reaction to double bonds (see Section 6.1.2(1)).

Fig. 3.5 Major product categories from ethylene.

(1) Polyethylene
Ethylene is polymerized to givepolyethylene. Polyethylene is the greatest useof ethylene and is a typical petrochemical thatis produced i larger quantities than any otherpolymers. Since the molecular structure ofethylene is CH2=CH2, the basic molecular
structure of polyethylene is -(CH2)-, andthousands to hundreds of thousands of-(CH2)- are connected. The molecular chainofpolyethylenemaybealmostone-dimensional/straightor
branched.
Furthermore, in addition to ethylene, acomonomer is used in small quantities tochange the performance of polyethylene byslightly modifying the structure of its
molecular chain. Thus, as shown in Fig. 3.6,
polyethylene is roughly classified into 4types: low-density polyethylene (LDPE),
ethylene-vinyl acetate copolymer (EVA),
high-density polyethylene (HDPE) and
L-LDPE.

Fig. 3.6 Type of typical polyethylenes.
High-pressure low-density polyethylene(LDPE) is polyethylene that was synthesized
for the first time in 1933. LDPE is made byradical polymerization [Footnote 9] at 200°C
and 2,000 atm using a trace of oxygen or
peroxide as a polymerization initiator[Footnote 10]. The autoclave (vessel) andtubular processes are available depending on
the type of reactor, but both of them are basedon the bulk polymerization process[Footnote 11]. Because the molecular chainof LDPE is branched substantially,[Footnote 9 ] Chemicals that generate radicals on heating, etc., thus
making radical polymerization start are called polymerization
initiators. Catalysts do not remain on the molecular chains ofpolymers, while some of the polymerization initiators become part ofmolecular chains.
[Footnote 10 ] Radical polymerization is one of the polymerization
reactions. In this reaction, the molecular chain that grows when thepolymer chain grows due to the reaction of the monomer is a radical.
In contrast, the reaction in which the growing molecular chain is an
ion is called ionic polymerization. (See Section 6.1.3 (1) 2), 3))[Footnote 11 ] See Secton 6.1.3 (1) for these polymerization method.

32

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

crystallization hardly occurs and as a result, it
has low density (0.915–0.925) compared withother types of polyethylene. As a transparent
flexible film, LDPE is used in large quantities
for packaging bags, garbage bags, mulch
films for agriculture, etc. It is also used formolded products such as blow-molded bottles
and extrusion-molded pipes. Crosslinked
LDPE is used as an insulating material forhigh-voltage transmission line cables.
However,
becauseexpensivesuperhigh-pressure facilities are required for
LDPE, LDPE has recently tended to be
replaced by L-LDPE mentioned below and as
a result, there are few new LDPE plants underconstruction.
Ethylene-vinyl acetate (EVA) resin is acopolymer obtained by copolymerization of
ethylene and vinyl acetate. Due to its
excellent adhesiveness, it is laminated withother types of polymer film and used as amultilayer film. It is also used as an adhesive(hot-melt adhesive) for paper bags, etc. and asa foamed product for shoes and sandals. EVA
resin can be produced using the same
manufacturing equipment as for LDPE.
High-density polyethylene (HDPE) is
made by ionic polymerization of ethylene[Footnote 10] at room temperature to 250°C
and atmospheric pressure to 150 atm.
Catalysts are needed for polymerization. By
using the Phillips process or Standard Oil of
Indiana process depending on the catalyst,
polymerization is carried out at a medium
pressure of several tens to 150 atm. On theother hand, if a Ziegler or metallocene
catalyst is used, polymerization of ethylene
can be performed under moderate conditions(atmospheric pressure and less than 90°C).
Linear polyethylene without branching can beobtained by both of the medium pressure andatmospheric pressure processes. Since such amolecular chain tends to be folded to produce
crystals, slightly higher density (0.955–0.965)
translucent polyethylene can be obtained.
HDPE
does
not
requirethesuperhigh-pressure manufacturing facilities
that are essential for LDPE and consumes
much less energy to manufacture than LDPE.
HDPE has been manufactured by solution
polymerization [Footnote 11] and slurry
polymerization [Footnote 11]. However,owing to the development of highly active
catalysts, production by gas phase
polymerization [Footnote 11] using a
fluidized bed reactor started in the 1980s andhas subsequently become widely used.
HDPE is often injection- or blow-molded
and used for convenience goods, containers,
automotive gasoline tanks, kerosene tanks
and bottles. HDPE with high molecularweight is extrusion-molded to give an
extremely thin but strong film, which is used
for disposable shopping bags and packaging
bags at supermarkets. As a synthetic fiber,
HDPE is used for fishing nets, ropes, filter
cloth and insect proof nets. The film is split
and extended to give flat yarn and split yarn,
which are used for blue sheets, flexible
containers, strings for packing, etc.
L-LDPE has low density, while keeping
the advantages of HDPE, i.e., low equipment
and operational energy costs. When ethylene
is copolymerized with a several-percent lower
α-olefin such as 1-butylene, 1-hexene or
1-octene [Footnote 12], C2–C6 side chains ofalkyl groups occur at random in the molecular
chain. Due to such side chains, unlike HDPE,
the linear main chain of L-LDPE cannot bechangedtocrystals,demonstrating
characteristics similar to those of LDPE
(density, transparency, flexibleness, etc.).
Moreover, because highly active catalysts canbe used for L-LDPE as well as for HDPE,
L-LDPE can also be manufactured by gas
phasepolymerization
withhigherproductivity. Slurry polymerization is also
applicable.
In addition to the four polyethylenes
mentioned above, many special polyethylenes
and reformed polyethylenes are being
manufactured. The molecular weights of thetypical polyethylenes mentioned above areapproximately
20,000to
250,000.
Polyethylenes of more than 1 million
molecular weight are called ultrahighmolecular weight polyethylenes. It is difficult
to mold them, but because of excellent
abrasion resistance and shock resistance,these polyethylenes are used as engineering
plastics. Polyethylene can be crosslinked by[Footnote 12] Olefins in which the double bond is at the end of the
carbon-carbon bonds are called α-olefins. Both lower α-olefins witha small number of carbon atoms and higher α-olefins with a large
number of carbon atoms are available.
Systematic Survey on Petrochemical Technology

33

exposure to radiation or blending with anorganic peroxide during or after molding.
Crosslinked polyethylene is clearly more
excellent with respect to heat resistance,
strength and weather resistance. Various
polyethylene copolymers in which ethylene is
copolymerized with vinyl compounds areavailable. Kuraray’s EVALTM is a copolymer
of ethylene and vinyl alcohol. Due to its
excellent gas barrier properties [Footnote 13],
it is used for lamination of packing containers
and automotive gasoline tanks. Polyethylene
is reacted with chlorine gas, etc. to givechlorinated polyethylene. Since chlorinatedpolyethylene has the characteristics of both
plastic and rubber, it is used as an impact
modifier for polyvinyl chloride. As
chlorinated polyethylene is resistant to flame
owing to the chlorine group, it is also used asa flame retardant for polyethylene and PP.
Ethylene is used for copolymerization
with propylene and also for copolymerizationof propylene and dicyclopentadiene (DCPD),
as shall be described later.
(2) Ethylene oxide
The greatest use of ethylene after
polyethylene differs by country. Ethyleneoxide, ethylbenzene/styrene and ethylene
dichloride/vinyl
chloridearealmostcomparable with respect to the use ofethylene.

[Footnote 13] Difficulty in passage by gas. Like rubber balloons thatdeflate on the following day, many polymers tend to let gas passthrough when pressurized to a certain extent. Gas barrier property isimportant performance in food packaging, because difficulty inpassage by vapor and oxygen is often required.

34

Ethylene oxide is manufactured bydirectly adding oxygen to ethylene in thepresence of a silver catalyst. Because carbon
dioxide is produced if ethylene is oxidized
excessively, selectivity [Footnote 14] isimportant. To improve selectivity, various
attempts have long been made, such as the
addition of a small quantity of alkali metalsalt as a promoter. As a result, selectivity has
improved from around 60% in the 1930s toover 90% at present.
Ethylene oxide is a very reactive gas. It
may be used as it is for disinfecting medical
apparatus. However, it is usually used forsynthesis of industrial organic chemicals andpolymers, as shown in Fig. 3.7.
The greatest use of ethylene oxide is
ethylene glycol (EG) from a reaction withwater. EG is used as an antifreeze for car
engines. It is also used in large quantities forthe synthesis of polyester (PET resin,polyester fiber and unsaturated polyester resin,etc.). During production of EG, EG obtained
is reacted with ethylene oxide to give
diethylene glycol, which is then reacted with
ethylene oxide to give triethylene glycol.
These byproducts are used for solvents andextractive distillation. When more ethyleneoxidemoleculesarepolymerized,
polyoxyethylene
isobtained.
Polyoxyethylene with the structure ofpolymerized EG is also known aspolyethylene glycol. Polyoxyethylene is used
as a raw material for polyurethane, etc. Since
it is nontoxic, it also has prospectice uses inmedical devices such as drug delivery
systems.

[Footnote 14] In chemical reactions, an unexpected substance isoften obtained as a byproduct in addition to an expected product.
The percentage of reaction producing the expected product is called
selectivity.

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Fig. 3.7 Major product categories from ethylene oxide.
Ethylene oxide is reacted with various
lower alcohols to form glycol ethers. Esters
with acetic acid are also made by using thehydroxy groups of glycol ethers. Glycol
ethers and glycol ether esters are used assolvents for coatings and cleaners.
Since ethylene oxide is reactive to thehydroxy and carboxy groups, it is reactedwith linear higher alcohols [Footnote 15],higher fatty acids and alkyl phenol to form aseries of compounds to which thepolyoxyethylene group -(CH2CH2O)n- is
added (these products are also known asethoxylates). Ethoxylates are used for
non-ionic surfactants. The polyoxyethylenegroup is hydrophilic, although it does notdissociate into ions. On the other hand,because the higher alkyl group is lipophilic,
ethoxylates are made to nonionic surfactants.
Ethylene oxide is successively reactedwith the hydrogen atoms of ammonia to givemonoethanolamine, diethanolamine andtriethanolamine. As organic intermediates,
ethanolamines are used as raw materials of
pesticides and pharmaceutical products, assolvents and pH controllers for synthetic
detergents and cosmetics and as carbon
dioxide absorbents.
Althoughcarbondioxideisalow-reactivity gas, ethylene oxide is also
reacted with carbon dioxide to form ethylene
carbonate. Ethylene carbonate is used as a[Footnote 15] In organic chemistry, “higher” means that the numberof carbon atoms is large, being more than 10, while “lower” meansthat the number of carbon atoms is small, being 1 to several.

polar solvent, recently attacting attention as
an electrolyte for lithium ion secondary
batteries. It is also used for the manufactureof polycarbonate in the absence of phosgene.
Carbon monoxide and hydrogen are oxo
reacted with ethylene oxide to give
1,3-propanediol
in
one
step
via
β-hydroxypropionaldehyde (see Section 3.4.1(2)). Shell industrialized this process in 1999.
It has gained attention as a new
manufacturing process in contrast with theprevious manufacturing process using
acrolein (see Section 3.4.3 (8)).
Furthermore,
ethyleneoxide
iscopolymerized with formaldehyde to givepolyacetal and also with epichlorohydrin togive epichlorohydrin rubber. However,
because ethylene oxide is not a main
monomer, these polymers are small-scale
uses of ethylene oxide.
(3) Ethylbenzene/styrene
Ethylene is reacted with benzene to give
ethylbenzene. For this reaction, various acidcatalysts and liquid- and gas phasemanufacturing
processes
have
been
developed. At present, the gas phase processusing a zeolite catalyst is usually used inconsideration of corrosiveness of facilities,
disposal of waste catalysts, recovery of heat,etc. (see Section 6.1.2 (1) 4)). Ethylbenzene isalso obtained as one of the C8-fraction
chemicals from cracked gasoline produced bysteam cracking of naphtha and also from
catalytic reformate of petroleum. However,
Systematic Survey on Petrochemical Technology

35becauseofthedifficultyinseparation/purificationfromxylene,ethylbenzene is mainly synthesized fromethylene and benzene.
Ethylbenzene is mostly used for the
manufacture of styrene. It is a typical organicintermediate. Styrene is mainly manufacturedby the dehydrogenation of ethylbenzene.
Since this reaction is endothermic, like steam
cracking of naphtha and ethane, it isperformed at 500–600°C while carbonization
is prevented by adding high temperature
steam to lower the partial pressure. Steamcracking of naphtha and ethane is thermal
cracking in the absence of a catalyst, while
dehydrogenation of ethylbenzene uses acatalyst. The co-production process of
propylene oxide and styrene is also an
important route for the supply of styrene (seeSection 3.4.3 (4))
As shown in Fig. 3.8, styrene is
exclusively used as a raw material forpolymers.

Fig. 3.8 Major product categories fromstyrene.
Polystyrene as a homopolymer is a hard,transparent polymer. It is made into molded
products, sheets and foamed products andused for daily necessaries, electricalappliances, containers, food trays, buffers andheat insulators. To improve the poor impact
resistance of polystyrene, high impact
polystyrene (HIPS) in which rubber ismodified, acrylonitrile-styrene resin (AS resinor styrene acrylonitrile [SAN]) in whichacrylonitrile is copolymerized, and ABS resin
in which butadiene and acrylonitrile iscopolymerized have been developed. ABS
resin is not transparent. As colored resin, it isoften used for casings of electrical products
such as television sets and personal

36

computers. Polystyrene, HIPS, AS resin, ABS
resin, etc. are generally known as styrenicpolymers.
Another great use of styrene is synthetic
rubber from copolymerization with butadiene.
Styrene-butadiene rubber (SBR) is a typicalsynthetic rubber and is used in large
quantities
fortires.
The
styrene-butadiene-styrene block copolymer(SBS) is a typical thermoplastic elastomer.
Since various styrene-based polymers areavailable as mentioned above, bulk
polymerization, solution polymerization,suspension polymerization and emulsion
polymerization are used on a case-by-casebasis. Styrene is also used as a crosslinking
agent for processing/molding unsaturated
polyesters.
(4) Ethylene dichloride and vinyl chloride
Ethylene dichloride (EDC) is obtained byadding chlorine to ethylene. It is then cracked
into vinyl chloride and hydrogen chloride by
non-catalytic thermal cracking. The reactants
are quenched with cold EDC spray. Hydrogenchloride gas is removed, and vinyl chloride isseparated by distillation. This process is very
similar to the reactant-quenching process
after steam cracking of naphtha. Hydrogenchloride gas is collected and used for ethylene
oxychlorination. Ethylene, hydrogen chloride
and oxygen or air are reacted byoxychlorination in the presence of a copper
chloride catalyst to give EDC and water.
Vinyl chloride is mostly polymerized andused for the production of vinyl polychloride(polyvinyl chloride). Initially, production ofvinyl polychloride by radical polymerization
was performed by emulsion polymerization
using water. However, it was subsequently
replaced by suspension polymerization withcharacteristically good product quality.
As shown in Fig. 3.9, not only polyvinyl
chloride but also many industrial organic
chemicals are obtained from EDC or vinyl
chloride. Vinylidene chloride is obtained
when 1,1,2-trichloroethane obtained bychlorinationof
vinylchlorideisdehydrochlorinatedusing
analkali.
Vinylidene chloride is subjected to radical
polymerization to give vinyliden polychloride.
Because vinylidene polychloride is excellent

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

in gas barrier property and adhesiveness, it isused as food cling films in daily life.
EDC and chlorine as a raw material gives
a mixture of trichloroethylene andtetrachloroethylene. The production ratio of
tetrachloroethylene to trichloroethylene canbe adjusted by changing the charge-in ratio of
EDC to chlorine.

Fig. 3.9 Major product categories fromethylene dichloride, vinyl chloride.
Trichloroethylene is used for solvents andextractive solvents. Tetrachloroethylene, also
known as perchloroethylene, is used as asolvent for dry cleaning and a degreasing
agent
for metal
processing.
These
chlorine-based solvents have the advantage ofbeing flame retardant. However, it is alsofeared that they could have adverse healthandenvironmental
effects.
1,1,1-Trichloroethane
as
well
as
tetrachloroethylene, manufactured from vinyl
chloride was used in large quantities as achlorine-based solvent until the early 1990s.
However, because it was classified as anozone depleting substance and its use wasregulated by the Montreal Protocol, its
production was discontinued in the
mid-1990s.
In vinyl fluoride, chlorine of vinyl
chloride is replaced by fluorine. Hydrogen
fluoride is added to vinyl chloride underpressure in the absence of a catalyst to give
1-chloro-1-fluoroethane, which is thendehydrochlorinated at approximately 500°C
to give vinyl fluoride. Vinyl fluoride is
exclusively made into vinyl polyfluoride andused as a coating material. It is an industrialorganic
chemicalsimilartotetrafluoroethylene obtained from the C1
fraction, although there are clear differencesin raw materials and manufacturing processes
between the two chemicals.

EDC is reacted with aqueous ammonia
under pressure to give ethylenediamine.
Ethylenediamine is used as an organicintermediate for the manufacture ofpharmaceuticalproducts
andrubberchemicals. It is also reacted withmonochloroacetic
acid
to
give
ethylenediamine tetraacetate (EDTA, edeticacid), which is used as a complex-forming
agent.
(5) Acetaldehyde and vinyl acetate
The production scales of other products
from ethylene shown in Fig. 3.5 are far
smaller than polyethylene, ethylene oxide,
ethylbenzene and EDC. However, a great
many products are included in this category.
Acetaldehyde as well as vinyl chloride
used to be a core industrial organic chemical
made from acetylene. Acetaldehyde became apetrochemical product in the latter half of the
1950s when the Hoechst-Wacker process wasindustrialized (see Section 6.1.2 (2) 1)).. In
the presence of a similar catalyst, ethylene,
acetic acid and oxygen are reacted to givevinyl acetate.
Acetaldehyde was mainly used for thesynthesis of acetic acid, butanol (butyl
alcohol) and octyl alcohol. However, in the
1970s, carbonylation of methanol, mentioned
previously, was industrialized as a new
method of manufacturing acetic acid and was
subsequently widely used worldwide.
Moreover,theoxo
process(hydroformylation) using propylene as astarting material was widely used for
manufacture of butanol and octyl alcohol. As
a result, acetaldehyde lost its main uses andits production rapidly decreased worldwide
from the 1980s onwards. At present, it is onlyused for the manufacture of small-scale
products such as pentaerythritol.
Showa Denko developed a method of
manufacturing acetic acid by direct oxidationof ethylene without going throughacetaldehyde and industrialized it in the latethe 1990s. However, this method has not been
widely enough used to replace carbonylationof methanol on a worldwide scale.
Vinyl acetate is polymerized to give
polyvinyl acetate (adhesives, coatings andfiber-finishing agents). Polyvinyl acetate issaponified and used for polyvinyl alcohol
Systematic Survey on Petrochemical Technology

37

(paste, coating agents and raw material of
polyvinyl butyral). Vinyl acetate is also used
as a comonomer for ethylene and vinyl
chloride.
(6) Ethanol
Ethanol (also known as ethyl alcohol) is
made by adding water to ethylene in the gas
phase in the presence of an acid catalyst(phosphoric acid/silica carrier, etc.). Ethanol
is widely used as a solvent and is also used asa raw material for ethyl esters such as ethyl
acetate. The ethanol market was developed
using the fermentation process before thepetrochemical industry was established.
Afterwards, the petrochemical industry took
over the market completely. Therefore,
ethanol was the main product of ethylene in
the 1950s when the petrochemical industry
began to develop rapidly. This was because
acetaldehyde could be produced by oxidizing
ethanol. However, as it became possible to
make acetaldehyde by the Hoechst-Wacker
process without first creating ethanol, thecommercial value of ethanol began to decline.
(7) α-Olefins and linear higher alcohols
C4 to C20 hydrocarbons with theterminal double bond (at the α-position) are
known generally as α-olefins. Among them,
C10 to C14 linear α-olefins are particularly
important as raw materials for surfactants andlubricants and are being produced industrially.
Meanwhile, there has been a growing recent
demand for C4 to C8 lower α-olefins for the
manufacture of various L-LDPEs.
Accordingtoonemethodofmanufacturing α-olefins by oligomerizationof ethylene, trialkylaluminium is reacted with
ethylene (Ziegler process). This process has
been modified and is used even now.
However, it has a disadvantage in that the
number of carbon atoms of the resulting
α-olefin varies considerably from 4 to 24.
Linear trialkylammonium is reacted withoxygen and then hydrolyzed to give higher
alcohols. When α-olefins are oxo reacted with38

syngas and then reduced with hydrogen,higher alcohols of odd carbon numbers
having one more carbon atom can beobtained.
There is another modification in which
the disadvantage of oligomerization of
ethylene by trialkylaluminium has been
improved to obtain the C6 to C14 olefins thatare in great demand. This method has the
disadvantage of an increased number ofbranched chains and internal olefins. The
SHOP process developed by Shell andindustrialized in 2003 is used for the
manufacture of C10 to C14 α-olefins and C11
to C15 higher alcohols with a terminalhydroxy group. α-Olefins with other lengths
are reutilized during the reaction.
3.4.3

Products from the C3 fraction(propylene-based products)
The C3 basic petrochemical is propylene.
Figure 3.10 shows the main productcategories made from propylene. For sometime after petroleum chemistry entered fullswing in the 1950s, the basic petrochemicals
ethylene, butadiene and benzene were in gooddemand, while production of propylene wasgreater than its consumption. This was
because it was not easy to develop methodsof synthesizing C3 industrial organic
chemicals (acrylonitrile, acrylic acid, glycerin,etc.) from propylene, although these products
had been manufactured in the fields of coalchemistry and oleochemistry since before theestablishment of petrochemistry. However, anumber of industrial organic chemicals werelater developed from propylene. Furthermore,
PP was developed and its production
increased rapidly, resulting in an increase in
the consumption of propylene. Propylene
demonstrates two types of reaction, i.e.,
addition reaction to the double bond, as isobserved with ethylene (see Section 6.1.2 (1)),
and reaction of the methyl group whileleaving the double bond (see Section 6.1.2(2)). Acrylonitrile, acrolein and allyl chloride
are manufactured using the latter reaction.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 3.10 Major product categories from propylene.
(1) Polypropylene
Unlike ethylene, propylene could noteasily be radically or ionically polymerized toobtain an industrial material. It was not until
the Ziegler-Natta catalysts were developed in1957 that polypropylene (PP) could be
produced for the first time. Unlike
polyethylene, PP has side-chain methylgroups on the main chain of the polymer andtherefore in order to obtain an industrial
polymer material with good physicalproperties, propylene must be polymerized insuch a way that the side chains are arranged
to face a fixed direction. Even the direction ofside chains is regulated in stereospecificpolymerization, and polymers thus obtained
are called stereoregular polymers. All side
chains are arranged to face a fixed direction
in isotactic polymerization, while insyndiotactic polymerization the side chainsare arranged to alternately face different
directions. The side chains are not arranged
regularly in atactic polymerization.
Since the Ziegler-Natta catalysts areavailable as fine crystals, polypropylene wasinitially produced by solution polymerizationin which the catalyst was dispersed in asolvent such as hexane and then propylene
was passed through the solution. As theactivityofthecatalyst
andthestereoregularity of the resulting polymer wereboth low, it required decalcification withmethanol to remove the catalyst and washingwith a solvent to remove low crystalline
polymer and low molecular weight polymer
after the reaction. As catalysts have improved
subsequently, slurry polymerization and mass
polymerization (polymerization in liquefied
propylene,
also
known
as
bulk
polymerization) have been developed,
makingwashinganddecalcification
unnecessary, resulting in a marked reduction
in equipment and energy costs. The
technology that has dramatically promoted
the improvement of catalysts was developedby Mitsui Petrochemical Industries (nowMitsui Chemicals). Japan can boast thispolymer synthesizing technoloogy to theworld (see Section 5.6.3 (1), Section 6.1.3 (1)4)).
Meanwhile, a metallocene catalyst thatwas found as an epoch-making catalyst forpolyethylene in the 1980s has also been
applied to the polymerization of propylene.
Isotactic PP has been the only stereoregular
PP that has been produced in the presence of
the Ziegler-Natta catalyst. If the metallocen
catalyst is used, syndiotactic PP can also be
produced. In 2011, Mitsui Chemicals
industrialized this process.
As shown in Fig. 3.11, PP is classified aseither homopolymer, in which only propylene
is polymerized, and copolymer, in which
propylene is copolymerized with ethylene.

Systematic Survey on Petrochemical Technology

39

Homopolymer
Polypropylene PP
Random PP
Copolymer
Block PP

Fig. 3.11 Types of typical polypropylenes.
The copolymer is further classified into
random copolymer, in which ethylene isirregularly copolymerized with the propylene
sequence by adding a small amount of
ethylene (5% or less), and block copolymer(also known as the impact copolymer), in
which the propylene homopolymer portion,
the random copolymer portion of ethylene
andpropylene,
andthepropylene
homopolymer portion are connected in thatorder. The homopolymer is highly crystalline,
hard and strong. It demonstrates higher heat
resistance than polyethylene and PP random
copolymers, and is used for films, sheets,
injection-molded products, fibers, unwoven
cloth and bands (binding for packaging).
Since the crystallinity of the random
copolymer is low, its heat-resistance is also
low (although it is still higher than the heat
resistance of polyethylene). As it can be madetransparent and is heat-sealable, it is usefulfor films and sheets. The film is categorized
into nonoriented cast polypropylene (CPP)film and biaxially oriented polypropylene(OPP) film. The random copolymer is also
used for injection-molded articles, such astransparent clothes cases and transparent foodcontainers, and blow-molded articles, such as
shampoo bottles. The block copolymer is an
impact-resistant material characterized byboth the hardness and strength of thehomopolymer and the flexibility of therandom copolymer. It is used for automobiles(car bumpers) and large home electric
appliances, having played the most importantrole in expanding the demand for PP since the1980s.
(2) Synthetic rubber (EPR)
EPR is a polymer in which ethylene,
propylene and an unconjugated diene such asdicyclopentadiene or ethylidene norbornene
as the third component are copolymerized in
the presence of the Ziegler-Natta catalyst

40[Footnote 16]. EPR is also known as ethylene
propylene diene rubber (EPDM) because it iscomposed of ethylene, propylene and a dienemonomer. EPR that can be vulcanized withsulfur is used as synthetic rubber. Most of the
conjugated diene-based synthetic rubbers
have double bonds in the main chain of thepolymer with unsaturated bonds still
remaining in the main chain even after it ispartially involved in vulcanization (seeSection 3.4.4 (1)). This is the primary causeof the deterioration of rubber on exposure tooxygen/ozone and light. In contrast, thebonds in the main chain of EPR are all
saturated, while unsaturated bonds are all inthe side chains. Since EPR is outstanding inresistance to weather, heat and chemicals, it is
widely used for automotive parts such as tires
and tubes.
(3) Cumene, acetone and phenol
Like
ethylbenzene,
cumeneismanufactured by the reaction of propylene
and benzene. In the same way that styrene isproduced by the dehydrogenation of
ethylbenzene, α-methylstyrene can beproduced by the dehydrogenation of cumene.
α-Methylstyrene is a small-scale industrialorganic chemical that is used in small
quantities as a comonomer for improving theheat resistance of ABS resin. Since
α-methylstyrene is obtained as a byproduct of
the co-production of phenol and acetone fromcumene as mentioned below, this process isactually the main source of supply of thiscompound.
The main use of cumene is the
co-production of acetone and phenol.
Cumene is oxidized with air to give cumenehydroperoxide. Treated with sulfuric acid, theperoxide is cleaved to give phenol andacetone. Since one mol each of acetone andphenol are produced simultaneously from 1
mol of cumene, the balance of demand
between acetone and phenol is important. In
the past, there was a great demand for acetone,
while the supply of phenol tended to be
excessive. In that case, acetone could be[Footnote 16] Olefines with two double bonds are called dienes.
Dienes sandwiching a single bond between two double bonds arecalled conjugated dienes, while dienes sandwiching two or more
single bonds between two double bonds are non-conjugated. Twodouble bonds react irrespectively of each other in the case ofnon-conjugated dienes.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

supplied by dehydrogenation or oxidative
dehydrogenation of isopropyl alcohol, as
mentioned below. Conversely, in recent years,
there has been a great demand for phenol,
while the supply of acetone has tended to be
excessive. Using a recently industrialized
method, acetone is reduced with hydrogen to
give isopropyl alcohol, which is thendehydrated to propylene and returned into a
raw material of cumene. However, because a

supply of hydrogen is needed, the process ismore costly than it would be in the event ofan acetone shortage.
As benzene-derived phenol is explainedin the “Benzene” section (see Section 3.4.5),
only propylene-derived acetone is describedin this section. Acetone is important not only
as a solvent but also as an organicintermediate, as shown in Fig. 3.12.

Fig. 3.12 Major product categories from acetone.
At present, the greatest synthetic use ofacetone is BPA obtained by reaction withphenol. This substance is also described in
the “Benzene” section. The next mostimportant use is methyl methacrylate (MMA)
that is synthesized via reaction with hydrogencyanide. Although for a long time thisreaction was the main process ofmanufacturing MMA, it has rapidly
decreased in importance recently. One of thereasons is that the supply of cheap hydrogencyanide as a byproduct of acrylonitrile has
markedly decreased. Another reason is thatmethods of manufacturing MMA by using C4isobutylene and tert-butyl alcohol as starting
materials have been developed and widelyused.
C6 methylisobutyl ketone is obtained byaldol condensation of 2 molecules of acetone
followed by several steps of reaction. This
compound is used as a solvent. Isophorone is
obtained by aldol condensation of 3 acetone
molecules. Isophorone is used not only as ahigh boiling point solvent but also as anorganic
intermediate.
Isophorone
diisocyanate is an important organic chemical
induced from isophorone. As aliphatic
diisocyanate, it is used for the production ofpolyurethane.
(4) Propylene oxide
Figure 3.13 shows the products frompropylene oxide. Compared with Fig. 3.7
showing the product categories from ethyleneoxide, the product line-up from propyleneoxide is very poor, comprising only
propylene glycol, polypropylene glycol andpropylene glycol ether, corresponding to EG,
polyethylene glycol and glycol ether.

Systematic Survey on Petrochemical Technology

41

Fig. 3.13 Major product categories frompropylene oxide.
Propylene oxide is entirely used forpolypropylene glycol as a raw material forpolyurethane. Polypropylene glycol, in which
polyhydric alcohol is polymerized withpropylene oxide, is called polyether polyol. It
is used as a raw material for thermosetting
polyurethane.
Propylene glycol is used for polyether
polyol and unsaturated polyesters. However,
it is just one of the polyhydric alcohols suchas EG, glycerin and pentaerythritol. Its
product scale is much smaller than EG.
Various propylene glycol ethers madefrom propylene oxide and lower alcohols are
solvents that compete with various glycol
ethers (cellosolves) made from ethylene oxide
and lower alcohols. However, they are not aslarge-scale.
In the structure of propylene oxide as
well as ethylene oxide, oxygen is directly
added to the double bond. The direct additionof oxygen to ethylene was achieved in the
1930s, while the direct addition of oxygen to
propylene has not yet been achieved. The
chlorohydrin process as a very old method ofsynthesizing ethylene oxide is still usedcommonly for the production of propyleneoxide. As this process is very wasteful, manyother manufacturing methods have been
investigated.
A method that has been industrialized is42

the oxidation of propylene with a peroxide togive propylene oxide. If the product obtained
after the reaction of the peroxide is useful, theprocess can be industrialized as a method of
manufacturing the product and propyleneoxide simultaneously. However, it is difficult
to manage co-production, because it isinfluenced by the supply-demand balancesand markets for the two products. Table 3.2
shows the main industrialized peroxides
together with their raw materials andproducts.
Of these methods of manufacturing
propylene oxide, process (1) was convenient
while MTBE required large quantities oftert-butyl alcohol. However, after the use of
MTBE for gasoline was prohibited, there wasno demand for tert-butyl alcohol. Process (2)has become a promising route to supply
styrene. According to process (3), because
cumene and then cumene hydroperoxide canbe produced from cumyl alcohol, the productfrom the peroxide is returned to the original
raw material. Thus the disadvantages ofco-production can be avoided. Sincehydrogen peroxide has recently been
produced on a large scale and supplied
cheaply, process (4) using hydrogen peroxide
as a peroxide has been industrialized. As only
propylene oxide and water are produced inthis process, the problems of co-production
can be completely solved.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)Table 3.2 Typical propylene oxide production process by peroxide(5) Isopropyl alcohol
In the same way that ethanol is produced
by adding water to ethylene, isopropyl
alcohol (IPA) is produced by adding water topropylene. Isopropyl alcohol is used as acheap alternative solvent to ethanol. It used to
be an important raw material of acetone.
However, as mentioned above, a significant
amount of demand for it was lost due to thefact that acetone became excessive in the
co-production of acetone and phenol.
(6) n-Butyraldehyde and isobutyraldehyde
n-Butyraldehyde and isobutyraldehyde
having one more carbon atom are producedby the oxo process of propylene (see Section
3.4.1 (2)). Figure 3.14 shows the main
products
fromn-butyraldehyde
andisobutyraldehyde.
n-Butyraldehyde is condensed with aldol
in the presence of an alkali catalyst,
dehydrated, and reduced with hydrogen togive
2-ethylhexanol(anoctanol).
2-Ethylhexanol is reacted with phthalicanhydride to give dioctyl phthalate (DOP). It
is also reacted with adipic acid or phosphoricacid to give esters with a 2-ethylhexyl group.
These esters from 2-ethylhexanol are used inlarge quantities as plasticizers for polyvinyl
chloride. n-Butyraldehyde is reduced withhydrogen to give n-butanol. Acrylic acid
esters of n-butanol and 2-ethylhexanol areused as raw materials for coatings.
Meanwhile, isobutyraldehyde is reduced withhydrogen to give isobutyl alcohol. Bothn-butanol and isobutyl alcohol are used assolvents, but n-butanol with higher solubility
is more popular as a solvent in coatings. In
this way, n-butyraldehyde has a greater
demand than isobutyraldehyde(7) Acrylonitrile
Propylene is reacted with ammonia andoxygen to give acrylonitrile. This reaction,
known as ammoxidation, is one of theepoch-making reactions in the technologicalhistory of petrochemistry. This reaction is
also called the “Sohio process” after thecompany that invented it. It is significant inthat it is not the double bond but the methylgroup of propylene is reactive. This reaction
was discovered in the latter half of the 1950s.
In the 1960s, it replaced many existing
methods of manufacturing acrylonitrile, suchas the hydrogen cyanide process to giveacetylene. Initially, because the the reaction
had low selectivity, large quantities ofhydrogen cyanide and acetonitrile were
produced as byproducts. Hydrogen cyanide
was used for many purposes such as methyl
methacrylate. Initially, the use of acetonitrile
was limited, but the demand for thiscompound as polar and extracting solvents
subsequently gradually expanded. However,
due to progressive improvements in catalysts
in recent years, the production of these
byproducts has decreased. Alternative
methods are available for manufacture ofhydrogen cyanide, but some measures must
be taken for acetonitrile, as it has long been
manufactured only as a byproduct ofacrylonitrile.

Systematic Survey on Petrochemical Technology

43

Fig. 3.14 Major product categories from butyraldehyde, isobutyraldehyde.
As shown in Fig. 3.15, acrylonitrile isused for many purposes.

Fig. 3.15 Major product categories fromacrylonitrile.
Acrylonitrile is polymerized to givepolyacrylonitrile (PAN). PAN is used foracrylic fiber. As a plastic with an excellent
gas barrier property, it is also used for
packaging containers. PAN-based carbon
fiber made by carbonizing acrylic filament isvery strong. Toray and other Japanesecompanies have used it for manufacturing
fishing poles, golf shafts, tennis rackets, etc.
since the 1970s. Since carbon fiber is light, it
has been used for aircraft parts since the late1980s. It has also been used in the mainwings and bodies of aircrafts, attracting
attention since the late 2000s. Since it is also
expected to be used for automotive parts andbodies, the demand for carbon fiber could
expand dramatically in the future.
As a comonomer, acrylonitrile is used for

44

manufacture of AS resin, ABS resin andsynthetic rubber (NBR). Acrylonitrile isdimerized by electrolysis to give C6
adiponitrile, which is then reduced withhydrogen to give hexamethylenediamine.
This process is one of the methods ofmanufacturing hexamethylenediamine as araw material for 6,6-nylon.
The nitrile group of acrylonitrile ishydrolyzed to give acrylamide. A copper
catalyst has been used for hydrolysis.
However, in 1985, Nitto Kagaku Kogyo (nowMitsubishi Rayon) industrialized a biologicalmethodusing
acrylamide-producing
organisms. Subsequently, biological methods
using enzymes characterized by high heat
resistance and good productivity have beendeveloped. These are unique petrochemical
techniques created in Japan. Acrylamide ispolymerizedtogivepolyacrylamide.
Polyacrylamide is used as a flocculant for
wastewater treatment, as a mud-solidifying
stabilizer for drilling oil wells, and in thepaper industry as a yield-improving agent, afiltering agent and a paper-strengthening
agent.
Since
polyacrylamide
asawater-soluble polymer increases the viscosityof water, it is also used as a thickener forenhanced oil recovery (EOR) [Footnote 17].
Compounds with reactive hydrogen suchas amine, alcohol and aldehyde are added to[Footnote 17] A method of increasing the production of crude oil byinjecting water and gas into oil wells that are running dry.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

the double bond of acrylonitrile to cause
cyanoethylation. Amine is obtained by the
reduction of cyanoethyl compounds withhydrogen, while carboxylic acid is obtainedby the hydrolysis of these compounds. These
processes are important reactions for
producing
cationic
surfactants
andamphoteric surfactants. As mentioned above,
acrylonitrile is used not only as a monomer
but also as an organic intermediate.
(8) Acrolein, acrylic acid and acrylic acid
estersThere have been several methods used for
manufacturing acrylic acid. However, atpresent, acrylic acid is mainly produced byoxidizing the methyl group of propylene andthen oxidizing the resulting acrolein (seeSection 6.1.2 (2) 4)). This process wasdeveloped by Nippon Shokubai and
Mitsubishi Chemical. Acrylic acid is reactedwith various alcohols to give acrylic acid
esters.
Acrylic
acid
undergoesradicalpolymerization to give polyacrylic acid as awater-soluble polymer. As polyacrylic acidcatches calcium ions, etc. in water, it is used

as a builder for synthetic detergents. However,in Japan, zeolite is used exclusively as abuilder, while polyacrylic acid is rarely used
for this purpose. When acrylic acid andacrylic acid sodium are copolymerized in thepresence of a polyhydric alcohol ester ofacrylic acid as a crosslinking agent,superabsorbent resin is obtained. While
starch-based superabsorbent resins, etc. arealso available, acrylic acid-based is the mostwidely used. Copolymers of acrylic acid
esters with metacrylic acid esters, vinyl
acetate, etc. are used as acrylic coatings. A
great variety of coatings such as aqueous,thermoplastic and ultraviolet curable coatings
can be made by using various ester groups.
Figure 3.16 shows the uses of acrolein.
The greatest use is acrylic acid. However,
because acrolein is a very reactive aldehyde,
it is also used as an organic intermediate formethionine as an essential amino acid (aminoacid pharmaceuticals and feed additives),
glutaraldehyde (sterilizing disinfectants,
leather tanning agents and fiber treating
agents) and 1,3-propanediol.

Fig. 3.16 Major product categories from acrolein.
(9) Allyl chloride and epichlorohydrin
When propylene is reacted with chlorineat 500°C, allyl chloride is produced by highly
selective chlorination of the methyl grouprather than an addition reaction to the doublebond. A major use of allyl chloride is the
manufactureofepichlorohydrin.
Epichlorohydrin is obtained when chlorinewater (hypochlorous acid) is allowed to actonallylchloride
and
is
then
dehydrochlorinated with an alkali. This
manufacturing process is the same as for
propylene oxide. Since epichlorohydrin has
two functional groups, i.e., epoxy andchlorine groups, it is used as a monomer forthe production of epoxy resin. Epoxy resin isused for adhesives and semiconductor sealing
Systematic Survey on Petrochemical Technology

45

materials. There has also been a growing
recent demand for epoxy resin as a matrix
resin (impregnation resin) for carbon fiber.
Glycerin can be synthesized from either
allyl chloride or epichlorohydrin, and theseprocesses were industrialized. However,synthesis of glycerin declined from the 2000s,
because biodiesel oil began to be produced inlarge quantities from fats and oils such as
palm oil, resulting in the production of highamounts of glycerin as a byproduct.
3.4.4

Products from the C4 and C5
fractionsC4 olefins produced by steam cracking of
naphtha include butadiene and four kinds ofbutylene, which are separated and purified asnecessary. Of these, butadiene is the mostimportant. Figure 3.17 shows the main
product categories from butadiene.

(1) Polymers from butadiene
Synthetic rubber called diene-based
rubber is produced by the polymerization andcopolymerizationofbutadiene.
Styrene-butadiene rubber (SBR) obtained by
the copolymerization of butadiene andstyrene and butadiene rubber (BR) obtainedby polymerization of butadiene alone aretermed as general purpose rubber. The
consumption of general purpose rubber ishigh, being comparable to that of natural
rubber and isoprene rubber (IR), mentioned
below. Both SBR and BR are used in large
quantities for tires and are also widely usedforrubbershoes,
industrial
parts,
rubber-coated cloth, paper coatings, etc. BR
is used for golf ball cores and high impact
polystyrene (HIPS).

Fig. 3.17 Major product categories from butadiene.
Nitrile rubber (NBR) is formed by the
copolymerizationofbutadieneandacrylonitrile. Hydrogenated nitrile rubber(HNBR), in which the double bond of NBR ishydrogenated almost completely, is improved
with respect to weather resistance. Both NBR
and HNBR are special rubbers that haveoutstanding oil resistance. These are used foroil-resistant hoses, tank lining and packing.
Chloroprene is obtained by reaction withchlorine and butadiene. Chloroprene ispolymerized to give chloroprene rubber (CR).
CR is used for belts, hoses, adhesives, wire
coating, etc.

46

The reaction used for the manufacture ofsynthetic rubber from conjugated diene is 1,4
polymerization [Footnote 18], which makes
use of the characteristics of conjugateddouble bonds. As a result of this reaction, thedouble bonds at positions 1 and 3 of[Footnote 18] When the double bond of conjugated diene(CH2=CH-CHR=CH2) is polymerized alone by addition reaction to
make the polymerization chain -CH2-CH (CHR=CH2)-, the reaction
is called 1,2 polymerization, while when the two double bonds areallowed to act concertedly to make the polymerization chain-CH2-CH=CHR-CH2-, the reaction is called 1,4 polymerization. The
double bond is left on the side chain in 1,2 polymerization, while itis left on the main chain in 1,4 polymerization. The binding directionof the main chain around the double bond (cis or trans) may be indisorder or regulated.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

conjugated diene move to position 2 andremain there. In the vulcanization of rubber,
this double bond is partially reacted withsulfur to make the rubber elastic. For
polymerization and copolymerization fromconjugated diene, radical polymerization andionic polymerization are used depending on
the expected product. Radical polymerizationisfurtherclassified
intoradicalpolymerization,using
anordinary
polymerization
initiator,
and
redox
polymerization, in the presence of a redox
system at low temperature. In ionicpolymerization, alkali metals, organic metals,
the Ziegler-Natta catalyst, etc. are used on acase-by-case basis. Polymerization is
performed as emulsion polymerization or
solution polymerization depending on thetype of rubber. Polymerized products are alsoclassified as solid products that arecoagulated so as to be used as raw materials
for rubber-molded products, and latex, whichis left emulsified.
Thermoplastic
elastomers
SBS(styrene-butadiene-styrene block copolymer)
are obtained by the block copolymerization of
butadiene and styrene. SBS is a block
copolymer that is composed of a polystyrene
portion as a hard segment and a BR portion asa soft segment. ABS resin is obtained by the
copolymerization of butadiene, styrene andacrylonitrile.
(2) Industrial organic chemicals frombutadiene
Butadiene that is used as a raw materialof polymers is also used for the manufactureofindustrialorganic
chemicals.
1,4-Diacetoxy-2-butene is obtained by
1,4-addition of acetic acid to butadiene.
1,4-Diacetoxy-2-butene is reduced withhydrogen and then hydrolyzed to give
1,4-butanediol and acetic acid. The acetic
acid is reutilized. 1,4-Butanediol is
copolymerized with terephthalic acid to give
polybutylene terephthalate (PBT), a general
purpose engineering plastic. Tetrahydrofuran(THF) is produced from 1,4-butanediol bydehydration. THF is used as a solvent andundergoes ring-opening polymerization to
give polytetramethylene glycol (PTMG).
PTMG is copolymerized with MDI to givepolyurethane elastic fiber.
When hydrogen cyanide is added in 2
steps to the double bond of butadiene,
adiponitrile that is a C6 industrial organic
chemical is obtained (see Section 3.4.1 (5)).
Sulfolene is obtained by 1,4-addition of
sulfur dioxide to butadiene, while sulfolane is
obtained by the hydrogenation of sulfolene.
Sulfolane is used as a solvent for extractive
distillation and gas purification.
(3) Industrial organic chemicals andpolymers from isobutylene
Isobutylene is the next most important C4basic chemical to butadiene. Figure 3.18
shows the product categories made from
isobutylene.
Isobutylene is readily reacted with waterto give tert-butyl alcohol in the presence of anacid catalyst. As mentioned above, thisreaction is also used for separating
isobutylene (see Section 3.3.3 (2)). tert-Butyl
alcohol is dehydrated to give isobutylene.
Methyl methacrylate (MMA) is madefrom isobutylene or tert-butyl alcohol as astarting material. This process is similar to
the reaction for producing acrolein and thenacrylic acid by oxidizing the side-chain
methyl group while retaining the double bondof propylene.
Isobutylene is copolymerized with small
quantities of isoprene to give butyl rubber(isobutylene isoprene rubber [IIR]). Butyl
rubber has specific physical properties,
because most of the bonds in the main chain
are saturated. It is outstanding in aging
resistance and ozone resistance and ischaracterized by very low gas permeability.
Due to these merits, it is used for tire tubes,
inliners for tires, roofing, etc.
Isobutylene is directly reacted withmethanol to give methyl tert-butyl ether(MTBE). MTBE was used as gasoline
additives, but its use was later prohibited.
This course of events is outlined in Section
5.5.2 (3) 3).

Systematic Survey on Petrochemical Technology

47

Fig. 3.18 Major product categories from butylenes.
(4) Industrial organic chemicals andpolymers from n-butylene
Figure 3.18 shows the industrial organic
chemicals and polymers made fromn-butylene (normal butylene) (a mixture of
1-butylene,
cis-2-butylene
andtrans-2-butylene). n-Butylene was often usedwithout separation for the production ofindustrial organic chemicals. However, theimportance of 1-butylene has increased
rapidly since the use of L-LDPE spreadworldwide in the 1980s, and it has since been
separated and purified.
n-Butylene is oxidized with air to give
maleic anhydride. However, since the methodof manufacturing maleic anhydride byoxidation with n-butane was developed,
production of maleic anhydride via
n-butylene has decreased in significance.
When water is added to n-butylene as a
mixture in the presence of an acid catalyst,
sec-butyl alcohol is obtained. sec-Butyl
alcohol is oxidized to give methyl ethyl
ketone (MEK), which is widely used as asolvent.
Butylenes that are not separated or48

purified are reacted with isobutane in thepresence of a fluoric acid catalyst to give C8
branched paraffins. Petroleum waste gas
containing propylene and butylene issometimes used as it is for reaction with
isobutane to give C7 to C8 branched paraffins.
These branched paraffins, also called
alkylates, are gasoline-based materials (seeSection 2.1.2 (5)).
(5) Main industrial organic chemicals andpolymers from the C5 fraction
Figure 3.19 shows the product categories
produced from the C5 fraction. Important
basic petrochemicals that are separated andpurified from the C5 fraction include
cyclopentadiene and isoprene (see Section
3.3.3 (2)). The methods of separating thesechemicals have already been mentioned. The
resulting residue after separating thesesubstances and the C5 fraction is polymerized
to give petroleum resin, a cheap polymer thatis used for coatings for white street markings
and adhesives.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 3.19 Major product categories from products with C5.
Dicycylopentadiene is the important third
component
for producing EPR
bycopolymerization
withethylene
andpropylene (see Section 3.4.3 (2)). Whenheated, dicyclopentadiene is cracked to give
cyclopentadiene.
Cyclopentadieneor
dicyclopentadiene undergoes ring-opening
metathesis
polymerizationor
copolymerization with ethylene followed by
reduction to give various kinds of COP(cycloolefin polymers) and copolymers. COP
is used as an optical material, because it isnoncrystalline, very transparent, and not
hygroscopic.
A significant use of isoprene is the
manufacture of synthetic rubber (isoprenerubber,IR).
Isoprene
undergoes
stereospecific polymerization in the presenceof a Ziegler-Natta catalyst to givecis-1,4-polyisoprene. The structure of thispolymer is the same as that of natural rubber.
Isoprene is added in small quantities forcopolymerization with isobutylene to givesynthetic rubber (isobutylene isoprene rubber,
IIR). Due to the addition of isoprene, IIR is asulfur-vulcanizable
rubber.
A
block
copolymer
withapolystyrene-polyisoprene-polystyrene
structure like SBS is obtained. It is athermoplastic
elastomer
calledstyrene-isoprene-styrene block copolymer(SIS). In addition, many synthetic perfumes
are produced by the dimerization of isoprene
followed by oxidation. Raw materials forcosmetics such as squalane, pharmaceuticalproducts and intermediates for pesticides are

made from oligomers of isoprene.
3.4.5 Products from the C6 fraction
The main C6 basic petrochemical is not
an olefin but benzene, an aromatichydrocarbon. Figure 3.20 shows the mainindustrial organic chemicals and polymers
made from benzene. In the same way that anaddition reaction is the core reaction in
olefins, a substitution reaction plays the mostimportant role in benzene reactions. In Fig.
3.20, all the reactions of benzene excepthydrogenation to give cyclohexane aresubstitution reactions.
(1) Ethylbenzene, cumene and linear
alkylbenzene
The formation of ethylbenzene by thereaction with ethylene and benzene and theformation of styrene by dehydrogenation
have already been mentioned in the “Ethylene”
section (see Section 3.4.2 (3)).
The formation of cumene by the reaction
with propylene and benzene and theformation of phenol and acetone by oxidizing
cumene to a peroxide and then cleaving itwith an acid have already been mentioned in
the “Propylene” section (see Section 3.4.3(3)) Since phenol is an important industrialorganic chemical, it is described in anothersection.
Linear alkylbenzene is also made from
α-olefin and benzene. The hydrogen in thearomatic ring of linear alkylbenzene is
replaced by a sulfonic acid group using
sulfuric acid anhydride to give linear
Systematic Survey on Petrochemical Technology

49alkylbenzene sulfonate. Linear alkylbenzene
sulfonate is an important anionic surfactant,which is used in large quantities for synthetic
detergents.
(2) Phenol
As shown in Fig. 3.21, many industrialorganic chemicals and polymers are madefrom phenol.
Phenol undergoes addition condensation
with formaldehyde to give phenol resin (seeSection 6.1.3 (2)).
Bisphenol A is obtained from acetone andphenol by reaction similar to the reaction offormaldehyde and phenol. As bisphenol A is
an industrial organic chemical with 2 hydroxygroups (-OH) of phenol, it is widely used as amonomer. It is polymerized with phosgeneand epichlorohydrin to give polycarbonate

and epoxy resin, respectively. Polycarbonate
is a polymer with superior transparency,
impact resistance and flame resistance. It is
widely used in consumer electrical appliances,automobiles, building materials, etc. A
common example is its in the transparent
substrates of CDs and DVDs. The productionof polycarbonate has increased since the1990s and it has grown into a large-scale
product. Epoxy resin has already been
mentioned in the “Epichlorohydrin” section(see Section 3.4.3 (9)). Other small-scale
polymers such as polysulfone andpolyetherimide are obtained from bisphenol
A. Polysulfone is often used for filters in
artificial kidneys. Polyetherimide is a superengineering plastic in which improves themolding processability of polyimide.

Fig. 3.20 Major product categories from benzene.

50

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 3.21 Major product categories from phenol.
Similar to the reaction between benzene
and ethylene or propylene mentioned in thepreceding section, alkylphenol is obtained bya reaction between α-olefin and phenol.
Ethylene oxide is reacted with the hydroxygroup of alkylphenol to give polyoxyethylene
alkylphenyl ether. It is used as a nonionicsurfactant.
The hydrogen atoms at positions 2 and 6of phenol are replaced by methyl groups
using methanol to give 2,6-xyrenol. When
2,6-xyrenol
undergoesoxidative
polymerization (oxidative coupling) in thepresence of a copper catalyst, only the para
position (position 4) of phenol reacts, giving
polyphenylene ether in which aromatic ringsand oxygen are connected linearly. The
processability of polyphenylene ether is poor.
However, because it mixes well with
polystyrene to give a marked improvement inprocessability, it is usually used as a mixture
with such a polymer (called a polymer alloy).
Polyphenylene ether is also known as
modified polyphenylene ether (PPE).
Phenol is reacted with chlorine to replacesome of the hydrogen atoms in the aromaticring with chlorine groups to givechlorophenol. Chlorophenol is used as anintermediate for pesticides.
The
methodofmanufacturing
caprolactam by hydrogenation of phenol via
cyclohexanone is an old process. However, it
is often used even now and is an importantuse of phenol in the United States and Europe.

The method of manufacturing caprolactam byhydrogenation of benzene is described later inthe “Cyclohexane” section.
(3) Nitrobenzene and aniline
Benzene is treated with a mixture ofconcentrated nitric acid and concentrated
sulfuric acid to give nitrobenzene (Fig. 3.20).
Nitrobenzene is reduced with hydrogen to
give aniline. Aniline is an important organicintermediate for synthetic dyes, and is also
used in large quantities as a raw material for
MDI (4,4’-diphenylmethane diisocyanate) in
the petrochemical industry. Aniline is reactedwith formaldehyde in the presence of analkali to give 4,4’-diaminodiphenyl methane.
This reaction is similar to the reaction to
obtain bisphenol A from phenol and acetone,
mentioned previously. Hydrogen at the para
position of the aromatic ring is replaced by amethylene group derived from aldehyde, andanilineisconnected.
When
4,4’-diaminodiphenyl methane is reacted withphosgene, the amino group changes to an
isocyanate group to give MDI. MDI isreacted with polyether polyol to givepolyurethane.
(4) Chlorobenzene
Benzene is reacted with chlorine to givechlorobenzene, in which some of thehydrogen atoms in the aromatic ring are
replacedbychlorine(Fig.
3.20).
Monochlorobenzene
isreactedwith
Systematic Survey on Petrochemical Technology

51trichloroacetaldehyde
toproduceaninsecticide(didchlorodiphenyl-trichloroethane [DDT]).
DDT used to be a significant chemical interms of public health and agriculture,
although its production is now prohibited.
Monochlorobenzene is mainly used as asolvent, for instance, in the reaction of
4,4’-diaminodiphenyl methane and phosgene,
mentioned in the preceding section.
Paradichlorobenzene
is
used
for
insecticides and deodorants. It is polymerizedwith sodium sulfide to give polyphenylene
sulfide (PPS). Due to its outstanding heat
resistance and mechanical strength, PPS is
used as an engineering plastic.
(5) Cyclohexane,
adipicacid
andcaprolactam
The reaction in which the aromatic ringof benzene is destroyed by hydrogenation to
give cyclohexane is very unique, because
benzene usually undergoes substitution
reactions. Cyclohexane is also contained in
catalytic reformates and cracked gasoline.
However, due to the difficulty in separationand purification, it is exclusively produced by
the hydrogenation of benzene. It is used as asolvent, and also oxidized to give
cyclohexanone and cyclohexanol, andsubsequently adipic acid and caprolactam(see Section 6.1.2 (4)). Adipic acid is reactedwith hexamethylenediamine by condensation
polymerization
togive
6,6-nylon.
Caprolactam
undergoesring-opening
polymerization to give 6-nylon. Nylon(polyamide) is used for synthetic fibers andengineering plastics.
3.4.6

Products from the C7 and C8
fractions
Like main C6 basic petrochemicals, main
C7 and C8 basic petrochemicals are notolefins, but rather aromatic hydrocarbons,namely toluene and xylene. Ethylbenzene, a
C8 aromatic hydrocarbon, is also obtained
from cracked gasoline. However, because it isusually synthesized from ethylene andbenzene, it has already been described as an
ethylene product. Figure 3.22 shows the main
product categories made from toluene andxylene.

52(1) Industrial organic chemicals fromtolueneAs a solvent, toluene is often used forcoatings, adhesives, etc. TDI, shown in Fig.
3.22, is one of the main industrial organic
chemicals obtained from toluene. In the same
way that aniline is made from benzene,
toluene is initially nitrated with concentrated
nitric acid and concentrated sulfuric acid togive dinitrotoluene. This process is a
substitution reaction in which the hydrogen in
the aromatic ring is substituted by nitro
groups. The dinitrotoluene is then reducedwith hydrogen to give diaminotoluene, whichis then reacted with phosgene to give TDI.
TDI, as well as MDI, is a diisocyanatethat is produced in large quantities. TDI isreacted with polyether polyol to givepolyurethane. Polyurethane is mainly used in
the manufacture of flexible polyurethane
foam and is also used for polyurethane
coatings, polyurethane adhesives andpolyurethane rubber.
However, apart from TDI, there are nolarge-scale industrial organic chemicals
produced from toluene. Consequently, , thedemand for toluene in the petrochemicalindustry is small in proportion to the amountof toluene produced alongside benzene andxylenewhen
extracting
aromatichydrocarbons from cracked gasoline andcatalytic reformates, resulting in excessive
amounts of toluene being produced. At
petrochemical plants, this excessive toluene ismade into benzene and xylene by adisproportionation reaction.
(2) Industrial organic chemicals fromxyleneXylene has three types of isomer (ortho,metha and para). The main industrial organic
chemical produced from xylene is carboxylic
acid obtained by the oxidation of both methylgroups (see Section 6.1.2 (3) 1)). This
reaction is not a substitution reaction, as ischaracteristic of aromatic hydrocarbons, but
is similar to the reaction in which the methylgroup of propylene is oxidized to give acrylic
acid. However, because the mechanism ofreaction is quite different, these reactions are
only similar in style.

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Phthalic anhydride is made from o-xyleneby oxidation. Phthalic anhydride is reactedwith 2-ethylhexanol to give a plasticizer(DOP). The plasticizer is used together with
polyvinyl chloride to produce flexible
polyvinyl chloride products (films, hoses,
leather, wire coating, etc.). Phthalic anhydrideis also reacted with various alcohols such as
isodecyl alcohol and used as a raw material
for various phthalate ester-based plasticizers.

It is also reacted with polyhydric alcohol andmaleicanhydridebycondensation
polymerization to give unsaturated polyester
resin. As a glass fiber-reinforced plastic,
unsaturated polyester resin is used for the
manufacture of large molded articles such as
fishing boats, tanks and bathtubs. It has also
long been used as a raw material for alkyd
resin.

Fig. 3.22 Major product categories from toluene, xylene.
m-Xylene is oxidized to give isophthalicacid. Isophthalic acid is used for unsaturated
polyester resin. However, unlike phthalicanhydride, it is not used as a main monomer,
only for reforming. When isophthalic acidchanges into a highly reactive acid chloride,then reacted with m-phenylenediamine bycondensation polymerization, it gives
meta-aramid (wholly aromatic polyamide).
Since meta-aramid has outstanding heat
resistance and flame resistance, it is used forspace suits, firefighting uniforms, curtains,etc., albeit in small quantities.
p-Xylene is oxidized to give terephthalicacid. Terephthalic acid is reacted with EG bycondensation polymerization to give PET.
Polyester fiber has dominated nylon andacrylic fibers and is currently considered tobe the most important synthetic fiber. In theform of PET resin, terephthalic acid is used inlarge quantities for bottles, films, tapes, etc. It

is also reacted with 1,4-butanediol bycondensation polymerization to give PBT.
PBT is widely used as an engineering plastic.
Terephthalic acid is changed to acid chloride
and
is
then
reactedwithparaphenylenediaminebycondensation
polymerization to give para-aramid. As a verystrong fiber, para-aramid is used for tire cords,
bulletproof vests, safety globes, etc. As
mentioned above, terephthalic acid is alarge-scale industrial organic chemical having
a much greater demand than not onlyisophthalic acid but also phthalic anhydride.
Compared with o-xylene and p-xylene,
m-xylene has a much smaller demand.
Meanwhile, the isomer ratio of xylene
obtained from catalytic reformates andcracked gasoline is almost constant.
Therefore, surplus m-xylene has beenisomerized in the presence of an acid catalyst
to give a mixture of o-, m- and p-xylene andSystematic Survey on Petrochemical Technology

53then o- and p-xylene have been separated andpurified (see Section 6.1.1 (6)).
3.4.7

Products from the ten or more
fractions
Industrial organic chemicals from the ten
or more carbon atoms include many
important surfactants. The greatest use of
surfactants is synthetic detergents. To prevent
environmental contamination with foam,synthetic detergents must be promptly
degraded by microorganisms after discharge
into the environment. To achieve this, thecarbon chains must be straight. However,basic petrochemical products with more thanC10 that can be used as raw materials of
ssurfactants cannot be produced by steam
cracking of naphtha. As shown in Fig. 3.23,
there are three starting materials.
One of the three routes is the extractionof linear n-paraffin from kerosene as apetroleum fraction having more carbon atoms
than naphtha (Fig. 3.23 [1]). n-Olefin is
obtained by the thermal cracking of
n-paraffin. The molecule of n-olefin is astraight carbon chain with a double bond at
the end or inside. The second route is the
production of α-olefin from ethylene as astarting material (Fig. 3.23 [2]), as mentioned
in Section 3.4.2 (7). In the third route, fats
and oils are used as raw materials rather thanpetroleum or natural gas (Fig. 3.23 [3]). For
this reason, this route is considered to conflictwith the definition of petrochemistry.
Nevertheless, petrochemical techniques canbe applied to the manufacture for surfactantsfrom the raw materials of fats and oils. Fatsand oils are higher fatty acid triglycerides.
Triglycerides composing fats and oils aremostly C12 to C18 linear carboxylic acids.

Fig. 3.23 System of product from C10.
(1) Industrial organic chemicals from
olefins with ten or more carbon atoms
Linear alkylbenzene is obtained by areaction between the n-olefins (including
α-olefin) shown in Fig. 3.23 [1], [2] andbenzene. Sulfonic acid is then introduced into
the aromatic ring using sulfuric acidanhydride and neutralized with an alkali togive linear alkylbenzene sulfonate. Linear
alkylbenzene sulfonate is a linear anionicsurfactant (linear alkylbenzene sulfonate[LAS]) with outstanding cleaning properties.
It is used in large quantities for detergents.

54

When α-olefin is sulfonated by reaction
with sulfuric acid anhydride and thenhydrolyzed, the double bond shifts internallyduring the reaction. This results in α-olefin
sulfonic acid being obtained, although theposition of the double bond is different in thismixture. It is neutralized with an alkali togive α-olefin sulfonate. This is used as ananionic surfactant (α-Olefin sulfonate [AOS])
with outstanding biodegradability.
After the oligomerization of ethylene,
linear higher alcohols are obtained byoxidation and hydrolysis. Linear higher

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

alcohols having one more carbon atom thanthe original olefin can also be obtained by theoxo process of α-olefin. The uses of linear
higher alcohols are described in the next
section.
(2) Industrial organic chemicals from fats
and oils
Higher fatty acid (C12–C18) obtained by
the high-pressure hydrolysis of fats and oils
(Fig. 3.23 [3]) is neutralized with an alkali togive soap and metallic soap. Soap that is asodium salt of higher fatty acids has long
been produced as a detergent and also as ananionic surfactant. Calcium salt, magnesium
salt, barium salt, zinc salt, etc. of higher fatty
acids are termed as metallic soap. Metallic
soap is used for plastic stabilizers andlubricants/mold release agents.
Higher fatty acids react with ethyleneoxide to give a polyethylene glycol fatty acid
ester that is used for nonionic surfactants.
Higher fatty acids also react with ammonium
to give amide, which is then dehydrated togive fatty acid nitrile. Fatty acid nitrile isreduced to give primary to tertiary fatty
amine, which is then reacted with methyl
chloride to give a quaternary fatty acidammonium salt. This substance is used as a
cationic surfactant. Acrylonitrile is added toprimary fatty acid amine (cyanoethylation)and then the nitrile group is hydrolyzed andneutralized to give an alkylamino fatty acidsalt. Since this substance has both amino andcarboxy groups within the molecule and also
has a long-chain alkyl group, it is used as an
amphoteric surfactant.
Higher fatty acid of fats and oils are also
reduced by high-pressure hydrogene to give
fatty alcohol (linear higher alcohol). In fact,
to accelerate the reaction, fats and oils are

subjected to ester exchange with methanol togive a higher fatty acid methyl ester, which isthen hydrocracked. Higher alcohol isesterified with chlorosulfuric acid or
anhydrous sulfuric acid and then neutralizedwith an alkali to give a higher alcohol sulfuric
acid ester salt. This is an anionic surfactant(alkyl sulfuric acid ester salt [AS]) used as aneutral detergent with stable quality. Higher
alcohol is polymerized with ethylene oxide togive polyoxyethylene alkyl ether. This is anonionic surfactant (AE). It is further
changed into a sulfate ester salt to givepolyoxyethylene alkyl ether sulfate. This is ananionic surfactant polyoxyethylene alkyl
sulfate (AES). Higher alcohol is reacted withdimethylamine to give tertiary aliphatic
amine.
Bibliography[1] “An outline of the development of polyvinyl chloride technology in Japan,
including a description of historicalmaterials,” Survey Report on the
Systematization of Technologies, no. 1,
National Museum of Nature andScience, March 2001.
[2] “Systematic survey of technologicaldevelopment in laundry soaps anddetergents,” Survey report on thesystematization of technologies, no. 9,
National Museum of Nature andScience, March 2007.
[3] K. Weissermel, H. J. Arpe, “Industrialorganic
chemistry,”
Tokyo
Kagaku-dojin Publishing Company,
Inc., 5th edition, 2004.
[4] H. A. Wittcoff, B. G. Reuben, J. S.
Plotkin, “Industrial organic chemicals,”
Wiley, 3rd edition, New York, 2013.

Systematic Survey on Petrochemical Technology

55

4 Industrial organic chemicals and polymers
predating petrochemistry

Even before the establishment of thepetrochemical industry, there had been
fully-fledged industrial organic chemicalindustries and polymer industries based onwood, carbohydrates (fermentation), fats andoils and coal since the late 19th century. Of
course, industrial organic chemicals andpolymers were being produced before that,such as highly-concentrated ethanol fromalcohol distillation, vinegar (acetic acidaqueous solution) from acetic acidfermentation of alcohol, soap made by boilingfats and oils with alkalis, coatings fromunsaturated oils and lacquers and adhesives
from glue or starch paste. However, thesewere by no means modern chemic alindustries.
Accordingly,
thischapter
discusses the industrial organic chemical andpolymer industries that existed from the late
19th century onwards.
These industrial organic chemical andpolymer industries developed in significantly
different ways in various different regions,depending on the availability of raw materials
and the different product demands. These
industries were individually taking shape in
the forest of petrochemstry, as mentioned in
the previous chapter. As shall be mentioned
later, two forests sprang up from wood, andthree from coal. In terms of technology,
Germany, the United States and the United
Kingdom were the developed nations.
However, even Japan developed fully-fledged
industrial organic chemical and polymer
industries from the 1930s onwards, using
various different raw materials. This laid thefoundation for Japan’s quick uptake and rapid
development of petrochemical technology
from the late 1950s onwards.
Petrochemistry originated in the UnitedStates in the 1920s, and existed alongsideother pre-existing industrial organic chemicaland polymer industries in the United States
up until the 1940s. The forest of
petrochemistry stayed small for the first three
decades of its existence in its native habitat,
the United States. There were many other56

forests that thrived more than the forest of
petrochemistry. However, that forest grew
rapidly within a short space of time in the
1950s and the 1960s, in the United States, inEurope and also in Japan. It either absorbed
or overshadowed the pre-existing forests ofindustry that had developed alongside it.
Accordingly, many of the petrochemical
products discussed in the previous chapter
were developed in industries predating
petrochemistry. This chapter discusses therise and decline of these chemical industries
that predated petrochemistry, citing examples
from Japan.

4.1 Industrial organic chemicals andpolymers from wood
There are two broad forests of chemistry
using wood as a raw material, as shown in
Fig. 4.1. One is industrial organic chemicals
made from byproducts produced during woodcarbonization, practiced since before themodern chemical industry began. The other isthe use of cellulose, a natural polymer that is
the main component in wood.
Industrial organic chemical industries
using wood carbonization came to an end in
the 1930s due to the rise of the carbide andacetylene industries, as shall be mentioned
later. This took place at almost exactly thesame time in Japan, the United States andEurope. Prior to the Second World War, thecellulose industries in Japan started producing
a few chemical products that reachedworld-class production volumes (celluloid,
rayon). In the late 1950s, as the
petrochemistry became industrialized, thecellulose industry forest dwindled into
decline as it came under pressure from thepetrochemistry forest. However, some
cellulose products have still survived to thisday, namely fine chemical products andfunctional products.
4.1.1 The wood carbonization industry
When wood is carbonized to produce

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

charcoal, wood tar, pyroligneous acid andwood gas are produced as byproducts.
Pyroligneous acid produces acetate of lime
and crude methanol. Acetate of lime produces

acetic acid and its salts and esters, as well as
producing acetone if dry distilled. Crude
methanol produces refined methanol, which
in turn produces formalin.

Fig. 4.1 Major product categories of wood as raw material.
Wood carbonization has been carried out
since the 18th century in forest-resource-richcountries and regions such as Austria,
Hungary, Northern Europe and the UnitedStates, while Germany and the United
Kingdom developed acetic acid refining
industries, importing acetate of lime andusing it to produce acetic acid.
The wood carbonization industry in Japanbegan in 1893 with the establishment of awood carbonization plant in Tochigi by
Shōichirō Katō, the wealthy founder of Kato
Chemicals in Nikko. Later, the demand for
acetic acid for dyeing grew, and the woodcarbonization industry developed, with anincreasing
numberofsmall-scale
manufacturers affiliated to charcoal-making
facilities.
However,suchsmall-scale
production could not meet the increasing
demand for acetic acid. In 1902, Shōichirō
Katō established The Nippon Acetic Acid
Manufacturing Company (capital ¥100,000)
in Honjo, Tokyo. This took over Kato
Chemicals and relocated its facilities to begin
large-scale acetic acid production, using
mainly imported acetate of lime. This movewas endorsed by the major players in thebusiness world at the time, including Magoshi
Kyōhei, Shibusawa Eiichi, Ōkura Kihachirōand Ōkawa Heizaburō. In 1907, The Nippon
Acetic Acid Manufacturing Company
increased its capital to ¥300,000. The
company newly imported acetic acidmanufacturing equipment (steam-heated,diminished-pressure crude acetic acidmanufacturing equipment, acetic acidconcentrated distillation apparatus, acetic acidrectification equipment) from the German
company Mayer. A new plant was completed
in 1908, and production of glacial acetic acid(100% acetic acid) commenced. To be more
self-sufficient in raw materials, The Nippon
Acetic Acid Manufacturing Company
increased its capital to ¥600,000 andestablished a new plant in Shiobara, Tochigi,
importing a suite of transportable woodcarbonization equipment from Mayer for the
new plant. This ushered in a new era ofmodern wood carbonization plants, wellbeyond the reach of small-scale charcoal
byproduct processing. The wood wascarbonized in a transportable retort or furnace(wood processing capacity of 1,000 cubic
shaku or 27.83 m3) and pyroligneous acidwas produced by removing the wood tar fromthe volatile component. The pyroligneousacid was then neutralized with milk of lime ina neutralization tank. The neutralized solution
Systematic Survey on Petrochemical Technology

57was heated to evaporate the methanol, thendistilled to produce crude methanol. The
residual liquid from the evaporation wasconcentrated in a double-effect evaporator to
produce a concentrated lime acetate solution.
This was then dried in a cylindricaldehydrator. Annual production of 80%
acetate of lime was 900 tons; annual
production of 80% crude methanol was 250
tons; these products were then sent to the
Honjo plant in Tokyo for refining.
Later, a number of manufacturers started
entering the wood carbonization industry as
the First World War disrupted the import ofacetate of lime, and the market soared.
Incidentally, during the war, Germany
industrialized synthetic acetic acid made fromcarbide and acetylene, which was imported
by many countries, including Japan, after thewar. This was followed by a sudden increasein acetate of lime imports from the American
wood carbonization industry, sending a
succession of Japanese wood carbonization
manufacturers into bankruptcy or mergers. In
1925, four surviving companies, including
The Nippon Acetic Acid Manufacturing
Company, formed the Dai Nippon Acetic
Acid Manufacturers’ Association, and tried torestrict production in order to achieve market
stability. However, the appearance ofsynthetic acetic acid meant there was no
future for the wood carbonization industry,
and the association turned its attention todomestic production of synthetic acetic acid.
The course of events that followed is
discussed in the section on carbide andacetylene. With the domestic production ofsynthetic acetic acid, the wood carbonizationindustry rapidly declined, and completely
disappeared by 1939, as shown in Fig. 4.2.

Fig. 4.2 Switchover from acetic acid fromwood carbonization to synthetic acetic acid in58

the early 1930s.
4.1.2 Nitrocellulose
Another forest sourced from wood is thecellulose chemistry industry. Cellulose is anatural polymer and is the main component inwood and grasses. It has been used sinceancient times in the form of hemp fiber,
cotton and paper. However, cellulose does
not melt or soften when heated, and also does
not dissolve in solvent. Accordingly,
naturally-available, short-fibered cellulosematerials had to be utilized through physicalmanipulation
suchasspinningor
paper-making. Chemical manipulation ofcellulose began in the late 19th century, when
it was discovered that it could be partiallynitrated in concentrated nitric/sulfuric acidmixture to produce nitrocellulose, which
could be dissolved in solvent, and had someplastic properties when mixed with camphor.
(1) Celluloid
An early cellulose product was collodion(liquid bandages) made by dissolving
nitrocellulose in a mixture of ether andethanol. This was followed by celluloid,
made from nitrocellulose and camphor in the
United States in the 1870s. In modern terms,
camphor served as a plasticizer. Whilecelluloid was arguably also industrialized in
the United Kingdom in the 1850s, it was not
until after it was industrialized in the UnitedStates that it became properly widespread.
Celluloid was the first plastic. Initially usedin daily necessaries and toys, it was also put
to use in photographic film by Eastman
Kodak in 1889, revolutionizing thephotosensitive materials industry.
Japan started importing celluloid sheetsin the late 1870s, not long after it was firstinvented. By the mid-1880s, celluloid sheet
imports were in full swing; it was being
processed to produce faux coral beads, combs,
hairpins and collars. In the 1890s, a numberof celluloid product manufacturers, inventors,
and entrepreneurs started planning to produce
celluloid sheets domestically. Despite
repeated failures, including some explosion
incidents, small-scale production of celluloid
sheets was achieved. By the late 1900s,
Mitsui, Mitsubishi, Suzuki Shoten, Iwai

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Shoten and other large-capital enterprises had
started production of celluloid sheets;
Japanese celluloid sheet production rapidly
increased around the time of the First World
War. Eight of these celluloid manufacturers
combined to form Dainippon Celluloid (nowDaicel) in 1919.
After the First Sino-Japanese War, Japanannexed Taiwan and promoted camphor
production there. By the early 1900s, Taiwan
was leading the world in camphor supply.
This gave the Japanese celluloid industry acompetitive edge, and by 1937 Japan was
producing the highest quantity of celluloid in
the world (12,760 tons). This accounted for
45% of the world’s celluloid; Japan wasexporting 7,500 tons of celluloid sheets.
Figure 4.3 shows the trends in celluloid
production volumes in Japan. Celluloid
production peaked between 1937 and 1940.
By the late 1930s, nearly 70 companies were
producing phenol resin, which had been
domestically produced since 1915. Together,phenol resin and celluloid dominated theplastics market. As a thermoplastic, celluloid
had an advantage over thermosetting phenol
resin, making for a formidable rival in themarket.

Fig. 4.3 Change of production volume ofcelluloid.
Thecelluloid
industry
resumedproduction soon after the Second World War,
exporting toys and daily necessaries. By thelate 1950s, however, it started to come underpressure from polyvinyl chloride in the risingacetylene industry; once the petrochemicalindustry started domestic production with asuccession of new polymers (mostly
thermoplastics
suchaspolyethylene,
polystyrene, etc.), the sun began to set on

celluloid. With the successive emergence of
celluloid-substitute thermoplastics, the maindrawback with celluloid – its combustibility –was a major factor in its losing much of its
demand in the market for toys and daily
necessaries. After that, celluloid production in
Japan started to wane, stopping altogether in
1996.
(2) Lacquer
A butyl acetate solution of nitrocellulose
was also used in coatings. This was called
nitrocellulose lacquer. Quicker to dry thanexisting coatings made from unsaturated fats
and oils, nitrocellulose lacquer revolutionized
the automotive coating industry. One
well-known brand was Duco coating,produced by DuPont in 1923. Nitrocellulose
lacquer is still used for coating leather,
synthetic leather, wooden articles, furniture,etc., due to its luster, durability and quick
drying speed.
(3) Rayon fiber from soluble nitrocellulose
Ether and ethanol solutions of
nitrocellulose could also be made into fibers
by extruding them through a glass tube.
Frenchman Hilaire de Chardonnet started
industrial production of artificial fiber (rayon
fiber from soluble nitrocellulose) in 1892.
Because silk had been the only long-fiber
material available before that, this artificial
long-fiber material was known as artificial
silk. As nitrocellulose had the drawback ofbeing highly flammable, de Chardonnet
denitrated the fibers by soaking them insodium sulfide. Swiss German chemist
Matthias Schweizer had discovered in 1857
that cellulose dissolved in a cuprammonium
solution. Cuprammonium rayon fibers werealso produced by spinning this solution in asulfuric acid bath. By the start of the 20th
century, this fiber was proving to be fierce
competition for soluble nitrocellulose rayon
fiber in Europe. Soluble nitrocellulose rayon
was never industrialized in Japan.
4.1.3 Viscose
The cellulose-based industries weresignificantly transformed by the invention ofviscose. Once viscose rayon fiber wasindustrialized in 1904 by British company
Systematic Survey on Petrochemical Technology

59

Courtaulds, this method quickly dominatedrayon production in the 1910s, having lower
production costs and better product quality
than the soluble nitrocellulose method or the
cuprammonium method. The cellulose istreated with a sodium hydroxide solution, andthen has carbon disulfide added to dissolve it
into sodium cellulose xanthate, in turnproducing a viscous liquid (viscose). Whenspun in sulfuric acid, the cellulose regenerates,
producing viscose rayon fiber. The viscose
can also be extruded through a film-shaped
slit to form cellophane.
(1) Rayon fiber
Industrialization of rayon fiber in Japanbegan with the viscose method rather than thesoluble nitrocellulose method or the
cuprammonium method. Mitsubishi, Iwai
Shoten and Suzuki Shoten, mentioned in theprevious section, were involved in theindustry; Japan Celluloid Artificial Silk (nowDaicel) was established in 1908 and its
factory in Aboshi started operating in 1911.
However, contrary to what the name implies,
the company did not actually produce
artificial silk, but solely produced celluloid
sheets. Since there was fierce competition in
Europe between the soluble nitrocellulose
method, the cuprammonium method and theviscose method, European companies were
not readily exporting technology or
equipment, which meant that Japan Celluloid
Artificial Silk was unable to acquire orindustrialize any artificial silk technology.
Meanwhile, Itsuzō Hata of Yonezawa
Higher Technical School (now Yamagata
University Faculty of Engineering), with thesupport of Suzuki Shoten, independently
developed a viscose rayon method using
literature from Europe. This technology wasindustrialized, and the Imperial Artificial Silk
Company (now Teijin) was established in
Yonezawa in 1918. After the First World War,German companies started to actively supply
technology, and many Japanese companies
entered the viscose rayon industry using
introduced technology. Short-fiber rayon wasdeveloped in 1931, and the Japanese rayon
industry joined forces with the Japanesespinning industry, the strongest in the world
at the time. This enabled Japan to become the60

world’s leading rayon-producing country(245,000 tons), overtaking the United States,by 1938. This was also aided by the fact thatthe core of the American chemical fiberindustry had shifted from viscose rayon toacetate, as shall be discussed in the following
section.
Figure 4.4 shows the trends in production
volumes for rayon fiber (including
cuprammonium rayon, which started being
produced in small quantities in Japan from
1931), acetate fiber and synthetic fiber. The
prewar peak production volume of rayon
fiber was around 20 times higher than the
prewar peak production volume of celluloid.
This figure shows how much smaller in scale
the plastics market was before the Second
World War. Chemical utilization of polymer
materials started with fibers rather than withplastics.

Fig. 4.4 Change of production volume ofrayon fiber, acetate fber and synthetic fiber.
Rayon fiber revived relatively quickly
after the Second World War, topping its
prewar peak in the late 1950s, as shown in
Fig. 4.4, and reaching 1.8 times its prewar
peak in 1957. Right at this time, full-scale
production of vinylon, nylon and othersynthetic fibers began. However, unlike
celluloid, rayon fiber did not cede defeat tosynthetic fiber, and did not fall into rapid
decline. Although its growth later markedly
slowed, production reached a record peak in
1967 (479,000 tons). This is thought to bebecause although rayon was not as strong as
synthetic fiber, it was still more absorbent
and also did not have any fatal flaws, such as
celluloid’s flammability. However, ongoing
improvements were made to synthetic fibers,
mainly polyester, and rayon production
volumes decreased from the 1970s onwards,
as shown in Fig. 4.5.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 4.5 Change of production volume ofrayon fiber after the production peak and its
being surpassed by acetate fiber.
The overall Japanese textile industry(synthetic fiber, spinning, fabric, knitting,dyeing, sewing) decreased in scale, and ispresently estimated to have a production
volume of only several tens of thousands oftons. By the 2000s, rayon no longer appearedin the statistics on its own, due to decreases incompany numbers. Rayon is currently
estimated to account for only several percentof the overall chemical fiber production
volume, consisting of rayon fiber, acetate
fiber and synthetic fiber combined.
(2) Cellophane
Cellophane was invented in 1908 by
Swiss chemist Jacques Brandenberger. It wasindustrialized in 1912 by French company La
Cellophane. It was industrialized in the
United States in 1914 by DuPont. DuPont
developed
nitrocellulose-coated,moisture-proof cellophane in 1927, anddemand grew significantly.
The Japanese cellophane industry started
later than the rayon industry, with Kōshinsha
starting production 1926. Like rayon, postwar
production reached a peak around 1937, withan article in the Manchuria Daily News (July21, 1938) estimating a production volume ofaround 6,000 tons. Cellophane production
rapidly recovered after the war, topping its
prewar peak in the early 1950s. Meanwhile,
LDPE imports began in 1951, and production
began the same year on highly productive
inflation film. This cheap polyethylene film
was thought to be a strong competitor againstcellophane. With domestic production of
LDPE starting in 1958, cellophane was
expected to go into decline. However, acellophane/polyethylene
film
laminate
product (called Polycello) had been achievedin 1954, and by leveraging the respective
strengths of both products (the flexibility andtransparency of cellophane combined with the
moisture
resistanceandheat
sealing-properties of polyethylene), the twowere able to develop alongside each other,mainly for packaging food products. This wasan unexpected development. While it isdifficult to estimate the weight of cellophane
due to its being a film, cellophane industry
statistics estimate that production increased
by 23 times in 20 years from 1950 to 1970,
reaching a volume of 100,000 tons.
However, domestic production of
bi-axially oriented polypropylene (OPP) film
began in 1963. OPP film could compete headon with cellophane film in terms of its
transparency and flexibility. While OPP film
initially made little headway due to its lack ofheat sealing properties and other factors
inhibiting its compatibility with packaging
machines, by laminating it with castpolypropylene (CPP) or polyethylene film
and with the improved heat sealing properties,
the market for it rapidly grew from the late1960s onwards. As a result, cellophane
production volumes peaked in the late 1960s
and rapidly declined in the 1970s. In 1974,
OPP film production overtook cellophane,
and the gap increasingly widened from thenon. In 1980, cellophane production had
dropped to around 50,000 tons, less than halfthat of OPP film. Although cellophane
production has continued to decline, there arestill applications for it, and it is still being
produced. More recently, cellophane has
gained some attention for its biodegradability.
4.1.4 Acetate
Acetate, which is produced by reacting
cellulose with acetic anhydride, wasdeveloped during the First World War as anaircraft coating resin. British company
Celanese started industrial production of
acetate fiber in 1924 by dissolving acetate inacetone and using a dry spinning method.
French company Rhône-Poulenc developed
similartechnology
andestablishedRhodiaceta in 1922 to start industrial
production of acetate fiber. Acetate also
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61began to be used for cinematographic film inparticular, and was not as flammable as
nitrocellulose. Acetate fiber could not easily
be dyed with normal cotton dyes, and so
special synthetic dyes were developed for it.
These disperse dyes were also later used fordyeing synthetic fibers. The production andutilization of acetate fiber necessitated thedevelopment of industrial organic chemicalindustries such as acetic anhydride andacetone, and also required far more advanced
technology than viscose rayon, such as
monoacetylation control technology, dry
spinning, solvent recovery and dyeing withdisperse dyes. Many of these technologies
carried over into synthetic fibers.
(1) Acetate fiber
Since Japan had not significantly
developed industrial organic chemicals prior
to the Second World War, a number ofcompanies prototyped acetate fiber in the
1930s and took it no further. Full-scaleindustrialization came in 1949. However, as
this overlapped with the period of full-scaleindustrialization of synthetic fiber, acetate
fiber was completely overshadowed by thedevelopment of synthetic fiber in Japan, andremained dormant, as shown in Fig. 4.4.
However, in the 1960s, acetate fiber was
adopted as a raw material for cigarette filters,
which were in widespread use in Japan. The
demand for cigarette filters expanded in both
the domestic market and the export market,
and this industry, rather than clothing,remains the main use for acetate fiber. Unlike
celluloid or rayon, acetate fiber has its own
area of use that is not in competition with any
petrochemical products, and its production
volumes have continued to grow steadily. By
the late 1990s, more than 100,000 tons werebeing produced; by the 2000s, production had
even overtaken rayon fiber, as shown in Fig.
4.5.
(2) Acetate film
Another use for acetate other than fiber isphotographic film. To ensure the fireproof
properties of photographic film, there was aworldwide trend away from nitrocellulose
film to acetate film. In 1948, Eastman Kodak
successfully industrialized a fireproof

62

triacetate film. Domestic production of
triacetate film in Japan started in 1953. As
early as the 1960s, a petrochemical productmade an entry into this field in the form of
PET film. However, PET film only went as
far as X ray films, with triacetate film
continuing to be used for ordinary
photographic film. With the popularization ofdigital cameras from the late 1990s,
production of ordinary photographic roll film
rapidly declined in the 2000s, and the demand
for triacetate photographic film decreased.
However, from the 1990s onwards, triacetate
film began to gain attention as a polarizing
film for liquid crystal displays. Acetate film
has thus survived as a new functional
product.
4.1.5

Fine chemical products from
cellulose
As cellulose polymers interact strongly
through their hydroxyl groups, cellulose does
not break down in water or organic solvents.
If part of the hydroxyl group is esterized or
etherized, the interaction between thepolymers weakens, and they can break downin water or organic solvent. Various
derivatives have been produced and used asfine chemicals. There are two main productsof this type in particular, as follows.
Sodium carboxymethyl cellulose (CMC)
is a polymer made by reacting cellulose
treated with sodium hydroxide withmonochloroacetic acid so the hydroxyl
groups in the cellulose form carboxymethyl
ether. The etherization makes the cellulose
water soluble. CMC solutions are viscous,and form protective colloids. Once applied asa coating and dried, this forms a transparent
film that has an adhesive effect. The solution
is physiologically harmless, and is approved
as a food additive both in Japan and overseas.
Due to these characteristics, CMC has a wide
range of uses, including as a dispersion
stabilizer for food, a binder for
pharmaceutical tablets, a wettable powder forpesticides and a surface sizing agent andinternal strengthening agent for papermaking.
Methylcellulose is produced by reacting
methyl chloride with cellulose treated withsodium hydroxide so some of the hydroxyl
groups in the cellulose form methyl ether.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Unlike CMC, it is a nonionic cellulose ether.
Since it is water-soluble and forms a viscous
solution, its uses include an emulsion
stabilizer and thickener in food and cosmetics,
a protective colloid agent for thermal paper
and a binder for pharmaceutical tablets.

4.2 Industrial organic chemicals andpolymers from fermentation-basedindustrialorganic
chemicalproducts
Industrial organic chemicals produced byfermentation process of carbohydrates
includefermentation
ethanolandfermentation acetone/butanol, as shown in
Fig. 4.6. Production of ethanol and butanol asgasoline-substitute
fuels
and
octaneenhancers increased in many countries by
national policy from the 1920s to the 1940s.
As this resulted in an abundant supply, anumber of chemical industries emerged using
these as raw materials.
However, in the 1950s, as crude oil from
the Middle East started being supplied inabundance to the rest of the world, thedemand for fermentation ethanol as a fuelsource decreased, and the fermentation-basedindustrial organic chemical industry lost its
industrial base. Fermentation-based industrialorganic chemicals and their derivatives were

almostcompletely
absorbed
into
petrochemical industry in the 1950s and the1960s. Incidentally, the fermentation ethanolindustry revived again in Brazil in the 1970s
as a result of the oil crises, and once again
experienced a sudden revival and subsequentdevelopment in the United States in the 2000s
as an environmental countermeasure.
4.2.1 Fermentation ethanol
There have been industries for obtaining
spirits with high ethanol concentrations by
distilling fermented alcohol since before themodern era. However, many of theseindustries could not really be called chemicalindustries, as they used batch methods. The
development of continuous distillation
process turned fermentation ethanol into anindustrial organic chemical industry.
(1) The start of ethanol fermentation inJapan
The military munitions factory imported
Ilges-method distillation apparatus from
Germany to produce solvents for making
gunpowder, and was able to start production
around 1902. This was the first introductionof continuous ethanol distillation apparatus toJapan.

Fig. 4.6 Product categories of industrial organic chemicals as raw material produced byfermentation process.
Ilges-method distillation apparatus wasmade up of two distillation columns. The
Systematic Survey on Petrochemical Technology

63mash distillation column was made up of abaffle tray overlaid with a plate shaped like agabled roof over the top of a parallel
arrangement of slit holes. This was designed
to prevent blockages, since the fermented
mash had a lot of solid content. However, thisequipment had poor distillation efficiency, as
a lot of liquid would flow down through theslits. The crude ethanol obtained from the
mash distillation column was refined in therectifying column, comprising a regular
bubble cap tray. The ethanol concentration
after refining was around 92%.
Prompted by this introduction by the
military munitions factory, Nihon Shusei
Seizo also imported Ilges-method distillation
apparatus and set up a factory in Asahikawa
in 1902. The company had aimed to produce
fermentation ethanol from potatoes, but it wasdisestablished the following year. However,similar attempts were made by Nippon Sugar
Refining Company and other companies. By
1919, Guillaume-method apparatus, with aninclined mash distillation column, was also
being imported; by 1920, there were 44 plants
with Ilges-method distillation apparatus and24 with Guillaume-method apparatus.
Alcohol tax was a major obstacle to using
ethanol for non-liquor purposes. Accordingly,
the government enacted the Industrial
Alcohol Tax Rebate Law in 1906, not longafter the introduction of Ilges-method
distillation apparatus. This meant that thealcohol tax could be exempted for designatedapplications for the alcohol. For the first time,ethanol was recognized as a chemical
substance that was distinct from liquor. The
first 12 tax-exempt applications were
designated in 1906: gunpowder (government
and private sector), tobacco fermentation(government), varnish (private sector, also thefollowing), ether, soap, tannic acid, borneol,vinegar, celluloid and its processing, perfume
for export and steam engine fuel. These weresuccessively added to until 1935. Thesedesignated applications provide a lot of detailon the uses of ethanol at that time; these arebroadly categorized in Table 4.1. The mostcommon applications were for solvents as
product components, such as in perfume or
collodion, for processing solvents, such as
celluloid processing, or other solvents, such64

as extraction or precipitation solvents for
digitalis extraction or diastase precipitation.
Ethanol has long been used as a raw
material for industrial organic chemicals,such as for vinegar and diethyl ether. Vinegar
accounted for around 20% of all ethanol
usage, while ether accounted for around 10%,although consumption levels plateaued.
Incidentally, from around 1933, there was anincreasing growth in demand for ethanol as araw material for ethers and other chemicalcompounds such as ethyl acetate, and theusage of ethanol for non-vinegar industrialorganic chemicals rose to account for aquarter of all ethanol usage. Behind this, there
are thought to be factors such as the domestic
production of photographic film, and changes
in varnish, lacquer and other coatingproducts.
Table 4.1 Major use of ethanol specified in
the industrial alcohol tax rebate law (1906 to
1935)(2) Petroleum-alternative fuelWith the First World War underlining theimportance of petroleum, there began to be a
growing interest in Europe in anhydrous
alcohol as a fuel alternative to petroleum. In
the 1930s, Germany, France, Italy andvarious other European countries enacted
compulsory alcohol blending policies. Since
ethanol forms an azeotrope with water at aconcentration of 96%, the azeotrope (hydrous
alcohol) obtained by ordinary distillation
could be easily isolated even if the ethanol
was mixed with gasoline. If it was made into
anhydrous alcohol, it could be mixed at ratios
of up to 20%. The anhydrous alcohol was
produced by reacting the azeotrope withquicklime. Azeotropic distillation wasdeveloped around 1930, and anhydrous
alcohol became more easily obtainable.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Azeotropic distillation was developed inGermany using the Drawinol process, whichuses trichlorethylene, and in France using the
Guinot process, which uses benzene or
benzine.
Distillation
technology
forfermentation ethanol had a significant impact
on the development of cryogenic distillation
technology by Linde, as mentioned in Section
2.3.2;
thisbecameafundamental
petrochemical
technology.
Similarly,
azeotropic distillation technology to produce
anhydrous alcohol also became an
indispensable petrochemical technology.
In Japan, Ryūkichi Takahashi also
developed an anhydrous alcohol azeotropic
distillation process using trichlorethylene.
Takahashi operated Takahashi Ironworks in
Osaka, manufacturing boilers and chemicalmachinery. The Takahashi Ironworks mash
distillation column comprised a bubble cap
tray designed to prevent mash blockages. In
1934, Teikoku Seishu in Nagareyama, Chiba,
started producing anhydrous alcohol (300 kL
per year) using Takahashi Ironworks
equipment. The following year, Showa Shuzoin Kawasaki started large-scale production(around 1,200 kL in 1935; around 4,500 kL in
1936; around 13,500 kL in 1937), also using
Takahashi Ironworks equipment. Bothcompanies were manufacturing synthetic sakefrom anhydrous alcohol. Showa Shuzo was asynthetic sake company founded by Chūji
Suzuki for processing waste liquid frommonosodium glutamate production. Synthetic
sake was invented by Umetarō Suzuki of
RIKEN in 1922, and was widely popularized
by Showa Shuzo under the “Sanraku” brand.
In 1939, Showa Shuzo established a newplant in Yatsushiro, Kumamoto, that wascapable of an annual production of 18,000
kL.
The Japanese government enacted the
Alcohol Monopoly Law and the Volatile Oil
and Alcohol Blending Law in 1937, a little
later than similar movements in Europe.
These aimed to rapidly increase ethanol
production for use as a fuel alternative topetroleum. Another aim was to rescue theflagging rural economy by increasing the
production of tubers as raw materials for theethanol. Under the Alcohol Monopoly Law,
the production, import and sale of ethanol

with a concentration of 90% or higher were
all deemed to be state business, and state-run
alcohol factories were established one after
another from Hokkaido to Kyushu, using
potatoes and sweet potatoes as raw materials.
Thirteen factories were set up and running
between 1938 and 1942. Most factories had
an annual production capacity of 3,600 kL,
while some had twice that at 7,200 kL. Whilethese factories were a little larger in scalethan many of the ethanol factories previously
operated by private sake brewing companies,
this was a far smaller scale than Showa Shuzo.
Rather than the conventional fermentation
technology of using malt to convert starch
into sugar, which is then fermented using
yeast, the state-run alcohol factories usedamylo fungus for sugar conversion, then yeast
for fermentation. The distillation apparatus
was mainly Takahashi Ironworks equipment,
the same as had been used by Showa Shuzoand other private companies. As a result of
the enactment of the Alcohol Monopoly Law,
the ethanol factories owned by private sakebrewing companies were put understate-consigned production with the products
supplied to the state; accordingly, freedom of
operation became increasingly impossible.
The enacting of the Alcohol Monopoly
Law and the Volatile Oil and Alcohol
Blending Law significantly altered thedemand volume for ethanol and the spectrumof its uses from 1937, as shown in Fig. 4.7.
Rapid growth was seen in the use of ethanol
for gasoline mixtures and for munitions. In
1935, the demand for fuel was less than 1,000
kL; this had risen to 19,000 kL by 1938 andto 66,000 kL by 1940. The breakdown ofdemand from 1941 to 1945 is unknown due
to the controls in place at that time.
As the construction of state-run factories
could not keep up with the growth in demand,a lot was being imported from Taiwan.
Fermentation ethanol production in Taiwan
also rapidly developed as a result of Japanese
government directives and technical guidance.
Since sugarcane was being used as a raw
material for fermentation in Taiwan,
production was more efficient, as it did not
require the sugar conversion step in theprocess, required when tubers were used as araw material. However, as wartime conditions
Systematic Survey on Petrochemical Technology

65intensified,marinetransport
becameproblematic; the volume of imports dropped
rapidly from 1944 onwards. This wascompensated for by increasing production atstate-run factories and increasing the volume
of production consignments to private sakecompanies.

Fig. 4.7 Change of demand for usage of
ethanol in the early Showa period.
(3) Thedevelopmentofchemicalindustries from fermentation ethanol
Figure 4.7 shows another area of growing
demand for ethanol other than gasoline
mixtures and munitions, namely, the demandfor ethanol for chemical industries. It has
already been mentioned that this demand
started growing from around 1933. As anample supply of fermentation ethanol became
available from 1937 onwards, there was anincrease in ethylene-based industrial organic
chemicals that used it as a raw material. The
demand for ethanol for chemical industries
grew from 16,000 kL in 1935 to 35,000 kL in
1939. Ethylene was produced by dehydrating
ethanol, as indicated in the product categories
shown in Fig. 4.6. Ethylene can also be
produced by partial hydrogenation ofacetylene; however, this method also
produces ethane, making the ethylene
difficult to refine. Producing ethylene bydehydrating ethanol required a fixed-bed,vapor-phase, continuous reactor using a solidacid catalyst such as acid clay. Since ethylene
and its halogen derivatives had already been
designated under the Industrial Alcohol Tax
Rebate Law in 1928, there is proof that
ethylene was being produced in Japan fromaround this time.
Ethylene chlorohydrin, EG (a raw
material for antifreeze) and ethylene

66

dibromide (a scavenging agent for octane
enhancers) were produced from ethylene.
Tetraethyl lead (an octane enhancer) was also
being produced on a large scale from ethanol
via ethyl chloride. Ethylene chlorohydrin was
also reacted with hydrogen cyanide to
produce acrylonitrile, a raw material for
oil-resistant synthetic rubber NBR. Antifreeze
was used on the northern war front, andoctane enhancers were indispensable inaviation fuel. Octane enhancers were used bymixing with scavenging agents, but up until
just before the Second World War, these were
all imported from the United States Ethyl
Corporation. These industrial organic
chemicals were all produced with domestic
technology developed in absolute secrecy.
The system of products made fromethanol via ethylene, shown in Fig. 4.6, arefar more highly specific than the system of
petrochemicals discussed in the previous
chapter, or the system of acetylene and coaltar products that shall be discussed later. The
industrial organic chemical ethanol is used to
produce the basic chemical product ethylene,
which in turn can be used to produce new
product categories. Calculating by theoreticalproduct output level, since the product output
level at the time is unknown, equivalentethylene production estimated from theproduction volumes of EG and other ethylene
products would have been 600–700 tons
between 1940 and 1944. Ethylene andethylene products were far smaller in scalethan the equivalent ethylene production
volume of 8,000–10,000 tons calculated fromcarbide/acetylene products (overwhelmingly,
synthetic acetic acid), discussed later.
However, assuming that all fermentation
ethanol was made from ethylene, given thespecificity of fermentation ethanol products,
the equivalent ethylene production volume
would have peaked at 60,000–70,000 tons in
1942, around 20,000 tons of which would
have been used by chemical industries otherthan fuel or vinegar. Thus, the fermentation
ethanol industry was a more significant
chemical industry in the early 1940s than the
carbide/acetylene industries.
(4) The decline and revival of thefermentation ethanol industry after the

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Second World War
In Europe and Japan alike, the greatest
demand for the chemical industries based on
fermentation ethanol from the 1930s to theearly 1940s was munitions. Consequently,
once the war was over, there was no revivalof the chemical industries based on
fermentation ethanol. As the demand forgasoline substitute fuels also faded, for a longtime fermentation ethanol production
remained dormant.
The late 1960s saw the start ofpetrochemical ethanol (synthetic alcohol)
production from ethylene in Japan. Within ashort space of time, this had overtaken thefermentation process, supplying the demand
for solvents, chemical raw materials, etc.
However, the rising cost of petrochemistry
resulting from the two oil crises, and the rapid
increase in applications for food preservatives(food additives) [Footnote 1], which weremonopolized by fermentation ethanol,
sparked a revival of fermentation ethanol in
the 1980s, turning the tables on the
petrochemical method once more. Survival
had been achieved by opening up areas ofdemand in which there was no competition
from petrochemistry. Refining technology
was licensed from French company Melle inthe 1950s using the Allospas distillation
process. This method involved adding waterto already highly-concentrated ethanol anddistilling it again. Adding water increased therelative volatilities of the ethanol and any
impurities, thus making it easier to remove
the impurities. This is called extractive
distillation using water. Such technologicalimprovements significantly lowered theamount of impurities (methanol, fusel oil,aldehydes) in the ethanol, meaning thegrowing demand in food product industries
could be met by fermentation ethanol.
Mostsignificantly,
renewedcost
competitiveness by dramatically altering thefermentation ethanol business also made amajor contribution to the revival offermentation ethanol in Japan. The industry
started importing crude alcohol fermented
and distilled overseas as a raw material,
leaving only the refining to be done in Japan.
[Footnote 1] All around the world, fermentation ethanol rather thanpetrochemical ethanol is used in vinegar, food preservatives, andother areas in which it may be absorbed into the human body.

As a result, there was a marked decrease indomestic fermentation.
Against this backdrop, the circumstances
surrounding the fermentation ethanol industry
worldwide completely changed after the oilcrises, and a stable supply of crude alcohol
became available. Brazil is the largest
supplier of crude alcohol. In an attempt to rid
itself of petroleum imports, Brazil started
large-scale production of fermentation
ethanolfromsugarcaneasapetroleum-alternative fuel right after the oilcrises.
The United States started making
extensive policies on alcohol additives togasoline in the 2000s. This was acountermeasure for automobile emissions anda means of raising octane values. As Fig. 4.8
shows, these policies saw a rapid increase in
the production of fermentation ethanol frommaize in the United States within one shortdecade.
Recentfermentation
ethanol
production volumes in the United States are
more than six times higher thanpetrochemical ethanol production in the early
1980s. Production volumes in the 2010s havereached around three times those of Brazil.

Fig. 4.8 Change of production volume ofethanol in the U.S.
Judging from equivalent ethylene (theamount of ethylene required calculated on theassumption that it was petrochemicallysynthesized from ethylene), production of
fermentation ethanol in 2010 reached 25
million tons in the United States. An
equivalent volume of ethylene was producedin the United States in 2012. From the 2000s,
fermentation ethanol has made a rapid
comeback for around a decade due toenvironmental policies.

Systematic Survey on Petrochemical Technology

674.2.2

Industrialization of polyethylene
and polystyrene from fermentation
ethanol
It has been noted in the history ofJapanese petrochemical technology thatLDPE and polystyrene made fromfermentation ethanol started being produced
domestically in Japan in 1944, towards theend of the Second World War, as there was aneed for high-frequency insulating materials
for radars. This is discussed in greater detailbelow.
It has now almost been forgotten thatLDPE and polystyrene made fromfermentation-ethanol-based ethylene wasproduced in Japan using Japanese technology.
The military had a pressing need for these
two new plastics at the time. However, thiswas a very small-scale demand, as theintended application was for insulating
components for radars. Accordingly, althoughthese plastics were industrialized, it was on a
far smaller scalethanthe early
industrialization in the petrochemical industry
after the war. Since the industrialization took
place towards the end of the war, there wereconcerns about a shortage of resources andraw materials. Ultimately, air raid damage
meant the fledgling industry had to cede
defeat after a short period of operation.
Almost none of this technology was passed
on, as the postwar industrialization was basedon introduced technology. Nevertheless, thisearly industrialization using domestic
technology indicates the heights reached by
Japanese organic synthesis technology andpolymer synthesis technology during theSecond World War.
(1) Polyethylene
LDPE was invented in 1933 by British
company ICI and industrialized in 1939,
using fermentation ethanol as a raw material.
Around 100 tons were produced in 1940, andits superior properties as a high-frequency
insulating material were recognized. The
Second World War had already begun; ICI
supplied the technology to Americancompany DuPont at the request of the UnitedStates Navy. In 1943, a plant with a 900 tons
annual production capacity was built in the
United States.

68

Meanwhile,
Japan
first
becameacquainted with LDPE in 1942 in the form ofa radar cable captured from the American
military. Domestic production of it became apressing issue in Japan. Research began in thefall of 1943 by three groups commissioned by
the navy through the ElectrotechnicalLaboratory. These were led by Prof. Yukichi
Go of Osaka University and Mitsui
Chemicals, Dr. Taizō Kume of the Noguchi
Institute and Nippon Chisso Hiryō and Prof.
Kodama Shinjirō of Kyoto University and
Sumitomo Chemical.
The
Noguchi
Institute
startedexperimenting in early 1944, with little
literature to rely on, and, with astounding
speed,
hadalready
establishedamanufacturing method using ethyleneliquefaction and filling by summer that same
year. In the summer of 1944, Nippon Chisso
Hiryō (now Chisso) started construction on aplant at its factory in Minamata. Fit-out of theplant was completed by the end of December
with a 1,000 atm compressor supplied by thenavy fuel factory. Operation started
successfully in early 1945, and by March the
Noguchi Institute researchers were no longer
needed. However, everything was completely
destroyed in an air raid in May 1945.
Following the Second World War, thisdomestic technology was completely buried.
In November 1944, Mitsui Chemicals
started construction on a facility with a 20 kg
monthly production capacity, but this ended
without reaching production stage. In January
1944, Kyoto University started research witha 40 cc reactor, but this came to an end in
March with only a small amount ofspecimens obtained. However, researchbegan again after the Second World War,with Kyoto University taking on acommission from the Nippon Telegraph andTelephone Public. The university conducted acontinuous industrialization experiment from1951 to 1953 with a daily output of 10 kg,
using fermentation ethanol as a raw material.
Based on this research, Sumitomo Chemical
used an industrialization testing subsidy from
the Ministry of International Trade andIndustry to build and operate an intermediate
testing plant with a 3-ton monthly output
capacity at its factory in Niihama in 1953.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

This record of achievement made Sumitomo
Chemical the company of choice when ICI
was looking for a technology licensing
partner in Japan.
(2) Polystyrene
A major challenge with polystyrene wascoming up with a manufacturing method to
produce the monomer styrene. German
company IG Farben had started industrial
production of styrene in the early 1930s using
a method of dehydrogenating ethylbenzene
withanalumina-chromia
catalyst.
Ethylbenzene was synthesized from ethylene
and benzene using an aluminum chloride
catalyst. This was a reaction often used in theoil refinery industry. However, theethylbenzene dehydrogenation reaction had alow yield and produced tar as a byproduct.
Accordingly, various alternative methods
were developed.
During the Second World War, Japan
industrialized styrene with three production
methods using different raw materials, as
shown in Fig. 4.9. These were the Hodogaya
Chemical method, from ethanol via ethylene,
ethylbenzene and 2-chloroethylbenzene; theNihon Yuki method, from acetylene via
acetophenone and α-phenyl ethyl alcohol(methyl phenyl carbinol); and the Shiono
Kōryō method, by dehydrating rose perfume
β-phenyl ethyl alcohol.

Fig. 4.9 Production method of styrene industrialized in Japan during the Second World War.
Hodogaya Chemical started research in
1938, with a request from the military toindustrialize polystyrene. It came up with thealternative method of reacting chlorine with
ethylbenzene
toproduce2-chloroethylbenzene,
which
was
dehydrochlorinated to form a styrene
monomer. This method was deemed to have ahigher yield than the IG Farben method.
However, the polymerized polystyrene wasbrittle with a low molecular weight, andcould not be made into a product. This wasfound to be caused by a secondary
dehydrogenation
reactioninthedehydrochlorination
reactionprocess,
producing traces of phenyl acetylene. This
impurity was preventing the radical
polymerization of the styrene. However, it

was difficult to remove these trace amountsof impurities by distillation. Instead, theresearchers at Hodogaya Chemical removed
the acetylene-based impurities by exposing
the styrene to an aqueous solution of copper,andthensuccessfully
synthesizedhigh-molecular-weight,
low-dielectric-loss
polystyrene. Care had to be taken with thegeneration of copper (I) acetylide, as there isa risk of explosion when handlingacetylene-based compounds. This was asuperb piece of refining technology, using
this to the opposite effect. This indicates thelevel of analysis technology and organic
synthesis technology Japanese chemicalcompanies had at the time. A year ofindustrialization experimentation took placefrom the fall of 1941; by the fall of 1942,
Systematic Survey on Petrochemical Technology

69

production technology had been completed to
Chaim Weizmann of the University of
produce polystyrene from ethanol via
Manchester (later the first president of Israel)
isolated a potent strain of bacteria in 1912,
ethylene. However, there was a shortage ofresources and the construction of plants took
and patented an acetone/butanol production
method using this strain in 1915. This
longer than anticipated; a plant with a 5-ton
fermentation process was industrialized in themonthly production capacity was finally
United Kingdom and Canada during the First
completed in August 1944 in Komatsugawa,World War, as acetone was needed forTokyo. The factory started out operating well,making gunpowder. In 1920, DuPont
but was damaged by a fire in January 1945
invented nitrocellulose coating, which used
and an air raid in March, and was never able
butyl acetate as a solvent; this resulted in
to reopen.
large-scale acetone/butanol fermentation in
Nihon Yuki, a joint venture between Kao
the United States as well. In 1931, Koei (nowSekken Nagase Shokai and Tekkosha, wasKoei Chemical Company) started industrial
established in 1940 with polystyrene
production in Japan as well. Sucrose wasproduction as one of its aims. The Tekkosha
used as the raw material.
factory at Sakata produced acetic acid, andsubsequently acetyl chloride, from acetylene
In 1936, three companies (Godo Shusei,
via acetaldehyde. The acetyl chloride was
Takara Shuzo and Dai Nippon Shurui Seizo)
reactedwithbenzenetoproducejointly established a research institute, andacetophenone, which was transported to thestarted researching isooctane aviation fuelfrom butanol [Footnote 2]. This led to the
Nihon Yuki factory at Hirai, Tokyo. The
acetophenone was then high-pressureestablishment of Kyowa Hakko Kogyo afterhydrogenated to produce α-phenyl ethyl
the war. The research gained the attention andalcohol. The high-pressure hydrogenation
support of the Imperial Japanese Army Air
Service. At the end of 1940, an isooctane
technology had been mastered by Kao
Sekken for producing higher alcohols fromsample was presented to the army, and thefats and oils. The α-phneyl ethyl alcohol was
Air Service headquarters urged industrial
then dehydrated to produce styrene, which
production. As a result, a pilot plant was built
was then made into polystyrene. Operations
at the Godo Shusei factory in Asahikawa,
started in 1944, producing 12 tons by 1945.
which had already been working on
However, the plant was hit by an air raid in
acetone/butanol
fermentation.
UnlikeMarch 1945, and was unable to reopen.
fermentation
ethanol,fermentation
Shiono Kōryō is a perfume and fragranceacetone/butanol research and production wascompany in Mikuni, Osaka, with a history ofspearheaded by private companies.
extracting and producing natural perfumes
At the start of the Pacific War, theand fragrances. The company developed itsgovernment was inclined towards isooctane
own technology to obtain styrene byproduction from fermentation butanol, as it had
dehydrating the β-phenyl ethyl alcoholannexed regions to the south with a ready supply
fragrance found in roses and other flowers,of sucrose. As a result, the Toyobo factory inand then independently developed theHofu was converted over to the production oftechnology to produce polystyrene from this.acetone/butanol and isooctane in 1943. A
Designated as a polystyrene supplier by thelarge-scale, 400 kL fermenter was constructed at
Ministry of Munitions in 1944, the companythe Hofu factory, and butanol production started
produced around 1 ton a month, although itat
the
end
of
1943.
had a 2 tons monthly production capacity.
This invention was a commendable idea thatturned the tables on the wartime slump in theperfume and fragrance business.
4.2.3 Fermentation acetone/butanol
Louis Pasteur discovered that butanol
could be made from anaerobic bacteria.

70[Footnote 2] n-butanol is dehydrated to produce n-butylene, which isthen isomerized to produce isobutylene. The isobutylene isdimerized and reduced further to produce isooctane. A method ofreacting isobutylene with isobutane to produce isooctane was also
known at the time.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 4.10 Production volume of butanol inJapan during the Second World War.
However, with the wartime situation
intensifying in 1944, it was no longer
possible to ensure possession of the regions inthe south, which made it difficult to obtain
sucrose. The government issued instructions
for the factory in Hofu to suspend productionof isooctane and switch from acetone/butanol
to producing anhydrous alcohol from tubers.
Accordingly, the factory in Hofu continued
anhydrous alcohol production from 1944 until
the end of the war.
Butanol can also be produced fromcarbide/acetylene.
However,
synthetic
butanol production stopped at the trial
production stage, as shown in Fig. 4.10, andthe butanol supply was almost entirely
provided for by fermentation process.
Right after the end of the war, themanagers and operators of the Hofu factory
devised a plan to resume production ofacetone/butanol from cheap, imported
molasses instead of sucrose. Although thepermit to import the molasses took more than
two years from the time of application, it was
finally granted in 1948. After several years,
the fermentation process overtook the
carbide/acetylene synthesis method resumed
shortly after the war.
The demand for butanol rapidly increased
as a raw material for polyvinyl chloride
plasticizers DBP and DOP. This resulted in a
rapid postwar revival of fermentationacetone/butanol, unlike fermentation ethanol.
This situation continued until the advent of
the petrochemical method in 1962. In theearly 1960s, the fermentation process
accounted for 27,000 tons of butanol per year,
while the carbide/acetylene synthesis method
accounted for no more than 6,000 tons per
year.

However, with plans afoot fortransitioning to petrochemical methods, theprice of acetone and butanol began to dropfrom the late 1950s onwards, with the
expectation that the cost of petrochemical
production would decrease. Accordingly,
fermentation companies and acetylene
synthesis companies alike abandoned their
existing facilities and quickly started shifting
to petrochemistry. As a result, fermentation
process production came to a halt within two
years of the start of the petrochemical method.
Unlike fermentation ethanol, fermentationacetone/butanol has not continued anywherein the world to the present day.

4.3 Industrial organic chemicals andpolymers from fats and oils
The main chemical products made fromfats and oils that have existed since before themodern chemical industry are soap andcoating. Soap has been produced sinceancient times by boiling fats and oils inalkalis.
Coatings have also been made sinceancient times by mixing pigments with dryingoil (oils containing large numbers of
unsaturated bonds, such as linseed oil or tungoil) or semi-drying oil (such as soybean oil).
The unsaturated bonds in the oil are oxidized
by the oxygen in the air and polymerize, thus
resulting in a weather-resistant polymer
product. While not an oil, Urushi lacquer has
similarly been made since ancient times inJapan and East Asia using an air oxidation
polymerization process. One drawback withthese coatings is that they were very slow todry (polymerize) once applied. In order toquicken the drying (polymerization) processslightly, the oil was mixed with lead,manganese, or cobalt oxide and then boiled.
With the development of oleochemistry
in the 20th century came the production of anumber of industrial organic chemicals andpolymers from fats and oils, as shown in Fig.
4.11.
4.3.1 Soap/hydrogenated oil
Soap took hold in Japan as an imported
product in the early Meiji Period. A numberof newcomers appeared in the market,
Systematic Survey on Petrochemical Technology

71expecting the demand to grow, andtechnology was introduced from the West.
However, this never grew beyond the domainof handicrafts using open-fire saponification
kettles and mold-kneading technology.

Fig. 4.11 Product categories of fats and oils as raw materials.
The Japanese soap industry became
established as a modern chemical industry
around 1900. Nagase Shokai (now Kao)
advocated the production of high-quality soap
and set up factory production facilities,
introducing steam saponification kettles andmachine mixing technology. In 1910, thecompany started production of high-purity
fatty acids and glycerin by high pressurehydrolysis of fats and oils using autoclave
equipment imported from Germany. This
made it possible to produce good qualitysoap.
Up until the First World War, all glycerin
had been imported. In 1911, Nagase Shokai
started recovering crude glycerin from theliquid waste from its soap, and many othercompanies followed suit. Refined glycerin
was needed by the military for gunpowder,and so glycerin became subject to the Law
Promoting the Production of Dyes andPharmaceuticals (1915). Based on this law,
the national policy concern Nippon Glycerin
was established in 1916 with a capital stockof ¥6 million to produce refined glycerin.
Around the same time, hydrogenated oilbegan being produced by hydrogenating fats
and oils. At the time, there was an abundant
supply of fish oil (sardine oil, etc.). Since fish
oil contains a lot of unsaturated fatty acids, itwould form solid hydrogenated oil at normal
temperatures when hydrogenated with anickel catalyst. The hydrogenated oil wasused as a substitute for the imported beef
tallow used for making soap.

72

4.3.2

Expansion into diversified
oleochemistry
In the 1930s, companies started moving
away from the soap/ fats and oils industries
and into diversified oleochemistry. For
reference, Fig. 4.12 shows the chemical
structures of the fats and oils and fat and oil
products discussed below, as it is difficult to
explain the developments in oleochemistry
using words alone. In the early 1930s,
synthetic surfactant higher alcohol sulfuric
acid ester salt (AS) (see Section 3.4.7 (2))
was imported for the first time from Boehme
in Germany. While this surfactant is still used
as a neutral detergent for washing high-end
garments, etc., at the time it was used more asa dyeing auxiliary for helping dyes permeate
and adhere uniformly to fabric than for
laundry. This product spurred Japan into
initiatives to produce its own higher alcohol
sulfuric acid ester salt.

Fig. 4.12 Major molecular structures of
oleochemistry products.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Dai-ichi Kogyo Seiyaku used sperm
whale oil (spermaceti) as a raw material. The
main component in spermaceti is a wax(higher alcohol ester of a higher fatty acid)rather than an oil (higher fatty acid
triglyceride). Specifically, it is the ester ofpalmitic acid and cetyl alcohol. Consequently,
it produces a higher alcohol (mainly cetylalcohol) when hydrolyzed, and esterizes withsulfuric acid. Dai-ichi Kogyo Seiyaku
developed this production technology in 1934,and started production in 1938. It was firstmarketed as the household neutral detergent“Monogen,” safe on wool and other delicate
fabrics. This was the first synthetic detergent
produced with Japanese technology. However,high pressure hydrolysis technology was
introduced in the 1910s that could extract thecetyl alcohol from spermaceti. Since it is a
wax rather than an oil, the higher alcohol
could be obtained by high pressurehydrolysis.
Kao used high-pressure reduction of
coconut oil to produce a higher alcohol,
which was then subjected to sulfuric acid
esterification and marketed as the synthetic
detergent “Exceline” in 1938. Kao’stechnology reduced the higher fatty acidusinghydrogenathighpressure.
High-pressure reduction technology had abroad range of applications, and marked the
beginnings of diversified oleochemistry. In
1939, Kao successfully produced an aircraft
lubricant by reducing a higher fatty acid athigh temperature and pressure using a zinccatalyst to obtain α-olefins, which were thenoligomerized with aluminum chloride. In
1940, the United States started imposing
high-octane gasoline and aircraft lubricant
embargoes on Japan. At the request of themilitary, at the end of 1941, Kao started
construction of an aircraft lubricant factorywith an annual production capacity of 100 kL.
High-pressure reduction technology was also
used in the production of sorbitol fromglucose (industrialized in 1943), and α-phenyl
ethyl alcohol from acetophenone (rawmaterial for styrene, mentioned in Section
4.2.2 (2), industrialized in 1943).
The production of one particular higher
alcohol by high-pressure reduction of fats andoils contributed to the postwar revival of theoleochemical industry. This was n-octyl
alcohol for the plasticizer DOP, used in PVC.
However, straight-chain octyl alcohol fromfats and oils was not as good a plasticizer as
branched-chain octyl alcohol synthesizedfrom acetylene/acetaldehyde, and the later
growth in plasticizers was through theacetaldehyde method.
Theemergenceandsubsequentsignificant
developmentofsynthetic
detergents from petrochemical products in the
1950s–1960s placed significant pressure on
soap and synthetic detergents made from fats
and oils. However, the early rapid growth insynthetic petrochemical detergents was
accompanied by some environmental issues(foam pollution in rivers) in the 1960s, bothin Japan and in the West. The cause of thiswas investigated, followed by initiatives to“soften” synthetic detergents [Footnote 3].
Environmentally biodegradable surfactants
began to be produced from straight-chain
higher alcohols and straight-chain α-olefinsusing fat and oil high-pressure reduction
technology.
Thesynthetic
detergent“softening” process only took six years inJapan, and was fully completed in the early
1970s. This process was accompanied by arevival in large-scale production of higher
fatty acids and higher alcohols from fats andoils. Diversified oleochemistry joined withpetrochemistry to expand in new directions.
4.3.3 Oil-modified alkyd resin
An alternative to the drying-oil coatings
that have been used since ancient times isnitrocellulose coating, made up of
nitrocellulose and an organic solvent. Due toits quick drying time, this coating suddenly
grew in popularity in the 1920s, alongside theflourishing American automotive industry.
Oil continued to be used in coating,thanks to the development of oil-modified
alkyd resin in the late 1920s, made fromdrying oil, semi-drying oil and phthalicanhydride. When oil (higher fatty acid
triglyceride)
reactswithglycerin,transesterification occurs, producing a mix ofhigher fatty acid monoglycerides and[Footnote 3] Detergents with poor environmental biodegradability
are termed “hard,” while those with good biodegradability are
termed “soft.”
Systematic Survey on Petrochemical Technology

73diglycerides [Footnote 4], as shown in Fig.
4.13. When this reacts with phthalicanhydride, the monoglyceride molecules,
which have two hydroxy groups, form several
bonds (oligomerization). The diglycerides,
which only have one hydroxy group, stop thebonds from extending, thereby regulating thelength of the oligomer molecules. Since theunsaturated bonds contained in the higher
fatty acid remain as they are, as indicated by
R1 and R2 in Fig. 4.13, once the coating has
been applied, oxidative polymerization occurs
through contact with the oxygen in the air,similar to drying-oil coatings. This is shownin Fig. 4.13 as alkyd resin.
Since the alkyd resin has moreunsaturated bonds per oligomer moleculethan the original unsaturated oil, it dries fasterand is also more weather-resistant and more
flexible. Like boiled oil, alkyd resin dries
even faster when combined with cobalt
naphthenate, lead naphthenate, or otheradditives. Alkyd resin has been produced
domestically in Japan since the start of the
1930s, and is also known as phthalic acidresin.
After the war, a mixture of alkyd resin
and amino resin (butylated melamine
formaldehyde
resin,
butylatedurea
formaldehyde resin, etc.) emerged in 1948 in
the form of amino-alkyd resin baked coating.
However, as the petrochemical industry
moved into domestic production andexpansion, a number of petrochemical
polymers began to be used in coatings,
significantly reducing the role played byoil-based coatings. Amidst such trends,
however, some products, such as epoxy alkyd
resin coating, are still being produced thatutilize the strengths of both petrochemicaland oil-based coatings.

resources in order to reduce greenhouse gases.
One such example is the rapid increase inproduction of fermentation ethanol in the
United States, discussed previously. These
initiatives have even extended as far as fats
and oils. Europe has seen a rapid increase in
the use of biodiesel oil from palm oil,rapeseed oil, sunflower oil and other such
sources. Biodiesel oil is a higher fatty acidmethylester
producedbythetransesterification of oil (higher fatty acid
triglyceride) and methanol. Technically, it
only refers to product that has already beenused in the course of higher alcohol
production.
However,
biodieseloilproduction has increased dramatically due toits use as an automotive fuel, with the
production of palm oil rapidly increasingfrom 300,000 tons in 1995 to 41 million tons
in 2009.

4.3.4 Biodiesel oil
There have been significant changes inthe directions taken in oleochemistry inrecent years. Policies such as the Biofuels
Directive issued by the EU in 2003 haveaimed to accelerate the use of renewable[Footnote 4] The molecular structure of glycerin is CH2OH – CHOH
– CH2OH. Oil (higher fatty acid triglyceride) has a molecular
structure of CH2OCOR1 – CHOR2 – CH2OR3, where R represents
the alkyl group. When the glycerin and oil are transesterified, one or
two alkyl groups in the oil break away to form hydroxy groups OH.
These are called diglycerides and monoglycerides.

74

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 4.13 Molecular structures of glycerides and oil-modified alkyd resin.

4.4 Industrial organic chemicals andpolymers from coal
Coal chemistry, or the forest of products
made from coal, flourished for a long time
before and after the advent of petrochemistry.
Coal chemistry falls into three broad
categories, each of which has developed sosignificantly that it has been assigned aseparate section here. These separate forests
are carbide/acetylene chemistry, coaltar/aromatic chemistry and coke/syngas
chemistry.
Another such forest was the use of gas(called coke oven gas or coal gas) producedin the dry distillation of coal chemicals. The
main components in coke oven gas arehydrogen and carbon monoxide; these were
widely used in city gas supplies, as well as
providing the raw material by which theammonia industry was established. Cokeoven gas also contains various othersubstances in addition to hydrogen andcarbon monoxide, including ammonia, sulfur
compounds and hydrocarbons – including
ethylene. It is difficult to extract and refine
the ethylene from coke oven gas to use it as araw material for industrial organic chemicals,
and this was largely not done in Japan.
However, it was done in Germany, and inwartime it ranked among the most significant
sources of ethylene next to dehydration of
fermentation
ethanolandpartialhydrogenation of acetylene; it was also asource of EG and other such substances. The
coke oven gas forest is not a significant one

in terms of industrial organic chemicals, andno further details have been included here.

4.5 Industrial organic chemicals andpolymers from carbide/acetylene
Carbides are made from coke, produced
by distilling coal, and as such are one of theforests of petrochemistry. Carbides areproduced by reacting coke with quicklime inan electric furnace at a temperature of
2,000°C or higher. This requires a lot ofelectricity and can also be counted as anelectrochemical industry.
Lime nitrogen is produced by exposing
carbides to a nitrogen flow at 1,000–1,100°C.
Lime nitrogen on its own is used as anitrogenous fertilizer. Since it producesammonia when reacted with steam, it can also
be absorbed into sulfuric acid and then used
as a nitrogenous fertilizer in ammonium
sulfate form (converted ammonium sulfate)[Footnote 5]. When carbides react with waterat normal temperatures, acetylene is produced.
This reaction was discovered in 1862 byGerman chemist Friedrich Wöhler, one of thefounders of organic chemistry.
While lime nitrogen was industrialized[Footnote 5] Ammonium sulfate (ammonium sulfate fertilizer) madefrom ammonia produced directly from nitrogen and hydrogen iscalled synthetic ammonium sulfate. By contrast, ammonium sulfate
made from ammonia produced by reacting lime nitrogen with steam
is called converted ammonium sulfate. Ammonium sulfate producedin the treatment of waste sulfuric acid from the production ofcaprolactam or other chemical compounds other than ammonium
sulfate is called recovered ammonium sulfate, while ammonium
sulfate made from ammonia found in coke-oven gas generated incoal carbonization is called byproduct ammonium sulfate.
Systematic Survey on Petrochemical Technology

75

several years after the industrialization ofcarbides, the acetylene chemical industry was
not established until the 20th century, around50 years after Wöhler’s discovery.
4.5.1 Carbides
Carbideswere
industrializedbyAmerican company Union Carbide in 1894,
and around the same time in Europe.
Acetylene was initially used as acetylene gas
for lighting. One useful application that wasdeveloped was safety lamps for mineshafts.
Later, a number of improvements were madeto carbide production, including shifting theelectric furnaces from single-phase to
three-phase current, and changing the carbon
source from charcoal to anthracite and thencoke. By 1915, 10,000 kW large-scale
electric furnaces were being built.
Lime nitrogen formation was discoveredin Germany in 1897. Later furnace
improvements resulted in the industrializationof the Frank-Caro furnace in 1908. This madeit possible to produce large volumes ofnitrous fertilizer from the nitrogen in the air,as well as ammonia, and lime nitrogen /converted ammonium sulfate plants began tobe established all around the world, such as
the American Cyanamid Company at Niagara
Falls in the United States in 1909.
In Japan, Tsuneichi Fujiyama andShitagau Noguchi successfully produced
carbides with a 50 kW electric furnace inSankyozawa, Sendai, in 1902. Later, Noguchi
established Nippon Chisso Hiryō (now JNC),
and in 1908 built a plant in Minamata withfour German-made 3,000 kW carbide
furnaces, and started producing lime nitrogen.
Meanwhile, Fujiyama established Hokkai
Carbide Plant (now Denka) in Tomakomai in
1912. He established a plant in Ōmuta,
Fukuoka, in 1916, and another in Ōmi,Niigata, in 1921, significantly expanding the
carbide, lime nitrogen and converted
ammonium sulfate industries.
Up until around 1950, 50–80% of
carbides were used for fertilizer, and 20–30%
were used for lighting, welding and cutting,as shown in Fig. 4.14.
The process of directly synthesizing
ammonia from nitrogen and hydrogen was

76

industrialized in 1911 by German company
BASF. This technology provided somecompetition for the method of manufacturingnitrogenous fertilizer from carbides. Directammonia synthesis spread around the worldin the 1920s, with a succession of Japanesecompanies also entering the direct ammonia
synthesis market and producing synthetic
ammonium sulfate in the 1920s and the 1930s,
following its industrialization in 1923 in
Nobeoka (now Asahi Kasei) by Nippon
Chisso Hiryō using the Casale method from
Italy. However, even the emergence ofsynthetic ammonium sulfate did not result ina dramatic decrease in demand for carbides
for fertilizer. After the Second World War,
there was a call to increase fertilizer
production, and the carbide industry quickly
revived in response.
A detailed examination of carbide
consumption reveals that from the 1950s
onwards, there was a decrease in carbide use
for fertilizer as the main area of demand,
replaced by a rapid increase in its usage in theacetylene chemical industry. However,acetylene chemistry came under pressure
from petrochemistry in the 1960s, and had
almost disappeared by the end of the decade.
Carbide production peaked in 1965 andrapidly declined after that.
4.5.2 Acetylene chemical industry
The acetylene chemical industry based onacetylene made from carbides was founded in
1916 by German company Wacker, with the
production of acetyl aldehyde by reacting
acetylene and water. Many companies soon
entered the market in Germany, Canada andthe United States, resulting in the demise of
the wood carbonization industry, as
mentioned in Section 4.1.1.
In Japan, the Nippon Synthetic Chemical
Industry started producing acetaldehyde in1928 as an intermediate for synthetic acetic
acid production. The acetylene chemicalindustry continued to expand in Japan foranother 40 years. Up until the 1950s, theJapanese acetylene chemical industry mainly
revolved around the production of
acetaldehyde and synthetic acetic acid.
During these two decades, organic synthesis(the acetylene chemical industry) accounted
for around 10% of all carbide consumption,

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

other than during the Second World War, as

shown in Fig. 4.14.

Fig. 4.14 Change of production volume and demand detail of calcium carbide.
The 1950s and the 1960s, however, saw asudden increase in organic synthesis. This
meant an accompanying rapid increase in
carbide production, far exceeding peakprewar volumes. The main reason for thisincrease was vinyl chloride, which was solely
used for making PVC. Acetylene chemistry
also rapidly expanded in scale, with growing
demand for monomers and polymers. Vinyl
acetate, chlorine-based solvents and manyother industrial organic chemicals were also
produced from acetylene, as shown in Fig.
4.15.
However, carbide production volumes
dropped rapidly at the end of the 1960s. The
main reason for this was also organic
synthesis.
Withtheproductionofacetaldehyde, vinyl chloride and nearly every
other industrial organic chemical made fromacetylene changing over to petrochemical
methods, the acetylene chemical industry fell
into rapid decline. The main reasons for thiswere the rising cost of electricity, whichmeant that carbide-based acetylene could nolonger compete with basic petrochemicals, aswell as the fact that a succession of low-cost
production methods were being developed for
producing industrial organic chemicals frombasic
petrochemicals,
such
as
the
Hoechst-Wacker
processandtheoxychlorination process.
Below, we shall discuss the main
products and technologies of the acetylene
chemical industry, as well as the industry
policies aimed at boosting industrial organic
chemical industries just before the Second
World War in Japan.
(1) Acetaldehyde
Acetic acid and acetone were supplied by
the wood carbonization industry from the late
19th century onwards. As mentioned
previously, acetylene-based acetaldehyde wasindustrialized by German company Wacker
during the First World War. Since acetic acidcould be produced cheaply from acetaldehyde
using manganese acetate as a catalyst,
Germany started exporting synthetic acetic
acid around the world after the war, putting
the wood carbonization industry at risk of
disappearing. Japan also investigated thedomestic production of synthetic acetic acid,and several negotiations were made withGerman company IG Farben over technology
licensing. However, a compromise on theconditions could not be met, so the four
companies of the Dai Nippon Acetic Acid
Manufacturers’ Association started jointly
researching under the supervision of the
Osaka Municipal Technical Research
Systematic Survey on Petrochemical Technology

77Institute and sharing their results. Theirindustrialization experiments ended in 1927.
That same year, the four companies jointly
funded the establishment of Nippon Gohsei
Kagaku Kenkyusho (now The Nippon
Synthetic Chemical Industry). Since carbides
were needed as a raw material, a factory wasconstructed in Ogaki on a site adjoining
carbide manufacturer Ibigawa Electricity
Company (now Ibiden), and production

started in 1928, with an output of 60 tons permonth. The lifting of the gold export embargo
in 1930 increased imports of synthetic acetic
acid, synthetic methanol and other imports,
prompting the four companies financing The
Nippon Synthetic Chemical Industry to
rapidly reduce their own wood carbonization
operations and instead boost the synthetic
acetic acid production capacity of The
Nippon Synthetic Chemical Industry.

Fig. 4.15 Product categories industrialized using acetylene as raw material in Japan.
Acetaldehyde, via acetic acid, was used
to produce acetone using lime acetate
pyrolysis. It was also possible to makebutanol by aldol condensing acetaldehyde in
the presence of an alkali catalyst, thendehydrating it to produce croton aldehyde
CH3CH=CHCHO, and then hydrogenating
this to produce butanol. The Nippon
Synthetic Chemical Industry constructed afactory in Uto, Kumamoto, in 1939 as a
production base for integrated acetone andbutanol production from carbides. Thisfactory directly synthesized its acetone fromacetylene and large quantities of steam usingiron oxide or zinc oxide as a catalyst, rather
than from acetaldehyde and acetic acid. This
process produced hydrogen and carbon
dioxide as byproducts. However, the start ofacetone/butanol fermentation from sucrose in
the 1940s and molasses in the 1950s saw thefermentation process overtake and dominate

78

the acetylene synthesis method, as shown in
Fig. 4.16 (see Section 4.2.3). Initially, there
were no other significant industrial organic
chemicals made from acetylene except for
acetaldehyde and acetic acid.

Fig. 4.16 Change in production volume ofacetone and butanol from the 1930s to the1950s.
(2) The Organic Synthesis Industry Law
The large-scale industrial organic

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chemical industry and synthetic polymer
industry underwent significant expansion in
Japan from the late 1930s, when the wartime
economy system came into force. This can beseen in laws such as the Artificial Petroleum
Production Industry Law and Alcohol
Monopoly Law of 1937 and the Organic
Synthesis Industry Law of 1940. The
Artificial Petroleum Production Industry Law
aimed to promote the synthesis of petroleum
from coal as a national policy. This isdiscussed later in the section on products
made from syngas (Section 4.7.2). The
Alcohol Monopoly Law promoted the rapid
increased production of fermentation
anhydrous ethanol for a petroleum fuelalternative as a national policy, as discussed
in Section 4.2.1.
The Organic Synthesis Industry Law
aimed for the rapid expansion of organic
synthesis businesses. Therefore, while freeentry into the main organic synthesis
businesses was restricted by government
licensing, license holders were given special
protection, such as commercial code
exemptions in relation to issuing corporate
bonds, land expropriation rights as needed,
import restrictions on goods that could hinder
theestablishmentofbusinessandmanufacturing incentive grants. Organic
synthesis businesses essential to the defense
industry (synthetic rubber, synthetic toluene,etc.) were given additional protection
measures, such as exemptions from income
tax and sales tax for certain periods,
exemptions from import tax on necessary
imported machinery and testing and research
incentives.
Under the Organic Synthesis Industry
Law, production expansion or urgent
commercialization was deemed necessary for
18 designated industrial organic chemical or
polymer products (Table 4.2). Many of thesewere industrial organic chemicals or
polymers made from carbide/acetylene. Of
these, the products that could still beclassified as being industrially produced fromcarbide/acetylene by 1945 were acetaldehyde,
acetic acid, acetic acid ester, acetone, vinyl
acetate (vinyl acetate resin), acetic anhydride(acetate), trichloroethylene, vinyl chloride(PVC), methyl methacrylate (methacrylate

resin) and polystyrene. Besides these,
chlorohydrin was also being produced fromethanol via ethylene, and small volumes ofpolystyrene were also being produced fromethanol and the fragrance β-phenylethyl
alcohol, besides from acetylene, as discussed
previously. Synthetic rubber will be discussed
in the following section. Methanol was being
produced from syngas since before theOrganic Synthesis Industry Law was enacted.
Synthetic tannin was industrialized by Nitta
Chemical, Nihon Kasei (now Mitsubishi
Chemical) and Mitsui Chemicals. Mitsui
Chemicals used spent sulfite liquor as a raw
material in its manufacturing process.
Table 4.2 Eighteen products designated by
the Organic Synthesis Industry Law inJanuary 1941

Meanwhile, benzene and toluene were
expected to start being produced bycarbide/acetylene synthesis rather than theconventional method of fractional distillationfrom coal tar (mainly a byproduct of cokeproduction for iron manufacturing). Tokyo
Industrial Research Institute developed thistechnology in 1938, and Nippon Carbide
industrialized 400 tons annual production
before the Organic Synthesis Industry Law
was enacted. However, it was not even able
to triple this volume before the end of thewar.
Synthesis of aviation fuel isooctane wassubject to the Artificial Petroleum Production
Industry Law rather than the Organic
Synthesis Industry Law. Domestic production
was not achieved by the end of the war,
although Chōsen Chisso Hiryō, a Korean
subsidiary of Nippon Chisso Hiryō, achievedlarge-scale production in 1942 at its industrial
complex in Hyungnam. By the end of the war,
Systematic Survey on Petrochemical Technology

79

production capacity had reached 45,000 tonsof acetaldehyde, 30,000 tons of butanol and
20,000 kL of isooctane. This scale ofproduction was incredibly large for industrialorganic chemicals at the time, and was madepossible by large-scale hydroelectric power
generation, which was not available inmainland Japan. The isooctane wassynthesized through an acetylene –acetaldehyde–butanol–evaporation/isomerization/dimerization/hydrogenation process. The process from acetylene
to butanol was carried out using Nippon
Chisso Hiryō technology, and then theprocess from butanol to isooctane was carriedout using technology developed by the navy
fuel factory.
From the enactment of the Organic
Synthesis Industry Law in 1940 through to
1945, the consumption of carbides was
discouraged for fertilizer, and encouraged fororganic synthesis, mineshaft lighting, welding
and cutting, as shown in Fig. 4.14.
Accordingly, while organic synthesis
accounted for around 10% of carbide
consumption before and after this time period,
it rose to around 15% of carbide consumption
during this period only. This usage wasentirely for the military.
The Organic Synthesis Industry Law
served as an opportunity to develop
large-scale industrial organic chemical andpolymer industries in Japan, and provided aplatform for launching a large-scale
petrochemical industry within a short spaceof time in the 1950s. These industrial
development laws, or business laws, were thestarting point for the Japanese government’s
idea of strong policy intervention in the
petrochemical industry from the 1950s to the
1980s.
(3) Synthetic rubber
Synthetic rubber was first industrialized
during the First World War by German
company Bayer, amidst a naval blockade.
The rubber produced was methyl rubberpolymerized from 2,3-dimethyl-1,3-butadiene.
Acetone was synthesized from acetylene,
then dimerized by pinacol coupling using
metallic magnesium, and then dehydrated to
produce dimethylbutadiene, which was then80

polymerized. While 2,000 tons of synthetic
rubber were produced during the First World
War, the industry fell into decline after thewar, as it could not match the performance of
natural rubber. However, a wealth of research
was conducted on butadiene manufacturing
and polymerization methods after the war,both in Germany and in the United States.
Some of this research found that abutadiene-styrene copolymer showed very
good performance and could be used in manyof the applications for natural rubber. This
copolymer was Buna-S, now calledstyrene-butadiene rubber or SBR. IG Farben
was granted the German and American
patents in 1929, and constructed a test plantin 1934. Meanwhile, DuPont developed CR
by emulsion polymerization of chloroprene,and started industrial production of it in 1932.
Although CR never became a substitute fornatural rubber, it had a use of its own due toits superior oil resistance. The Standard Oil(New
Jersey)developedIIR,
anisobutylene-isoprene copolymer, and started
industrial production of it in 1943. IIR wasused in tire tubes due to its low gas
permeability.
During the Second World War, theUnited States had to focus on developing andproducing synthetic rubber as a national
policy, as Japan had quickly annexed much ofSoutheast Asia. The United States produced
2,400 tons of SBR in 1942, 180,000 tons in
1943, 670,000 tons in 1944 and 720,000 tons
in 1945. By the end of the war, Germany had
an annual production capacity of 150,000
tons and produced 110,000 tons in 1944.
The industrialization of synthetic rubber
in Japan was one of the main objectives forenacting the Organic Synthesis Industry Law.
Table 4.3 shows the companies that produced
synthetic rubber in Japan during the Second
World War, as well as their production
methods and products. The Osaka Industrial
Research Institute of the Ministry ofCommerce and Industry started researching
synthetic rubber in 1935, and established amethod of producing butadiene from ethanolbydehydration,
dimerizing
anddehydrogenating using a magnesium oxide
catalyst (the alcohol method). The Institutealso perfected a method of extracting

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

butadiene using cuprous chloride, and in 1938
constructed a plant with a 10 kg daily
production capacity. The institute also
conducted research on polymerization using
metallic sodium, as well as copolymerization
with acrylonitrile and styrene. In 1939, a
number of engineers from the Osaka

Industrial Research Institute transferred to
Nihon Kasei (now Mitsubishi Chemical),
while a butadiene plant with a 1-ton daily
production capacity was completed in 1942
under the Organic Synthesis Industry Law.
Production then started on NBR synthetic
rubber.

Table 4.3 Synthetic rubber manufactured in Japan during the Second World War

At the same time, Prof. Junji Furukawa of
Kyoto University perfected the technology to
produce butadiene by monovinyl acetylene(MVA) reduction. This technology offered asimpler butadiene production process than thealcohol method, and the equipment was also
cheaper. Although Nihon Kasei also built an
MVA-reduction NBR plant, the war ended
without it reaching an adequate production
stage due to a shortage of raw materials.
Sumitomo Chemical shifted the Kyoto
University pilot test facilities to its plant in
Niihama, and also separately built anacrylonitrile plant and started producing small
quantities of NBR synthetic rubber.
Kanegafuchi Industrial Company (nowKaneka) also completed an MVA-method
butadiene-NBR plant in early 1945, but the
war ended without it having reachedsufficient production levels due to air raids
and other factors.
Mitsui Mining started its own research in1937 and perfected a method of producing
butadiene via acetaldol by dimerizing
acetaldehyde (the aldol process), and also
developed NBR synthetic rubber production
technology. In 1941, the company started

construction of a butadiene plant with a 1-ton
daily production capacity under the Organic
Synthesis Industry Law. It also built anacrylonitrile plant at the same time, andproduced NBR synthetic rubber from 1944
until the end of the war.
Nippon Carbide made some advances
into chloroprene rubber research, based onstudies by Prof. Munio Kotake of Osaka
University, and developed a production
method using an amino hydrochloric acidcatalyst rather than the ammonium chloride
used by DuPont. The company completed aplant with a 1-ton daily production capacity
in Uozu in 1943, but its actual production was
significantly lower than its nominal capacity
due to a shortage of raw materials andresources.
Up until the start of the war, the Japanese
government
andmilitary
took
thedevelopment of a wide range of synthetic
rubbers, including SBR, very seriously.
However, with Japan annexing the southern
regions very soon into the war, it was able tosecure a plentiful supply of natural rubber.
After that, it only encouraged thedevelopment and production of the highly oil
Systematic Survey on Petrochemical Technology

81resistant NBR and chloroprene synthetic
rubbers. From 1943 onwards, once thewartime situation intensified and the supplyof natural rubber started becoming
problematic, there were not enough resourcesin the country and it was not possible to build
general-purpose synthetic rubber plants nomatter how much the government supportedit.
(4) Vinyl chloride and PVC
When Japan lost the war in 1945, it lostits munitions demand in one fell swoop. The
carbide industry turned its focus to fertilizer
once more, as shown in Fig. 4.14. The
postwar shortages of food and supplies alsomeant an increase in the demand for fertilizer,
and carbide production volumes revived.
Organic synthesis went back to accounting
for around 10% of carbide usage. However,acetic acid manufacturers began exploringareas for large-scale demand outside of theconventional areas of acetic acid use(solvents, acetic acid esters, vinegar). One
such area of exploration was theindustrialization of acetate fiber using acetic
anhydride. Another was the development of
products from vinyl acetate. Vinyl acetate
could be made into vinyl acetate resin,
polyvinyl alcohol, and the synthetic fiber
vinylon. Production of vinylon started in1949 by Kurashiki Rayon (now Kuraray),with high hopes for domestically invented
and producible synthetic fiber. This wasfollowed by the production of vinylon by
Dainippon Spinners (now Unitika), using
technology developed by Ichirō Sakurada of
Kyoto University. Industrial production of
acetate fiber was started in 1955 by Teijinusing introduced technology; the following
year, Ryoko Acetate also started production
under Mitsubishi Rayon.
Acetic anhydride and vinyl acetate werelinked in their production. The reaction ofacetic acid and acetylene co-produces vinyl
acetate and ethylidene diacetate, as shown in
Fig. 4.15. Over-supply of acetylene at low
temperatures raises the vinyl acetate yield,
while the opposite yields more ethylidene
diacetate. Since pyrolysis of ethylidene
diacetate produces acetic anhydride andacetaldehyde, the acetaldehyde can be82

oxidized and reused as acetic acid.
However, in the 1950s, a large-scaledemand emerged that completely differedfrom the acetaldehyde-acetic acid productsthat had been the main focus of the acetylene
chemical industry since before the Second
World War, and within a short space of time,
became the mainstay of the acetylene
chemical industry. This was vinyl chloride
and PVC.
Vinyl chloride is synthesized by reacting
acetylene with hydrogen chloride. Emulsion
polymerization of vinyl chloride produces
PVC. PVC was industrialized in the late
1920s in Germany and the early 1930s in the
United States. It appeared in Japan as animported sample in 1937, and initiatives
towards domestic production started rightaway. In 1941, Nippon Chisso Hiryō
industrialized production of PVC (3-tonmonthly capacity) at its plant in Minamata,with the idea of exploring new applications
for carbides. It also developed its own
monomer and polymer production technology.
In 1939, it also produced vinyl chloride
copolymers. However, the Nippon Chisso
Hiryō plant in Minamata was destroyed in an
air raid in 1945.
After Japan lost the war, Western
technology and market information began toflow into Japan once more. In 1948, Japan
imported PVC scraps from the United States,
which were distributed out to a dozen
manufacturers to research. From 1950
onwards, companies started importing a
succession of Western PVC processing
equipment. The imported PVC made it
possible to create a number of molded
products, including wire coatings, film, sheets,
leather, belts, tubes and hoses. A number ofcompanies noted these market trends andembarked on domestic PVC production.
Nippon Chisso Hiryō, which had been in
production during the war, started out in 1949
with a monthly production capacity of 5 ton,followedbyanumberofothercarbide-acetylene manufacturers in 1950 and
1951, including Nihon Kasei (laterindustrialized in 1951 as Mitsubishi
Monsanto Chemical, now Mitsubishi
Chemical), Mitsui Chemicals, Kanegafuchi
Chemical Industry (now Kaneka), Tekkoosha

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)and Denki Kagaku Kogyo (now Denka). The
Yokohama Rubber Company, which had
trialed PVC production during the war,
established Zeon in 1950, in conjunction with
Nippon Light Metal, Furukawa Electric andAmerican company B. F. Goodrich
Chemicals. Once Mitsubishi MonsantoChemical and Zeon started producing PVC
using suspension polymerization method,other Japanese PVC manufacturers noted its
superior product quality compared toemulsion polymerization, and all started
switching over to suspension polymerization
method in 1952 and 1953 using introduced
technology.
The growth in PVC production volumes
was astounding. As Fig. 4.17 shows, it
quickly dominated the acetylene chemicalindustry, overtaking acetic acid, which had
been the mainstay of the industry since theacetylene chemical industry began, as well as
acetic anhydride/acetate and other acetic acidproducts with expected postwar growth, andalso vinyl acetate and vinylon.

Fig. 4.17 Change of production volume ofmajor acetylene products after the Second
World War.
(5) Reppe reactions
Industrial development of acetylene
chemistry in Japan was mainly throughatmospheric pressure reactions, as shown in
Fig. 4.18. The main products wereacetaldehyde and vinyl acetate synthesis byhydroxy group addition reactions at
atmospheric pressure, and trichloroethylene

and vinyl chloride synthesis by chlorine orhydrogen chloride addition reactions. Various
other acetylene-based industrial organic
chemicals were mainly synthesized using
acetaldehyde as an intermediate. Acetylene
dimerization and pyrolysis reactions rarelyattained to product production.
Meanwhile, Walter Reppe of IG Farbenin Germany was building up fundamental
studies on pressurized acetylene anddeveloped technology to handle it safely, as it
carried a risk of explosive decomposition.
Reppe went on to discover four major
reactions, shown in Fig. 4.19, andsystematized acetylene chemistry.
Addition reactions of hydroxy groups andhydrogen halide at atmospheric pressure weregeneralized as vinylation to produce vinyl
compounds, whereby alcohols with activehydrogen, phenol, carboxylic acid, amines,
amides and sulfur compounds add to triple
bonds under pressure, as shown in Fig. 4.19.
Dimerization reactions expanded into
trimerizedortetramerized
cyclicoligomerization. This is also called cyclic
polymerization.
Reactions not found among acetylene
reactions at atmospheric pressure include
ethynylation and carbonylation, as shown in
Fig. 4.19. Ethynylation is a reaction ofmethine hydrogen (hydrogen immediately
adjacent to a carbon-carbon triple bond) inwhich the carbon triple bonds in the acetylene
are preserved. The method of using an
ethnylation reaction of acetylene andformaldehyde to produce 1,4-butynediol, thenhydrogenating and dehydrating it to obtainbutadiene was industrialized in Germany
during the Second World War. This was oneof the methods of producing butadiene, theraw material for synthetic rubber, in Germany.
Carbonylation is a reaction of acetylene,carbon monoxide and substances with activehydrogen, using a carbonyl complex of cobalt,
nickel and iron as a catalyst. This produces
acrylic acid derivatives.

Systematic Survey on Petrochemical Technology

83

Fig. 4.18 Technology system and major products of acetylene chemistry in Japan before andafter the Second World War.

Fig. 4.19 Technology system and major products of Reppe reaction.

Reppe reactions were a type of organic
synthesis technology from Germany, which
had no petroleum or natural gas resources,
only coal. After the Second World War, inthe late 1940s, both the academic world andthe industrial world in Japan started
enthusiastically researching this topic, armed
only with the domestic resources of coal andhydroelectric power. When the United States
published the PB Report on German wartime
science and technology, there was a lot ofinterest in Reppe reactions. However, once
large quantities of petroleum soon began tobe imported from the Middle East, and as
petrochemistry developed, the move to84

industrialize Reppe reactions in Japan soon
died out, and Reppe reactions were forgotten.
Nevertheless,theidea
behindthedevelopment of Reppe reaction technology
continuedoninlater-developed
petrochemical reactions, such as the allylhydrogen reaction [Footnote 6 ] and the oxo
process [Footnote 7] to produce carbonylcompounds by reacting olefins with carbon[Footnote 6] A reaction that preserves the double bonds of the olefin
but reacts with the hydrogens in the surrounding methyl groups,
producing acrylonitrile, acrylolein/acrylic acid, allyl chloride, maleic
anhydride, etc. See Section 6.1.2 (2).
[Footnote 7] A reaction that produces butyraldehyde from propylene,
higher aldehydes from α-olefins, and propionaldehyde from ethylene.
See Section 6.1.2 (1) 5).

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monoxide and hydrogen, although thereaction mechanisms differ from Reppe
reactions. It is fair to say that Reppe reactions
had a significant impact on later
developments in petrochemical technology.

4.6 Industrial organic chemicals andpolymers from coal tar
The coal carbonization industry began in
the 18th century for producing coke for ironmanufacturing, as well as for city gas
production (street lighting, fuel, heating).
Coal tar was an unwanted byproduct of coalcarbonization. Distilling coal tar produced
benzene, naphthalene, anthracene and otheraromatic hydrocarbons, as well as phenols,cresols, pyridines and other aromatic organic
compounds, as shown in Fig. 4.20, with aresidue of around 60% (pitch). Whilearomatic hydrocarbons from petroleum
distillation are mainly monocyclic (benzene,
toluene, xylene), coal tar also produces a
numberoffused-ringhydrocarbons(naphthalene, anthracene). For reference, Fig.
4.21 shows the chemical structures of themain aromatic hydrocarbons produced fromcoal tar, as well as the main industrial organic
chemicals produced from them.
The coal-tar-based industrial organic
chemical industries were based around themain products produced by distilling coal tar:benzene, toluene, naphthalene and anthracene.
The synthetic dye industry started in 1856 by
William Henry Perkin, with industries later
developing in Germany and Switzerland as

well. The synthetic pharmaceutical industry
started at the end of the 19th century, as
typified by Bayer’s aspirin (acetylsalicylicacid). Perfumes and fragrances and flavorings,
artificial sweeteners and a number of otherfine chemical industries also began at thistime. After the Second World War, coal tar
products also came to serve as raw materials
for DDT, BHC, 2,4-D, PCP and otherpesticides. A very diverse range of aromatic
chemical
synthesizing
technologies
developed before the advent of thepetrochemical industry. The coal tar chemicalindustries produced the most diverse range of
products and had the most complex structuresof all the forests of coal chemistry.
However, many of these low-quantity,
high-diversity coal tar chemical industries
had no relation to petrochemistry. The
mass-produced aromatic industrial organic
chemicals that were related to petrochemistrywere phenol and phthalic anhydride. Phenol
was produced from benzene, while phthalicanhydride was produced from naphthalene, as
shown in Fig. 4.20. Other mass-produced
aromatic industrial organic chemicals
included TDI and MDI from coal tar
chemical industries. TDI and MDI wereclassic coal tar chemistry products: aromatic
amines made by nitrating and reducing
aromatic hydrocarbons. However, they areomitted in this section as their mostsignificant developments took place in the
petrochemical era.

Systematic Survey on Petrochemical Technology

85

Fig. 4.20 Major product categories of coal tar as raw material.
4.6.1 Phenol
Phenol can be directly obtained from coaltar, and was used in disinfectants andsynthetic dyes in the 19th century. The
demand for phenol increased significantly inthe 1880s when picric acid started being used
as an explosive, and the production scale had
to shift from that of a dye intermediate to thatof an industrial organic chemical. Meanwhile,industrial production of phenol by coal-tar
benzene sulfonation process started inGermany in the 1890s. The benzene wassulfonated in concentrated sulfuric acid, thenneutralized and melted with sodiumhydroxide to produce phenol sodium salt,
which was then neutralized to produce phenol.
This was a very complicated andlabor-intensive method of production. In
Japan, Yura Seiko (now Honshu Chemical
Industry) industrialized production using its
own developed technology in 1915, while theMitsui Mining Mitsui Dye Plant (now Mitsui
Chemicals) did the same using licensed

86

technology in 1916.
With the industrialization of phenol resinin the United States in the 1910s, the demandfor phenol grew even more. A chlorobenzene
process was industrialized in the UnitedStates in the 1920s. This method chlorinatedbenzene to produce monochlorobenzene, thenreacted this with solution of sodiumhydroxide in an autoclave to produce phenol
sodium salt, which was then neutralized withhydrogen chloride to produce phenol.
The Raschig process was developed andindustrialized in the 1930s. This method
reacted benzene with hydrogen chloride andair with a copper oxide - iron oxide - alumina
catalyst to produce monochlorobenzene,
which was then hydrolyzed at the gas phaseusing a silica catalyst to produce phenol. The
byproduct hydrogen chloride was thenre-used. The Raschig process was a far moresophisticated method of production.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 4.21 Aromatic hydrocarbons and industrial organic chemicals from coal tar.
In 1939, American company DuPont
industrialized 6,6-nylon. The adipic acid used
as a raw material for this was made fromphenol. DuPont claimed it was “fabricatedfrom such common raw materials as coal,water and air … as strong as steel, as fine as
the spider’s web.” German company IG
Farben industrialized 6-nylon in the early
1940s, slightly later than DuPont. The raw
material for 6-nylon, ε-caprolactam, was also
made from phenol. With nylon production
increasing rapidly after the Second World
War, the demand for phenol also suddenly
increased. In Japan, phenol production also
rapidly increased from the late 1950s, whenindustrial production of nylon began inearnest, as shown in Fig. 4.22. Productionlevels after the war in the early 1950s were on
a completely different dimension from prewar
levels.

Fig. 4.22 Change of production volume ofsynthetic phenol after the Second World War.
The rapid increase in demand for phenol
meant a rapid increase in the demand forbenzene as well. However, since coal tar was
only produced as a byproduct of coke, it
could not support the rapidly-growing
demand for benzene.
In 1953, the cumene process, a newphenol production method, was developed in
the United States and United Kingdom, andindustrialized first in Canada. The cumene
process produces cumene from benzene andpropylene, which is then oxidized andcleaved to co-produce phenol and acetone.
During the Second World War, cumene wasproduced by petroleum companies as agasoline-base material for high-octane
gasoline. The cumene process was certainly atechnology suited to petrochemistry. Rightwhen the petrochemical industry wasbooming in the West, this method took holdworldwide, ahead of the chlorobenzene andRaschig methods. It was industrialized inJapan in 1959 by Mitsui Petrochemical
Industries using introduced technology.
Despite having produced the highest
demand for coal-tar benzene, phenol now
became completely removed from the coal tar
industry, in terms of both supplying raw
materials and production technique.
4.6.2 Phthalic anhydride
Phthalic anhydride was industrialized in1896 by BASF as an indigo dye intermediate.
It was produced by stoichiometricallyoxidizing coal-tar naphthalene using anoxidant such as oleum. An atmosphericoxidation process was developed andSystematic Survey on Petrochemical Technology

87industrialized in 1916 using a vanadium
pentoxide catalyst. The development ofoil-modified alkyd resins in the late 1920s
saw an increase in demand for phthalicanhydride. In Japan, synthetic dye companies
started producing phthalic anhydride for theirown use in the 1930s, while in the 1940s it
started being marketed for use in alkyd resins.
In the United States, where o-xylene wasreadily available from catalytic reformate, theraw material switched from naphthalene too-xylene in 1945, using the same catalyst.
However, in Europe and Japan, the raw
material continued to be naphthalene fromcoal tar.
The rapid increase in PVC production
after the Second World War was
accompanied by a rapid increase in the
demand for phthalic ester as a plasticizer for
flexible PVC. In 1952, the first Henkel
process, which isomerizes orthophthalic acidmade from phthalic anhydride, wasdeveloped as a production method for
terephthalic acid, a raw material for polyester.
In 1958, Kawasaki Kasei Chemicals was thefirst in the world to industrialize this,followed by Teijin in 1963, resulting in
greater increased demand for phthalicanhydride. However, the first Henkel process
never became a mainstream method of
producing terephthalic acid; even in Japanproduction had stopped by the early 1970s,
and the demand for terephthalic acid did notlast long.
In 1960, Nippon Shokubai started
producing phthalic anhydride from o-xylene.
Later, a number of other companies alsotransitioned to production using o-xylene,
resulting in the rapid popularization of thismethod in the late 1960s, as shown in Fig.
4.23. Whereas production from coal-tar
naphthalene lost two of the naphthalenecarbons as carbon dioxide, o-xylene process
lost no carbons. Therefore, the naphthalene
method was expected to go into rapid decline.
However, following the 1970s oil crises,
there was a revival of the naphthalene
production method, as shown in Fig. 4.23.
The naphthalene method continues tocompete with the o-xylene method despite its
prevalence.
Unlike phenol, coal-tar-based production

88of phthalic anhydride continued long after the
petrochemical method came into being, andcontinued to compete with it. This is thought
to be firstly because the catalyst was almost
the same and there was no significant
difference in production process costs, unlike
phenol, and secondly because there was no
demand for naphthalene other than forphthalic anhydride, so it ensured theconsumption of products from byproduct coaltar.

Fig. 4.23 Change of production volume ofphthalic anhydride for each raw material after
the Second World War.

4.7 Products and technologies fromcoke syngas
Syngas is a gas mixture of carbon
monoxide and hydrogen. Up until the Second
World War, syngas was produced by passing
red-hot coke through air and steam.
Consequently, the forest of chemical products
from syngas came to being as the third of thecoal-based forests. When coal is carbonized,
it produces large quantities of coke oven gas,
which contains carbon monoxide andhydrogen. While the synthetic ammonia
industry started in the 1910s using thehydrogen from coke oven gas, coke oven gas
was not enough to supply all the ammonia on
its own. Therefore, large-scale production ofsyngas from coke started in the 1910s. Thiswas followed by the large-scale production ofsyngas in the 1920s as a raw material formethanol synthesis, as shown in Fig. 4.24.
Production of artificial petroleum fromsyngas also started in Germany in the 1930s,
using the Fischer-Tropsch process, increasing
the production of syngas even further.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 4.24 Major products made from syngas
before the emergence of petrochemistry.
Another use for syngas is carbon
monoxide. Carbon monoxide is used forcarbonylation of acetylene with a Reppe
reaction. Carbon monoxide also reacts withchlorine to produce phosgene, which is used
as a carbonylation agent in the production ofdye intermediates and other compounds.
Phosgene production and application
technology was used after the Second World
War to aid the upscaling of isocyanateproduction as a raw material forpolyurethane.
4.7.1 Methanol and formaldehyde
Methanolwas
extracted
frompyroligneous acid in the wood carbonizationindustry and used as a solvent and chemical
raw material. When methanol synthesis fromsyngas was industrialized in Germany in1925, wood-carbonization-based methanol
suddenly came to an end. Methanol synthesis
technology could be said to be an extensionofammoniahigh-pressure
synthesis
technology. It was industrialized in Japan in1932 by Gosei Kogyo (now Mitsui
Chemicals) based on research from the
Temporary Nitrogen Research Institute (later
the Tokyo Industrial Research Institute; now
the National Institute of Advanced Scienceand Technology). This was followed by anumber of other companies entering theindustry.
The main use for methanol was, and stillis, formaldehyde. Formaldehyde was used asa raw material for phenol resin, and was
produced by dehydrogenation or oxidative
dehydrogenation of methanol. A copper
catalyst process originated in Germany in
1889; in 1910, a silver catalyst process wasdeveloped as well, with a liquid phasereaction carried out with excessive methanol.

In Japan, Edogawa Industrial (nowMitsubishi Gas Chemical Company) started
production of formaldehyde in 1926, with anumber of other companies later following
suit. This was right when phenol resin
production was rapidly increasing, as shownin Fig. 4.25. By 1937, there was enoughformaldehyde being produced domestically tocover all phenol resin production. The
Organic Synthesis Industry Law designatedmethanol and formalin (formaldehyde) as raw
materials for phenol resin, aiming to boost
production from syngas.

Fig. 4.25 Change of production volume ofplastic and usage of phenols before theSecond World War.
While there were essentially no changes
in methanol production methods after theSecond World War, the raw material forsyngas shifted from coke to natural gas. In
Japan, Japan Gas Chemical (now Mitsubishi
Gas Chemical Company) started producing
syngas and methanol from natural gas from
Niigata as early as 1952. This was thefoundation of the Japanese petrochemicalindustry, as shall be discussed in Section
5.3.3. In 1958, Toyo Koatsu (now Mitsui
Chemicals) started methanol production using
natural gas from Mobara, while Akita
Petrochemical (a joint venture between
Sumitomo Chemical and Teikoku Oil) did thesame using natural gas from Akita, followed
in 1962 by Nissan Chemical Industries using
natural gas from Nagaoka and Kyowa Gas
Chemical using natural gas from Nakajo.
Petrochemical industries developed all overJapan using this rare domestic resource. Thus,
although the production technology formethanol, the core product for syngas
chemistry, had been developed in the coal
Systematic Survey on Petrochemical Technology

89

chemistry era, it continued on into thepetrochemical era and survived.
While many other raw materials forsyngas came along later, such as naphtha,
petrochemical waste gas and LPG, ultimately,
there was not enough affordable natural gas
in Japan, and it came to a sudden end in the
1980s.
An oxidation method of producing
formaldehyde using excessive air and an ironoxide or molybdenum oxide catalyst wasdeveloped during the Second World War andindustrialized by DuPont. Many of theprocesses in this gas-phase oxidation method
were developed after the war by eliminating
the reaction heat, and increasing theconcentration of formaldehyde produced.
Formaldehyde gained new areas of postwar
demand for urea resin and melamine resin,along with phenol resin. Urea resin inparticular had the highest production volumeof all plastics, overtaking phenol resin fromthe late 1940s to the early 1950s, as shown in
Fig. 4.26. It was used in adhesives andelectrical components, like phenol resin, andalso in tableware, buttons and other everyday
molded products, as it did not go brown likephenol resin.

4.7.2 Artificial petroleum
The Artificial Petroleum Production
Industry Law was enacted in 1940, aimed at
reinforcing artificial petroleum research,
industrialization, and increased production in
Japan as a matter of national policy. The
following four technologies were the maintechnologies targeted.
(1) Low-temperature coal carbonization(2) The Bergius process (direct liquefactionof coal)(3) The Fischer–Tropsch process(4) Oil shale retorting
Of these, the processes that became themainstay of production from 1941 to 1945
were (4) followed by (1), as shown in Table
4.4. Oil shale retorting (4) is an oldtechnology
that
hadalreadybeen
industrialized in the mid-19th century. Since
Japan had access to a thick oil shale layer
above the Fushun coal mine in Manchuria, it
had been exploring uses for it between 1912
and 1926. However, it was not very
economical to use European technology, as
the Fushun oil shale had a lower oil content
than the oil-rich European oil shale, at 6–8%.
Manchuria
Railway
developed
aninternally-heated retorting furnace, and built afactory in 1929. As the shale oil obtained washeavy, a Dubbs process pyrolysis furnace waspromptly brought in from the United States,and production started in 1935.
Table 4.4 Production volume of artificial
petroleum in Japan and Manchuria during theSecond World War

Fig. 4.26 Change of production volume ofmajor plastic after the Second World War.
Thus, formaldehyde maintained an
important position as a raw material forplastic for around a decade following theSecond World War. However, in the late
1950s, urea resin was dispossessed by PVC
as the chief among plastics, and furthermore
it was outstripped by polyethylene, themainstay product of petrochemistry, in theearly 1960s. Thus, formaldehyde lost its place
as a key raw material to acetylene, and thento ethylene.

90

The technology for (1) low-temperaturecoal carbonization was also very oldtechnology, originating in 18th-century
Germany. In Japan, Osaka Kanryu Kogyo
started production using this technology in

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1922. During the Second World War, eightlarge-scale plants were established: Chōsen
Chisso Hiryō in Hamgyong (1932), Japan
Iron & Steel in Muroran, Ube Nitrogen
Industry in Ube, Mitsubishi Mining in
Naihoro, Tokyo Gas in Tsurumi, Nissan
Chemical in Wakamatsu, Ube Yuka in Ube
and Sakhalin Artificial Petroleum in Naibuchi.
While six of the plants used non-caking coal
as a raw material and were able to use
introduced technology from Germany, theJapan Iron & Steel plant in Muroran and theTokyo Gas plant in Tsurumi used caking coal
as a raw material and so had to use their own
technology.
By contrast, technology for (2) the
Bergius process (direct liquefaction of coal)and (3) the Fischer–Tropsch process wasdeveloped early in the 20th century inGermany. The Bergius process (2) was
developed in the 1910s by Friedrich Bergius.
In this process, coal powder was added toheavy oil and then liquefied by high-pressurehydrogenation. IG Farben acquired the patent
from Bergius in 1927 and carried out further
research and improvements. A low levelsulfur poisoned catalyst was developed, andindustrial production started in 1932 using
lignite as a raw material. The resulting
product was high in aromatic hydrocarbons
and served as the artificial petroleum mostsuitable for aviation fuel. Since IG Farben
kept the technology a secret, in Japan, thenavy fuel factory carried out its own
independent research. In 1935, the navy
commissioned the construction of plants inFushun by Manchuria Railway and Aoji by
Chōsen Chisso Hiryō. However, these neverreached sufficient production levels by theend of the war as the technology wasincomplete, as shown in Table 4.4.
Meanwhile, the Fischer–Tropsch process (3)used a cobalt catalyst to synthesize liquidhydrocarbons from syngas at pressure levels
from 1–10 atm. Since the resulting productwas a straight-chain hydrocarbon, it had thedisadvantage of a low octane number. It also
had a wide carbon number distribution andwould not always produce adequate quantities
in the necessary gasoline fraction.
Nevertheless, when the German patent wasdisclosed in 1925, researchers all around theworld started working on how to improve it.
In Japan, this was done at the Genitsu Kita
Laboratory at Kyoto University, and later
developed independently using an ironcatalyst.
In
Germany,
theprocesswas
industrialized in 1936 by Ruhrchemie, with anumber of other companies following suit. As
a result, Germany had a production capacityof 740,000 tons during the Second World
War, with production levels reaching as highas 570,000 tons. In Japan, Mitsui Mining
signed a technology licensing agreement as
early as 1936, constructing a plant in Omuta
and starting operation in 1940. While thecompany underwent a variety of changes
during the war, the majority of product madeusing the Fischer–Tropsch process wasproduced at this factory in Omuta, as shownin Table 4.4.
In 1937, the government enacted theImperial Fuel Industry Company Act, andestablished a special company for the purposeof producing artificial petroleum. Plants using
a 10 atm increased pressure method wereconstructed in Takigawa (Hokkaido Artificial
Petroleum) and Amagasaki (Amagasaki
Artificial Petroleum), and the Takigawa plant
started production in 1943. In 1944, theOmuta, Takigawa and Amagasaki artificial
petroleum companies merged to form the
Nippon Artificial Petroleum Company, withthe aim of boosting artificial petroleum
production through technology exchange,
utilizing materials and facilities, dedicating
Omuta to catalyst production and otherinitiatives. However, although the Fischer–Tropsch process was where the government
spent most of its efforts, artificial petroleum
production using this method also remained
low at the end of the war, as shown in Table
4.4.
The artificial petroleum division at
Omuta branched out on its own as Miike
Gosei Chemical Industry in 1946, using theartificial petroleum plant coke ovens andsyngas facilities to supply syngas toneighboring Toyo Koatsu as a raw material
for ammonium sulfate. The company later put
the rest of the unused artificial petroleum
facilities to use and started producing
petroleum-based synthetic detergent.
Systematic Survey on Petrochemical Technology91

Of all the Mitsui chemical companies,
Miike Gosei Chemical Industry is notable as
the first postwar petrochemical industry andfor having played a pioneering role indomestic petrochemical production. The
company’s
experiencewith
artificial
petroleum technology arguably gave it theinsight to see the potential in the
petrochemical technology developed in the
United States. However, in the late 1950s, as
the raw material for ammonia gas started
changing in earnest from coke and coalgasification to petroleum gasification, natural
gas and petrochemical waste gas, Miike
Gosei could no longer support its coke oven
operations. Thus, all operations using
inherited artificial petroleum facilities cameto an end.
There are various opinions on the role
played by artificial petroleum technology inthe formation of petrochemical technology.
IG Farben, which had worked on the directliquefaction of coal, (2) above, collaborated
with the Standard Oil (NJ) and othercompanies in the early 1930s by providinghydrogenation patent rights. Since thiscontributed to the development of heavy oilhydrocracking
technology
and
other
American technologies, there is an idea that
this formed the basis for the creation of
petrochemical technology. However, heavy
oil pyrolysis technology developed in the
United States in the 1910s, and ethane steam
cracking technology in the early 1920s,
before artificial petroleum technology wasdeveloped. Accordingly, it is difficult to givecredence to the idea that artificial petroleum
technology gave rise to petrochemical
technology. In terms of mastering large-scale,continuous operation technology, methanol
and artificial petroleum can be viewed ashaving laid the foundation for the readyadoption in the 1950s of American
petrochemical technology in areas like
Europe and Japan, where no large-scale
petroleum refining technology had developed.
Bibliography[1] T. Watanabe, ed., “History of thedevelopment of the modern Japaneseindustries 13: chemical industries (I),”
Kojunsha, 1968.

92

[2]

T. Watanabe, ed. “History of postwar
Japanese chemical industries,” The
Chemical Daily, 1973.
[3] T.
Iijima,“Japanesechemicaltechnology,” Kogyo Chosakai, 1981.
[4] T. Takahashi, “History of the chemicalindustry,” Sangyo Tosho, 1973.
[5] “History of the Japanese chemical fiberindustry,” Japan Chemical Fibers
Association, ed., Japan Chemical Fibers
Association, 1974.
[6] H. Uchida, “New revised edition: The
synthetic fiber industry,” Toyo Keizai,
1970.
[7] K. Fukushima, “Viscose rayon (1), (2),(3),” Kagaku Kōgyō., pp. 623-631,
711-719, 800-807, 1988.
[8] I. Iwai, Polyfile., vol. 52, 2013, pp.
12-15.
[9] H. Ōsuga, Journal of Packaging
Science & Technology, Japan, vol. 22,
pp. 254-261, 366-373, 2013.
[10] “A 30-year history of the alcoholmonopoly,” Ministry of International
Trade and Industry, Chemical Industry
Bureau,Alcohol
Division,ed.,
Fermentation Association of Japan,
1969.
[11] “A 50-year history of the alcoholmonopoly Business,” Ministry ofInternational Trade and Industry, Basic
Industries Bureau, ed., Japan Alcohol
Association, 1987.
[12] K. Kurono, “Alcohol and anhydrous
alcohol,” Senbai Kyokai, 1937.
[13] B. Katō, ed., “The history of alcohol inJapan: Its industries and technologies,”
Kyowa Hakko Kogyo, 1974.
[14] “A 50-year history of Sanraku,”
Sanraku History Compilation Office,Sanraku, 1986.
[15] “History of Japanese naval fuel, I & II,”
Fuel Society, ed., Hara Shobo, 1972.
[16] T.
Kume,“Earlypolyethylene
production in Japan,” Journal of theSociety of High Pressure Gas Industry,
vol. 21, pp. 274-281, 1957.
[17] “20th-century
Japanesechemistrytechnology,” The Japanese Society for
the History of Chemistry, ed., The
Japanese Society for the History ofChemistry, 2004.

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[18] “Magazine for the 50th anniversary of
the institute,” Hodogaya ChemicalInstitute, ed., Hodogaya Chemical
Central Research Institute, 1989.
[19] “The 200-year journey of Shiono Koryo
Kaisha Limited,” Shiono Koryo Kaisha,ed., Shino Koryo Kaisha, 2010.
[20] “From there to there: Kyowa Hakko’s
50-year journey and the foundation for
the new century,” Kyowa Hakko 50th
Anniversary
History
Compilation
Committee, ed., Kyowa Hakko Kogyo,
2000.
[21] “A 70-year history of Kao Sekken,”
Kao Sekken, 1960.
[22] “100-year history of Kao,” Kao History
Compilation Office and Japan BusinessHistory Institute, Kao, 1993.
[23] H. Nagata, “The organic synthesis
industry law,” Journal of the Society of
Rubber Science and Technology, Japan,
vol. 13, pp. 537-544, 1940.
[24] “Chemical industries: The postwar
half-century and 21st century prospects,”
Chemical Economy Research Institute,
1996.
[25] “History of the carbide industry,”
Calcium Carbide Association, ed.,Calcium Carbide Association, 1968.
[26] K.
Ishibashi,“Petrochemicals,”
Kyoritsu Shuppan, 1953.
[27] “German organic synthesis technology:
PB report compilation I,” The Societyof Synthetic Organic Chemistry, Japan,
ed., Maruzen, 1954.
[28] S.
Murahashi,“StudiesofReppe-reaction in Japan”, Journal of
Synthetic Organic Chemistry, Japan,
vol. 13, no. 5, pp. 195-202, 1955.
[29] H. Akune, “Development and futurechallenges of synthetic petroleum (1),(2)”, Kagaku Kōgyō, pp. 1058-1087,
1988; pp. 99-111, 1989.

[30] E. Munekata, “Coal liquefaction byinternally-heatedreactiontube,”
Kagaku Kōgyō, pp. 189-199, 1989.
[31] M. Esaki, “Synthetic methanol (1), (2),”Kagaku Kōgyō, pp. 958-967, 1036-1043,
1990.
[32] “History of Mitsui Toatsu Chemicals,Inc.,” Mitsui Toatsu Chemicals, Mitsui
Toatsu Chemicals, 1994.
[33] “An outline of the development of polyvinyl chloride technology in Japan,
including a description of historicalmaterials,” Survey Report on the
Systematization of Technologies, no. 1,
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[34] “Systematic survey of technologicaldevelopment in laundry soaps anddetergents,” Survey Report on the
Systematization of Technologies, no. 9,
National Museum of Nature andScience, March 2007.
[35] “Systematic survey of the developmentof paint technologies,” Survey Reporton the Systematization of Technologies,
no. 15, National Museum of Nature andScience, March 2010.
[36] “Systematic survey of dye technologies,”
Survey Report on the Systematization ofTechnologies, no. 16, National Museumof Nature and Science, March 2011.
[37] “Historical development of pesticides inJapan,” Survey Report on the
Systematization of Technologies, no. 18,
National Museum of Nature andScience, March 2013.
[38] H.A. Wittcoff, B.G. Reuben, J.S.
Plotkin “Industrial Organic Chemicals,”
Wiley, New York (Third Ed.), 2013.
[39] S. Kodama, “The road to research anddevelopment,” Tokyo Kagaku Dojin,
1978.

Systematic Survey on Petrochemical Technology

93

5 History of the petrochemical industry
As mentioned at the beginning of theprevious chapter, petrochemistry began as asmall forest in the United States in the 1920s,
existing alongside and competing with forestsfrom other more prevalent materials for 30
years. The field as we know it today did notexist in Europe and Japan; however, it began
making inroads into Europe in the 1950s andchanged dramatically with the incorporationof European chemical technology. Crude oil
was discovered in the Middle East in the
1930s, but major exports did not begin until
the 1950s, after which time it became acheaper source of energy than coal andproducts derived from fermentation. This is
another major reason for the change in the
petrochemical industry.
The 1960s proved to be a period of Sturm
und Drang for petrochemistry. Researchers in
the field were developing a rapid successionof technologies that could enable the cheaper
production of products typically yielded
through other chemical processes. Thus,
petrochemistry soon overtook other fields
engaged in the mass production of chemical
products to assume sole possession of thechemical industry. From the 1970s onward,
several crises, from environmental andenergy issues to chemical pollution andglobal warming, have threatened to unseat
petrochemistry. This has led to a partial
revival of the fields of oleochemistry andfermentation chemistry, with some countries,
such as China, trying to put policy measuresin place to restore coal chemistry for the sakeof economic security. For over 50 years,
however, the field of petrochemistry has
successfully maintained its position at thefoundation of the chemical industry byoffering solutions to various problems thathave arisen.
From its origins in the developed nations,petrochemistry began to spread to every
corner of the world in the 1970s.
Consequently, regions rich in raw materialsof oil and natural gas came to develop astrong competitive edge in the field of
petrochemistry. In many cases, this shift waspolitically motivated, such as Saudi oil prices,94

and fraught with many issues. Since letting
the chemical industry deteriorate was not an
option, regions that were not blessed withthese resources went through a process oftrial and error to keep petrochemistry alive.
From this came initiatives in functional
chemistry that stretched beyond theconventional scope of the field of
petrochemistry as well as the development of
new technologies with the potential totransform petrochemistry from its roots.

5.1 The 1920s: An industry is born in
the United States
The oil industry in the United States
began with the successful drilling of an oil
well in Pennsylvania by Edwin Drake in 1859.
By the end of the 19th century, a raft of newoil fields had sprung up across the UnitedStates, in states such as Illinois, Kansas,
Oklahoma, Texas, Louisiana and California.
Initially, kerosene was the primary driver ofthe demand for oil; however, when the Model
T Ford went on sale in 1908 and ushered inan era in which the automobile became
accessible to everyone, the demand for oil in
the United States shifted to gasoline, which
remains the case to the current day.
It was in this context that oil refining
technologies were developed, as shown in
Table 5.1, and from this grew thepetrochemical industry.
5.1.1 Thermal cracking of heavy oil
The oil refining system for continuous
distillation was introduced in 1910. Gasoline
accounted for a large portion of the oil
demand in the United States, but thedistillation of crude oil resulted in an excessof heavy oil. Therefore, to increase thegasoline yield from crude oil, refineries began
to thermally crack oil, and in particular,
heavy oil. The Burton process was developedin 1912, followed by the Dubbs process in
1914, and multiple other thermal cracking
processes
weredeveloped
thereafter.
Thermally cracked heavy oil yields gasoline
and other light distillates, as well as

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

petroleum waste gas containing hydrogen,alkanes and lower olefins (i.e. ethylene,

propylene and butylene) and large amounts ofcarbon.

Table 5.1 Oil refinery and petrochemical industry in the U.S. in the 1920s to the early 1930s(excluding organic chemicals or polymers made from raw materials other than natural gas or oil)

5.1.2. The birth of the petrochemicalindustry
In 1920, chemists at Standard Oil (NJ)
Bayway Refinery caused a reaction between
the propylene from petroleum waste gas andsulfuric acid to create propyl sulfate, which
they then combined with water to produce
Isopropyl alcohol (IPA). This is considered tobe the beginning of the petrochemicalindustry. Isopropyl alcohol was oxidized togive acetone, and also used as a solvent.
Using a similar technology, Shell altered theconcentration of the sulfuric acid in butylene,
yet another substance in waste gas, tosuccessfully separate out n-butylene andisobutylene. In 1931, the company went on to
produce sec-butyl alcohol and MEK fromn-butylene. MEK, like acetone, was also used
as a solvent.
5.1.3 Steam cracking of ethane
Meanwhile in 1920, Union Carbide andCarbon founded a subsidiary called Carbide
and Carbon Chemicals which began
producing ethylene in its Clendenin, West
Virginia facility by the steam cracking of
ethane separated out from natural gas. Unlike
the old process that entailed the thermal
cracking of heavy oil at a high temperature
under high pressure, this innovative method

reduced partial pressure and shortened
retention time with the addition of steam.
Thus was born the method for steam cracking
oil and natural gas, which remains to this day
an important technique for the production ofbasic petrochemicals. The technique used toseparate ethane from natural gas and ethylene
from product gas was low-temperature
distillation. Linde Air Products, one of thefour companies involved in the establishmentof Union Carbide and Carbon, contributed
significantly to the development of thistechnology in 1917. Linde AG, the German
parent company of Linde Air Products
initially achieved the successful industrial
application of air liquefaction equipment andequipment that used the distillation of liquid
air for separation from around the end of the
19th century to the turn of the 20th century(see Section 2.3.2).
5.1.4 Development of ethylene products
In 1925, Union Carbide and Carbon
reacted ethylene and chlorine with water tocreate ethylene chlorohydrin, which it thenhydrolyzed to produce EG. At that time, EG
was solely used as automotive antifreeze, andthe company held a monopoly over thesubstance up until the Second World War
broke out. By developing a use for ethylene
Systematic Survey on Petrochemical Technology

95dichloride (EDC), a byproduct from theproduction of ethylene chlorohydrin, thecompany also pioneered the market for dry
cleaning solvents. In 1929, the company
began
producing
polyvinyl
chloride(monomer), which was created from thethermal cracking of EDC. Around this time inGermany, a polyvinyl chloride was developed,
although polyvinyl chloride had beenrecognized as a compound since the 19th
century. Union Carbide and Carbon had
also attempted to polymerize this compound,but failed for the lack of thephotostabilization and molding technologies
required to produce polyvinyl chloride. Notlong after this, however, the company
succeeded in developing a special polyvinyl
chloride by copolymerizing polyvinyl
chloride and vinyl acetate; this polyvinyl
chloride started being used by the vinyl
record industry in the United States.
In 1926, Union Carbide and Carbon
synthesized
ethyleneoxide
bydehydrochlorinizing ethylene chlorohydrin in
an alkaline solution. As mentioned in Section
3.4.2 (2), ethylene oxide is a highly reactive
organic intermediate that now has myriad
applications. At that time, however, it wasreacted with cellulose to produce Cellosolve,
an ingredient in lacquer solvent. In 1931, theFrench chemist T.E. LeFort invented amethod for creating ethylene oxide by the
direct oxidation of ethylene using a silver
catalyst. Union Carbide and Carbon adopted
this method, and launched the first industrial
application of this method in 1937. After this,it was found that EG could be produced byreacting ethylene oxide with water, thereby
eliminating the need to first produce ethylene
chlorohydrin. In the early days of thepetrochemical industry, the invention of
methods like LeFort’s, which permitted the
direct oxidation of olefins with a solid
catalyst, was astonishing.
In 1930, Union Carbide and Carbon
began producing ethanol from ethylene by
applying the sulfuric acid process to ethylene.
This was the same technique that Standard
Oil (NJ) used to produce IPA and Shell used
to produce sec-butyl alcohol, as mentioned
previously. Around this time, Union Carbide
andCarbonalso
beganproducing96

acetaldehydebyoxidizing
ethanol.
Coinciding with this, the company ceased
producing acetylene-based acetaldehyde at its
Niagara Falls plant.
In 1922, Standard Oil (NJ) begancommercially manufacturing tetraethyl lead, agasoline octane enhancer discovered by GM
the year before at its Bayway refinery. The
ethyl chloride used in this process wasderived from ethylene contained in the waste
gas produced during the thermal cracking ofheavy oil. There was more ethylene in thewaste gases produced during thermal
cracking than in the catalytic cracking ofheavy oil, a process that was developed later
and adopted widely. In 1923, DuPont also
opened a factory to produce tetraethyl lead.
DuPont used fermentation ethanol to produce
ethyl chloride. GM and Standard Oil joined
forces to establish a tetraethyl leadmanufacturer called Ethyl, thus putting the
production of the compound into high gear.
To supply Ethyl with the ethylene it needed,Standard Oil built a propane steam cracking
facility to replace the old practice ofcollecting ethylene from heavy oil pyrolysis
waste gas. This technology was based on theethane steam cracking process used by Union
Carbide and Carbon, but using propane
yielded more products, so new separation andcollection technologies were needed. The
company also pursued research into the steam
cracking of naphtha and gas oil, as will be
discussed in the next section.
Thus, the petrochemical industry
gradually grew in step with the expansion of
the oil refining industry during the 1920s andthe 1930s. Notwithstanding, the demand forcompounds other than tetraethyl lead waslimited to solvents and antifreeze agents suchas oxygen-containing alcohols and ketones.
At this point, no connection had been madewith polymers, and the industry remained
small. The biggest oxygen-containing
compound of this era was still fermentation
ethanol. Therefore, even though it is true thatthe petrochemical industry originated in the
United States, its scale remained limited.
5.1.5

Wood chemistry and coal chemistry
usher in the polymer era
The United States of the 1920s was the

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

world’s first mass consumer society. In 1930,
the first supermarket was opened. Concurrent
with this, the use of plastic began to spreadthroughout the United States from the 1920s
onwards, ushering in the dawn of an era ofpolymer materials. These polymers, however,were not derived from oil, but from wood andcoal. The polymers that were frequently usedin the United States in the 1920s included
celluloid, phenolic resin, viscose rayon andacetate. By the 1930s, these were joined bymoisture-proof cellophane, urea resin,
polyvinyl acetate, polyvinyl chloride,methacrylate resin and chloroprene rubber.
Nylon was developed at the end of the 1930s,
leaving a lasting impression on people theworld over, and marking the dawn of thepolymer era, not only for the United States,
but for the rest of the world as well.
Other than the United States, many of thecountries that developed these polymers werein Europe. Consumerism had yet to take root
there at that time. Plastic was seen as a cheap
substitute for other materials, and its benefits,
such as the freedom it allowed in productdesign, were not as highly regarded as they
were in the United States. Accordingly, thepolymer age had not yet begun in Europe.
In Japan, meanwhile, the industrial
production of celluloid and viscose rayon had
begun in the early 20th century and started
booming in the 1920s. By 1937, Japan had
become the world’s biggest producer of bothof these polymers (see Section 4.1). This,
however, was merely in response to export
demand from the United States; Japan had not
yet experienced the full effects of consumer
society. The production of synthetic
compound phenol resin began in the 1910s,
and the use of electric lamps, radio parts andotherelectricalcomponents,
rayon
manufacturing pots and spinning machinerycomponents started spreading in the 1930s, ,although Japan was still a far cry from thedawning of the polymer era.

5.2 The 1940s: Advances in theAmerican petrochemical industry
After roughly 20 years, the petrochemicalindustry in the United States transitioned out
of infancy with a major boom in the Second

World War, with the mass production ofsynthetic rubber as the catalyst. An outline of
the advancements in oil refining andpetrochemical technologies in the latter halfof the 1930s can be found in Table 5.2.
Table 5.2 Oil refinery and petrochemicalindustry in the U.S. in the late 1930s to the1940s(excluding organic chemicals or polymers
made from raw materials other than natural
gas or oil)

5.2.1 Catalytic cracking of heavy oil
In 1938, French engineer Eugene Houdry
developed the fixed-bed catalytic cracking
process as a replacement for the thermal
cracking of heavy oil, with the aim ofincreasing gasoline yield. Once thistechnology was adopted in the United States,
it spread like wildfire. Fluidized catalytic
cracking (FCC), the process currently usedaround the world today, was developed byStandard Oil (NJ) and was adopted at their
Baton Rouge refinery in 1942. However,
FCC was not widely adopted in the UnitedStates or anywhere else in the world until
after the war. Since catalytic cracking
employed a different reaction mechanism
from thermal cracking, it generated much
more petroleum waste gas. This, however,
had a different composition from thepetroleum waste gas generated by thermal
cracking; it contained very little ethylene andlarge amounts of propylene and butylene.
With the widespread adoption of catalytic
cracking, the supply of lower olefins began toskyrocket in the United States in the early
1940s. Thus began the fully-fledged
development of olefin chemistry.
5.2.2

Mass production of gasoline-basedmaterials from petroleum waste gas
Systematic Survey on Petrochemical Technology

97

As mentioned previously, alcohol is
produced by causing a reaction between an
olefin and sulfuric acid. By changing thereaction conditions and using hot sulfuric
acid, butylene undergoes acid-catalyzed
dimerization to generate polymer gasoline[Footnote 1]. This polymer gasoline can thenbe hydrogenated to obtain isooctane.
Isooctane was a key ingredient in aviation
fuel, which has to have a high octane number.
Shell opened an isooctane plant in 1934, andStandard Oil (NJ) soon followed suit.
In 1939, both companies succeeded incommercially producing alkylate gasoline
through the alkylation of isobutane withbutylene and propylene. As opposed topolymer gasoline, alkylate gasoline does notneed to undergo hydrogenation after
dimerization. In 1942, Shell successfully used
an acid catalyst to synthesize cumene frombenzene in coal tar and propylene inpetroleum waste gas. Cumene, polymer
gasoline, isooctane and alkylate gasoline all
have high octane numbers and were used as
keyingredientsingoodqualitygasoline-based materials. In particular, they
were in high demand as essential aviation
fuels during the Second World War. Whilethese gasolines were mass produced using
olefin chemistry, it was the petroleum
refining industry that created and used them,rather than the chemical industry.
Also in 1939, German company IG
Farben developed a process for the catalytic
reforming of naphtha (using a molybdenumoxide-alumina catalyst). During the war, thistechnology was applied by Standard Oil (NJ),Standard Oil (Indiana), and the Kellogg
Company, which helped boost the supply ofhigh-octane gasoline. However, since a
sufficient supply of aromatic hydrocarbons tothe chemical industry in the United States
could be obtained from the distillation of coaltar, it was exclusively obtained this way
during the Second World War, other thansome obtained from toluene [Footnote2] 1..
5.2.3

Steam cracking of naphtha[Footnote 1] Polymer gasoline is an imprecise term used in the
petroleum refining industry. It is an established term, although as ahydrocarbon with around C8, it is not a true polymer.
[Footnote 2] The demand for toluene during the war focused heavily
on its use as a raw material for explosives.

98

As mentioned previously, Standard Oil(NJ) successfully developed a method for thesteam cracking of naphtha, which it put into
commercial use in its Baton Rouge refinery in
1941. Unlike the processes based on ethaneand propane, the use of naphtha enabled the
production of butadiene, an importantcompound for the United States during theSecond World War, as outlined below. In
order to obtain butadiene from a C4 fraction
from the steam cracking of naphtha, Standard
Oil (NJ) first developed an extraction method
using a copper ammonia solution.
5.2.4

Synthetic rubber production
increases
During the Second World War, theUnited States government put the Synthetic
Rubber Program into action, which was aplan to build factories to boost the productionof synthetic rubber. This served as the largest
trigger for the advancement of the American
petrochemical industry. As the Japanese army
had captured the Malay Peninsula andIndonesia early in the war, it became clear to
the United States that it would soon suffer ashortage of natural rubber. Accordingly, thegovernment devised a plan to dramaticallyincrease the production of synthetic rubber.
The United States needed a particularly large
amount of SBR, which was used to make tires(see Section 4.5.2 (3)). It also needed thehighly oil-resistant NBR. These synthesizing
technologies were part of IG Farben’s
synthetic rubber research conducted under an
expanded technology alliance agreement
concluded between IG Farben and Standard
Oil (NJ) in 1930; thus, it was throughStandard Oil (NJ) that the government
became aware of these technologies.
Accordingly, the government was able toexecute its Synthetic Rubber Program within
an extremely short time frame. By contrast, as
mentioned in the previous chapter, Japan wasmuch further behind in its efforts tocommercialize synthetic rubber.
5.2.5 Butadiene
There were several avenues for the
supply of butadiene, the primary raw material
in synthetic rubber. In 1943, Humble Oil, asubsidiary of Standard Oil (NJ), built a

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

butylene dehydrogenation plant. When the
supply of butylene from petroleum waste gas
grew short, it then developed a method todehydrogenate butane (i.e. the Houdry
process). This technology was abandoned
after the Second World War due to its highcost. In addition, the company also used theaforementioned process developed byStandard Oil (NJ) to extract butadiene from aC4 fraction from the steam cracking of
naphtha. Surprisingly, however, the greatest
source of butadiene was fermentation ethanol.
In the United States, fermentation ethanol
was made from corn. Due to the influence of
the agricultural lobby, the mainstream
process was a long one: acetaldehyde andaldol were condensed from fermentation
ethanol, then hydrogenated and dehydrated.
During the war, Union Carbide significantly
shortened the process with the developmentof a new method for producing butadiene bycondensing ethanol and acetaldehyde using asilica catalyst. Union Carbide mass produced
synthetic ethanol from the ethylene obtainedby the steam cracking of ethane and used thisas the raw ingredient for butadiene.
5.2.6

Linking olefin chemistry andpolymers
Styrene, the other main ingredient in SBR
synthetic rubber, was first put into production
by German company IG Farben in 1930 in
the form of polystyrene. In the United States,
Dow Chemical began producing polystyrene
in 1937, but the scale of the operation was so
small that almost no one in the market knew
about it. However, during the Second World
War, styrene became an indispensable raw
material for SBR tires, so efforts to step up
production were undertaken by four
companies: Dow Chemical, Monsanto,
Koppers, and Union Carbide. The benzene
for synthetic rubber was obtained entirely
from coal tar. During the war, styrene
demand was essentially driven by SBR alone.
Meanwhile, polystyrene production volume
remained small, as it was primarily only usedby the military as an insulating material forradars. Another essential material used inradar insulation was low-density polyethylene(LDPE), invented by British company ICI in
1933 and put into production in 1939. In The

United Kingdom, fermentation ethanol was
the raw material used to make ethylene.
During the Second World War, ICI provided
its technology to the United States, and in
1943, both Union Carbide and DuPont
opened ethylene factories.
Meanwhile, Standard Oil (NJ) developed
and commercialized butyl rubber, which has
an excellent gas barrier, making it ideal foruse in tire tubes. This was a special rubber
produced by the polymerization of
isobutylene and a small amount of butadiene
at low temperatures. After the war, isoprene
obtained from the steam cracking of naphtha
was used in place of butadiene.
In this way, the United States
petrochemical industry, which had been
unable to create any lasting linkages withpolymers up through the 1930s, finally started
doing so during the Second World War withpolymers such as synthetic rubber,polyethylene and polystyrene. Meanwhile,
private-sector demand shrank during theSecond World War for celluloid, phenol resin,urea resin, polyvinyl chloride, methacrylate
resin and nylon, which had already ushered in
the polymer age in the United States in the
1920s and 1930s, while demand coming
almost exclusively from the military led to
stepped up production. For example, thenylon fibers that first went on sale in the formof stockings were used during the war forparachutes, tents and ropes as well as avariety of other wartime goods, such as
mosquito nets used to protect soldiers in thetropics. Polyvinyl chloride, used to make soft
vinyl chloride products, was also important asa flame-retardant wire coating material.
However, these plastics and synthetic fibersthat were mass produced in the United States
during the war were still mostly derived fromwood and coal.
5.2.7 Interest in polymers increases
The United States army brought with it
American-made plastic and synthetic fiber
products to the European front, resulting inthe superiority of these products coming to berecognized in Europe as well. Meanwhile, inGermany, which had also ramped up its
synthetic rubber production during the war
like the United States had, demand for
Systematic Survey on Petrochemical Technology

99butadiene increased rapidly. The demand forthe antifreeze EG and ethylene, the source ofthe styrene used in synthetic rubber, also
skyrocketed. In Germany, the primary raw
material for these chemical products was coal(from acetylene, coke oven gas and coal tar),but fermentation ethanol was also an
important raw material.
Products that were manufactured in the
United States as important military goods
were also known in Japan, such as polyvinyl
chloride, polyethylene, polystyrene, synthetic
rubber and nylon fiber. Japan scrambled toramp up its domestic production of thesegoods, and, as mentioned in the previous
chapter, research was undertaken, backed by
the government and the military. The raw
materials
for
these
products
weredomestically-available coal and fermentation
ethanol.
Researchanddevelopment
progressed despite the lack of informationfrom the West, and, during the war, Japan
managed to put several polymers into
production, although production volumes
were minimal. 1940s Japan had yet to see thedawning of the age of synthetic polymers thatwould replace the cellulose-based polymersof the 1930s.

5.3 The 1950s: The fusion of American
petrochemical technologies andEuropean chemical technologies
By the 1950s, the petrochemical industry
was no longer confined to the United States;
it had spread to Europe and Japan. The
integration of petrochemical technologies
with manufacturing technologies for the mass
production of chemical products, which had
made advances in Europe even before
petrochemistry began, kick-started a massive
expansion of those products and technologies.
Since Europe and Japan did not produce
their own ethane-containing natural gas, theprimary method for obtaining basic
petrochemicals was the steam cracking of
naphtha and other light petroleum products.
The steam cracking of naphtha and othersubstances yielded a variety of olefins andcracked gasoline. Cracked gasoline became
the main source of aromatic hydrocarbons
due to the large amount and high100

concentration of these compounds it contains.
Meanwhile, in the United States, a method
was developed to extract and recoveraromatic hydrocarbons from catalyticallyreformed naphtha, mass produced in an effort
to obtain high-octane gasoline, and it wassoon adopted widely. This technology was
also used to recover aromatic hydrocarbons
from cracked gasoline. Throughout the 1950s,
the source of aromatic hydrocarbons in boththe United States and in Europe shifted
significantly from coal tar to petroleum. The
same shift began in Japan in the late 1950s,
about five years behind Europe.
In the field of industrial organic chemical
production technologies, a direct catalytic
hydration process was also developed inplace of the sulfuric acid process traditionallyused in the production of ethanol and IPA;
this was commercially applied in 1948. Thus,
technologies were developed that used
catalysts, in particular solid catalysts toachieve direct production, or production oforganic intermediates from olefins andaromatichydrocarbons,
and
these
subsequently became the mainstream in the
petrochemical industry.
In the 1950s, polymer production
technology took a great leap forward with thediscovery of Ziegler-Natta catalysts. The
discovery of these organometallic complex
catalysts not only became, and continues tobe, the key driving force behindadvancements in polymer production
technology, it also triggered dramatic leaps inthe petrochemical industry in terms of
production volume. What is notable is that
this discovery was made in Germany and
Italy, not in the United States, which had
been the birthplace of the petrochemicalindustry. By this point, the United States nolonger had sole reign over petrochemical
technologies; this was the beginning of new
advances through the marriage between
American and European technologies.
5.3.1

The American petrochemicalindustry expands(1) Olefins
From the 1920s to the 1940s, the growthof the petrochemical industry in the UnitedStates was based on olefins, such as thoseNational Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)sequestered from petroleum refining waste
gas and those obtained from steam cracking
ethane and propane in natural gas. By the
1950s, the steam cracking of ethane andpropane in natural gas became themainstream method for producing ethylene in
the United States. At the same time, the rapid
spread of fluidized catalytic cracking (FCC)
led to an increased supply of propylene andbutylene, thereby achieving a production
system for other olefins in which the key
ingredient was waste gas from oil refining.
Naphtha steam cracking was still being
used, although it only accounted for a small
percentage of olefin production in the UnitedStates. In contrast to steam-cracked naphtha
gas, steam-cracked ethane gas and oil refining
waste gas contained almost no butadiene;
accordingly, the supply of butadiene in the
United States was obtained via butylene
dehydrogenation. Furthermore, the practice ofobtaining butadiene from fermentation
ethanol was abandoned in peacetime for costreasons.
(2) Aromatic hydrocarbons
Major changes also occurred in the
production of another basic petrochemical,
aromatic hydrocarbons, which were supplied
exclusively from coal tar during the Second
World War. During the war, a process for thecatalytic reforming of naphtha was developed
and commercialized. Not long afterwards, in
1949, UOP developed the Platforming
Process, which used platinum as a catalyst
instead of the conventional molybdenumoxide. In no time at all, this became theprimary process used for catalytic reforming.
In 1952, UOP developed the Udex process torecoveraromatichydrocarbons
fromreformates (i.e. mixtures of hydrocarbons). It
has been known for some time thatreformates contain large quantities ofaromatic hydrocarbons, but, in contrast tocoal tar distillation, reformates contained
many azeotropes, meaning that thesearomatic hydrocarbons could not be
efficiently recovered by distillation. The
Udex process enabled the recovery ofaromatic hydrocarbons from reformates byskillfully combining extraction with a solvent
mixture of glycol and water and extractive

distillation. Meanwhile, having peakedaround 1950 steel production in the UnitedStates began to decline. As a result, coal tar
production also began to decline, andmanufacturers were becoming unable to copewith the rapidly growing demand foraromatichydrocarbons
neededforpolystyrene, nylon and other products.
Between 1950 and 1959 in the United States,
the source of aromatic hydrocarbons shifted
completely from coal tar to reformates andcracked gasoline, obtained from the steam
cracking of naphtha. In particular, as theUnited States relied primarily on the steam
cracking of ethane, cracked gasoline supplies
were scarce, and aromatic hydrocarbons had
to be sourced mainly from reformates.
(3) Industrial organic chemicals
The alcohol production processes thatgave birth to the petrochemical industry in the
1920s also experienced major technologicalinnovation in the 1950s. A direct hydration
process using a solid catalyst was developed
and put into commercial use, replacing theold indirect hydration process using sulfuric
acid. With the sulfuric acid process, olefins
were reacted with sulfuric acid to createorganosulfate, which was then hydrolyzed toobtain alcohol. The diluted sulfuric acidbyproduct was concentrated by heating andthen reused. In essence, this process was a
combination of stoichiometric reactions. By
contrast, Shell developed and commercialized
a method to synthesize ethanol by using aphosphate-silica catalyst to react ethylene inits gas phase directly with steam in 1948. The
same process was also developed by British
Petroleum (BP), who achieved the industrial
application of it in 1951. Also in 1951,
British company ICI commercialized an IPA
production method involving a direct reactionof propylene with steam using a tungsten
oxide-silica catalyst.
As previously mentioned, manufacturers
in the United States were mass producing
cumene from propylene and benzene for use
in high-octane gasolines. Again in 1951,
Hercules Inc. developed a method for the
co-production of phenol and acetone fromcumene. This process was first applied
industrially in Canada in 1953. The following
Systematic Survey on Petrochemical Technology

101year, it was adopted in the United States andthroughout Europe. This was a majorinnovation that changed how phenol was
produced the world over. Compared to pastprocesses, this enabled production undermuch milder conditions and yielded fewer
byproducts; it remains the mainstream
process utilized throughout the world to thepresent day.
(4) Polymers
At the end of the Second World War, theUnited States government sold off its
state-owned synthetic rubber and otherfactories
inexpensivelytochemicalcompanies. With the sudden loss of thismassive demand from the military, synthetic
rubber and a host of other chemical products
experienced a temporary decline inproduction;
however,thenation’s
well-equipped factories did not remain idle
for long as the mass consumer demand in the
United States was quick to blossom, having
been suppressed during the war.
Unsaturated
polyester,
polytetrafluoroethylene and silicone joined
the lineup of polymers in addition to thosedeveloped in the 1940s; furthermore, LDPE
andpolystyrene
triggeredsignificant
advances in the United States petrochemicalindustry, having gone into full-scale
production for military use during the war
andthenemergingasall-purpose
commercial-use polymers. Following on theheels of nylon, the demand for synthetic
fibers acrylic and polyester started growing in
the United States in the 1950s. Meanwhile,
manufacturers leveraged the advances madein production and molding technologies
achieved during the Second World War tobring about even more widespreadcommercial use of a raft of polymers that had
been made primarily from coal since the1930s, namely, vinyl chloride, phenolic resin,urea resin, methacrylate resin and nylon.
Manufacturers began using the EDC process
to make vinyl chloride, the raw material forpolyvinyl chloride, from ethylene, and thecumene process used to make phenol, the raw
material for phenol resin and nylon, andacetone, the raw material for methacrylate
resin. Thus, these polymers were incorporated

102

into the petrochemical industry.
Great strides were also achieved inpolymer forming technologies during theSecond World War. In addition to theconventional techniques of compression
molding and calendar molding, the 1950s saw
the growth of extrusion molding, which had
already been used extensively during the war
to produce synthetic fibers, pipes, films,
sheets and wire coating, as well as growth in
the size of the machinery used. Injection
molding, which was already in use before thewar for the fabrication of small plastic
components, also made leaps after the war, as
the size of machinery grew and processes
wereaccelerated
andautomated.
Consequently,
theUnitedStatespetrochemical industry was able to develop
rapidly in the postwar years with twothermoplastics, polyethylene and polystyrene,as the main driving force.
5.3.2

The birth and development of theEuropean petrochemical industry
An industry evolved from the mass
production of chemicals from coal andfermentation ethanol in the first half of the20th century in Europe, the birthplace of themodern chemical industry. During the Second
World War, coal liquefaction using
high-pressurehydrogenation
andtheproduction of artificial petroleum via the
Fischer-Tropsch process were both carriedout on a large scale in Germany.
Technologies for large-scale production andcontinuous operation comparable to thoseused to make petrochemicals made great
strides in Europe; however, since it lacked theabundant supply of natural gas that the UnitedStates had, the petrochemical industry did not
emerge there until the 1940s.
(1) European energy revolution
In the 1930s, large reserves of oil werediscovered in the Middle East. After theSecond World War, this crude oil started
being exported around the world in large
quantities. Given these circumstances, large
oil refineries were erected, primarily in the
coastal areas of Europe, as part of the UnitedStates’ Marshall Plan for European
reconstruction. Refining oil in oil-consuming

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

areas rather than in oil-producing areas was amajor shift, resulting in Europe transitioning
from coal to crude oil-based energy. This was
the European energy revolution. However,passenger cars had a low penetration rate inEurope, unlike the United States, so thedemand for petroleum products focusedheavily on heavy fuel oil rather than on
gasoline. For this reason, European refineries
did not undertake catalytic cracking andcatalytic reforming on as large a scale as their
American counterparts, nor did they supply
large amounts of petroleum waste gas.
Nevertheless, refineries in France began
producing small volumes of propylene-based
solvents from petroleum waste gas in 1949,
which can be deemed as the start ofpetrochemistry in Europe.
(2) Origins of the European petrochemicalindustry
The full-fledged development of thepetrochemical industry in Europe originatedwith the steam cracking of naphtha, gas oil
and other liquid hydrocarbons produced from
European refineries to generate olefins andaromatic hydrocarbons. In 1950, British
company ICI adopted a superheated steam
cracking process from American company
Kellogg and built Europe’s first naphthasteam cracking plant in Wilton in northeast
England, thus forming the beginnings of apetrochemical complex in the area. The
United Kingdom was also home to the BP
refinery in Grangemouth, northern Scotland,
and the Esso Fawely refinery in the suburbsof Southampton, in the south of England.
Thus, an increasing number of large
petrochemical complexes grew up aroundlarge oil refineries. In the early 1950s, France,
Italy and the Netherlands also began theirown petrochemical industries. Meanwhile,(West) Germany, which had just suffereddefeat in the Second World War, remained
far behind its European neighbors, and was
not able to establish a petrochemical industry
until the latter half of the 1950s. In West
Germany, reconstruction began with the fieldof coal chemistry.
Given its origins in the steam cracking of
naphtha, the European petrochemical industry
was typified by each complex producing an

extremely large number of products, since
they had to make effective use of the many
types of olefins and aromatic hydrocarbons
that were co-produced. It was also typified bya large number of joint venture companies
backed by American or British oil orchemical companies paired with chemicalcompanies in the various countries of Europe.
For instance, in West Germany, BASF joinedwith Shell to form Rheinische Olefinwerke(ROW), while Bayer joined with BP toestablish Erdölchemie to undertake the steam
cracking of naphtha; both were fifty-fifty
joint ventures. Yet another feature of theindustry in Europe was the formation ofcomplexes that included industrial organic
chemical and polymer production plants
centered around the naphtha steam cracking
plants, which themselves were adjacent to oil
refineries in the coastal areas. A similar
situation emerged in Japan, but not in the
United States (see Section 2.5.2)(3) Successive development of European
petrochemical technologies
Europe was home to a large number ofcompanies
with
top-tier
chemicaltechnologies. Therefore, although theindustry began with the steam cracking of
naphtha, by the time olefins and aromatichydrocarbons could be supplied in abundance,
European petrochemical technologies werebeing developed in rapid succession.
In the 1950s, European governments
were heavily involved in the setting of prices
for crude oil and petroleum products, and fora time the pricing system was distorted, as
shown in Table 5.3. Accordingly, ethylene
production technologies that were developedin the United States were adopted, but thatwas not all. Soon, a raft of domestic ethylene
production technologies, including theCatarole process, sand cracking process, theBASF process and the Hoechst process, weredeveloped and put into commercial use by
European companies. Some of thesecompanies co-produced ethylene with not justolefins but also acetylene in an effort to makeuse of their existing acetylene-based
technologies and facilities. However, as
pricing for petroleum products normalized
and technologies were developed that enabled
Systematic Survey on Petrochemical Technology

103the production of almost all of the industrialorganic chemicals from olefins without
having to depend on acetylene, the primarymethod for producing ethylene transitioned toexternal heat-pipe steam cracking by the endof the 1960s.
Many
importantmanufacturing
technologies for industrial organic chemicals
were developed in Europe. Factories began
using the Hoechst-Wacker process in 1959
(see Section 6.1.2 (2) 1)). This enabled the
production of acetaldehyde through the air
oxidation of ethylene. As mentioned in theprevious chapter, acetaldehyde was animportant intermediate product of carbide andacetylene chemistry, and after the war, itremained one of the two pillars of acetylene
chemistry, along with vinyl chloride. The
Hoechst-Wacker process spread around theworld almost immediately, and in 1962,
Union Carbide and other Americancompanies converted their factories to
employ this process. Thus, one of the major
pillars of acetylene chemistry was undone by
the Hoechst-Wacker process.
In 1960, a method was developed in theSoviet Union to synthesize vinyl acetate fromethylene and acetic acid in the liquid phaseusing the same catalyst from the
Hoechst-Wacker process; this was put into
practical use by British company ICI andAmerican company Celanese in 1965. Notlong after, Bayer and others developed a gas
phase process.
The biggest contribution from Europe in
the history of the petrochemical industry was
the discovery of Ziegler-Natta catalysts. It is
fair to say that the class of polymers produced
using Ziegler-Natta catalysts (namely, HDPE,
L-LDPE, PP, EPR, BR, IR, etc.) now accountfor more than half of all olefin consumption.
As has been already mentioned, LDPE wasinvented by British company ICI in 1933. It
wasmanufactured
using
radicalpolymerization under a high pressure (2,000
atmospheres) with oxygen or other initiator.
Meanwhile, German chemist Karl Ziegler
developed a technique for producing
polyethylene at atmospheric pressure using a
Ziegler catalyst. This method was put into use
by Italian company Montecatini in 1954,
West German company Hoechst in 1955, and104

French company Rhone Poulenc in 1956.
This polyethylene, which possessed very
different functions and applications thanpolyethylene produced using a high-pressure
process, was called high-density polyethylene(HDPE). In the United States, meanwhile,
Phillips Chemical used a chromium oxide
catalyst, while Standard Oil (Indiana) used
catalysts such as molybdenum oxide in theirrespective technologies developed in 1957 forthe polymerization of HDPE at pressures of
30 to 40 atmospheres. For this reason,
manufacturing methods using the Ziegler
catalyst are referred to as low-pressure
processes, while those used by Phillips andothersimilarmethods
arecalledmedium-pressure processes.
However, even with the high-pressure
process for producing LDPE (i.e. radical
polymerization)andthecatalytic
polymerization of HDPE, it was not possible
to obtain high performance polymers bypolymerizing propylene. Italian chemist
Giulio Natta successfully obtained highperformance PP by developing a method forthestereospecificpolymerizationofpropylene in the presence of a Natta catalyst.
Montecatini was the first company to put
polypropylene into commercial production. In
1957, it produced resins for plastics at its
Ferrara (Italy) plant, and in 1960 it began
producing synthetic fibers in its Terni (Italy)
plant. Ziegler and Natta catalysts are now
collectively referred to as Ziegler-Nattacatalysts.[Footnote3] 2[Footnote3] Refer to Section 3.4.2 (1) for the performance andpurposes of various polyethylenes, Section 3.4.3 (1) for PP, Section
3.4.4 (1) and (5) for various rubbers and Section 6.1.3 (1) for
polyethylene and PP manufacturing processes and Ziegler-Nattacatalysts.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)Table 5.3 A variety of ethylene production technologies developed in the 1940s to
the 1960s

Ziegler-Natta catalysts have a wide range
of applications. Using them in tandem with
thestereospecificpolymerizationofbutadiene yielded high performance BR, andin 1960, Phillips Petroleum put this process
into practical use in the United States. IR was
also developed as a result of thestereospecific polymerization of isoprene, andthis went into commercial use in the UnitedStates in 1959. In 1958, Montecatini
developed an ethylene-propylene copolymer,
but was unable to vulcanize it. Then, in 1961,
British company Dunlop commercialized
EPDM rubber by adding a third component
for vulcanization.

(4) The European polymer revolution
In terms of demand, Europe’s transition
to mass consumerism in the 1950s led tolarge quantities of polymers being used; thisis sometimes called the polymer revolution.
This is when a large number ofpetrochemical-based
general-purpose
polymers and all-purpose synthetic rubbers
were developed and put into practical use inEurope. Examples include ICI’s LDPE (theUnited Kingdom), IG Farben’s polyvinyl
chloride, polystyrene, and SBR synthetic

rubber (Germany), Hoechst’s low-pressure
HDPE (Germany) and Montecatini’s PP(Italy). Therefore, once factories were built
for the steam cracking of naphtha, and thenolefins and aromatic hydrocarbons could be
supplied in abundance in Europe, polymer
production rapidly expanded.
The same was true for synthetic fibers.
During the Second World War, Germany
produced Nylon 6 from phenol. In 1946, theCalico Printers’ Association (the United
Kingdom) won approval for its polyester
fiber patent. With the transfer of this patent to
the rest of the world excluding the UnitedStates, ICI began conducting research with aneye on commercialization, and in 1955, ICI’s
Wilton (the United Kingdom) plantcommenced full-fledged production. In themeantime, DuPont, which had received theright to use the patent, started full-scale
production in the United States in 1953.
DuPont had already begun production ofacrylic fibers in 1949, while West Germany’s
Bayer AG launched production in 1951 in
Dormagen (in the outskirts of Leverkusen). In
this way, not only did European companies
begin producing synthetic fibers soon after
their counterparts in the United States, it wasoften the case that they developed their own
Systematic Survey on Petrochemical Technology

105technologies instead of relying on technology
transfers.
5.3.3

The birth of the Japanesepetrochemical industry
In many ways, Japan was in a situation
similar to that in Europe. Lacking access tolarge amounts of oil and natural gas, Japandeveloped a large-scale chemical industry
based on coal and fermentation ethanol
before and during the Second World War.
Like Germany, Japan had to start fromscratch upon its defeat in the war.
Reconstruction of the industry started withcoal
chemistry
centeringon
coal,hydroelectric power, limestone and otherdomestically available resources.
(1) The advent of Japan’s polymer age
By the late 1940s, Japan had access to anabundance of information about theadvancement of the petrochemical industry
and utilization of polymer products in the
United States. Japan resumed production oftheimportantorganic
intermediate
acetaldehyde from acetylene soon after theend of the war. Not long after that, in theearly 1950s, the production of a range ofacetylene-based compounds, including vinyl
chloride, polyvinyl chloride, vinyl acetate,
polyvinyl alcohol, vinylon and methacrylate
resin was in full swing. Japan alsocommenced production of phthalic anhydride,
phenol, caprolactam and nylon from coal.
The production of urea resins from urea,
methanol and formaldehyde generated fromcoke oven gas and coke-based syngas
increased rapidly. Together with celluloid,
phenol resins and rayon, which Japan had
been producing before the war, vinylon,
nylon, polyvinyl chlorides, urea resins andother polymers spread rapidly throughout
post-war Japan. LDPE and polystyrene
imported from the United States were added
to the lineup, and Japan found itself thrust
fully into the polymer era even before its
petrochemical industry had fully gotten off
the ground. As shown in Fig. 5.1, thepolymers that were used particularly
frequently from the late 1940s to the 1950s
were polyvinyl chlorides and urea resins.

106

Fig. 5.1 Change in production volumes ofmajor synthetic polymers in Japan in the
1950s.
(2) Natural gas kick starts petrochemistry
in JapanAs shown in Table 5.4, domestically
produced natural gas (primarily methane
without ethane or other gases) became theraw material for syngas. From this, Japan Gas
Chemical began producing methanol in its
Niigata plant in 1952, followed by ammonia
and urea in 1957. The following year, Toyo
Koatsu began producing methanol fromnatural gas at its Mobara factory. In terms of
how petrochemistry is defined in this study,
1952 can be considered to be the year inwhich the field came into being in Japan.
Table 5.4 First production of petrochemical
products in Japan in the 1950s.
Year
1951
1952

Product
Household mineraloil-based synthetic
detergent
Methanol from natural
gas

1957

Polystyrene

1957

sec-Butyl alcohol, MEK

1957

Ammonia, urea

1957

IPA, acetone

1958

Ethylene (naphtha steam
cracking)

Company, factory
Lion Fat and Oil
Japan Gas Chemical,
Niigata
Monsanto Kasei Kogyo,
Yokkaichi; Asahi
Dow,Kawasaki
Maruzen Petroleum,
Shimotsu
Japan Gas Chemical,
NiigataNippon Petrochemicals,
Kawasaki
Mitsui Petrochemical
Industries, Iwakuni;
Sumitomo Chemical, Oe

Low-density polyethylene
Sumitomo Chemical, Oe(ICIprocess)
Ethylene oxide glycol (SDMitsui Petrochemical
1958
process)
Industries, Iwakuni;
1959
Ethylene oxide glycol
Nippon Shokubai, Kawasaki(Nisshoku process)High-density polyethylene
Mitsui Petrochemical
1958(Ziegler process)Industries, Iwakuni
1958

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

1958
1958
1958
1958
1958
1958
1959
1959
1959
1959
1959
1959
1959
1959

Aromatic hydrocarbons
from cracked gasoline(UOP process)Polyester fiber
Aromatic hydrocarbons
from reformates

Mitsui Petrochemical
Industries, Iwakuni
Toyo Rayon, Mishima
Mitsubishi Oil, Kawasaki

Nissan Chemical Industries,
Ltd., Nagoya
Phenol, acetone (cumene
Mitsui Petrochemical
process)
Industries, Iwakuni
Terephthalic acid (SDMitsui Petrochemical
process)
Industries, Iwakuni
Mitsubishi Rayon, Otake;Acrylic fiber
Japan Exlan, Saidaiji; Asahi
Kasei, Fuji
High-density polyethylene
Mitsui Chemicals, Nagoya
film
Yokkaichi Chemical
Non-ionic surfactant
Company
Propylene oxide, glycol
Asahi Denka, Oku
Mitsubishi Petrochemical,
Styrene monomer
Yokkaichi; Asahi Dow,
KawasakiNippon Petrochemicals,
Butadiene
KawasakiHigh-density polyethylene
Showa Yuka, Kawasaki;(Phillips process),
Furukawa Kagaku Kogyo,
High-density polyethylene
Kawasaki(standard process)Zeon Corporation,
Nitrile rubber, SBR latex
KawasakiHard type alkylbenzene

Source: Reference [12] and others

Not only did Japan Gas Chemical use
domestic resources to produce its methanol, italso used domestic technology in the form of
repurposed scrap equipment from an old
Imperial Navy fuel factory. At that time, theonly other competitors making methanol wereusing coke oven gas, as they had done since
before the war. However, in order to survive,
they soon had to switch from the raw
materials they were using to natural gas, andthen to naphtha and LPG. In this sense, thebold choice of raw materials by Japan Gas
Chemical, which was established in 1951,
was the precursor of subsequent innovations
in petrochemical technologies. Methanol andurea were the key ingredients in urea resins,
whose production was skyrocketing.
(3) The run-up to petroleum-based
petrochemistry
In Japan, the situation regarding
large-scale refineries, which would later
become the basis for the establishment of thenation’s petrochemical industry, was entirely
different from that in Europe. After the war,
the occupation forces ordered the shutdownof the refineries along the Pacific coast, andthese remained closed for more than four
years. In July 1949, the refineries were finallyallowed to be reopened after United Statesoccupation policy shifted due to theintensifying Cold War. Nevertheless, many of
the refineries did not commence actual
operation until 1950. During this time, manyof the Japanese oil companies had enteredcapital and business tie-ups with major
Western oil companies.
The restarting of the oil refineries
combined with Japan’s shift towards
consuming Middle Eastern crude oil imports
served to lay the foundation for the
petrochemical industry in Japan. Stimulated
by stories of petrochemical breakthroughsfrom Europe and the United States, Japan’sinterest in petrochemical commercialization
continued to grow. As a result, many plans
were devised from the late 1940s onwards tofoster the growth of petrochemistry in Japan.
However, compared to the mass-production
chemical industry that Japan had employedthus far, the petrochemical industry had
product categories with a larger number ofco-products, and required much vaster
expanses of land, which in turn necessitatedmassive funding. In addition, many new
products were not known in the Japanesemarket (e.g. polyethylene, polystyrene,
polyester fibers, acrylic fibers, synthetic
rubbers etc.), and companies were often
reluctant to enter into production of thesealone due to the risks involved. For thisreason, Japan needed more time even more sothan Europe, for its petrochemical industry tobe established. The involvement of thegovernment was also significantly more
substantial than in Europe or the UnitedStates, and this was a major factor in thelength of time it took for plans to reachfruition. In fact, there were many areas ofgovernment involvement on several fronts,
namely, permits for the sale of former army
and navy fuel factories, permits for coastal
reclamation, restrictions on foreign capital
inflows,
low-interest
financingfromgovernment-affiliated financial institutions
and other kinds of aid, and permits fortechnical transfers. By using these kinds ofcarrot-and-stick measures, the Japanese
Systematic Survey on Petrochemical Technology

107

government was not only trying to cultivate
the petrochemical industry, it was also
embarking on a sustained period ofintervention, which lasted until the 1980s,
with regard to the construction and expansionof facilities, supply and demand and raw
material pricing and procurement. This
marked the return of the Organic Synthesis
Industry Law, as mentioned in the previous
chapter. From the 1970s onwards, these kindsof policies were repeated in various
developing countries as they nationalized
their petrochemical industries, although theperiods of government intervention differed
greatly from country to country.
In 1957, seven years after the refineries
resumed operation, Maruzen Petroleum began
using catalytically cracked petroleum waste
gas to produce sec-butyl alcohol and MEKfrom n-butylene at its Shimotsu Plant. Also
around this time, Nippon Petrochemicals
began using catalytically cracked petroleum
waste gas to produce IPA and acetone
propylene at its Kawasaki Plant. Somehistorians identify this as the birth of thepetrochemical industry in Japan (Table 5.4).
These refineries had catalytic crackers andused the petroleum waste gas they generated
themselves. However, as in Europe, thedemand for petroleum products in Japan atthat time was dominated by heavy fuel oil;accordingly, catalytic cracking and catalytic
reforming were not carried out on a verylarge scale. Therefore, unlike in the UnitedStates, the subsequent growth of thepetrochemical industry was not based on
petroleum waste gas.
That same year, Monsanto Kasei Kogyo
produced polystyrene at its Yokkaichi Plant
using styrene monomer imported from theUnited States, while Asahi-Dow did the sameat its Kawasaki Plant. The objective behind
this was to quickly gain control of the fast
growing polymer market, assuming that
petrochemical complexes with naphtha steam
crackers would soon become able to produce
these products. In the 1960s, both companies
grew to become leaders in Japan’s
petrochemical industry.
(4) Steam cracking of naphthaThefull-fledged
birth

108

of

petrochemical industry in Japan began withthe steam cracking of naphtha (Table 5.4), as
it had in Europe. The first steam cracking
plant to go online in Japan was Mitsui
Petrochemical Industries’ Iwakuni Plant. In
addition to its polyethylene plant, thecompany launched plants to produce aromatichydrocarbons, ethylene oxide and glycol at
almost the same time, and its facility for the
production of phenol and acetone using thecumene process went into operation several
monthslater.
Meanwhile,
Sumitomo
Chemical’s Oe Plant, which started operationin the same year, began producing
polyethylene alone. It turned surplus
hydrocarbons into syngas using a steam
reformer to create the raw material for
producingammonia.
Mitsubishi
Petrochemical began domestic production ofstyrene monomer and butadiene at its
Yokkaichi Plant, which went into operation
the following year. By 1963, five years after
the first ethylene plants opened in Japan, thepercentageof
ethylene
consumption
dedicated to polyethylene had grown to 60%(see Fig. 5.2), significantly higher than in the
United States or Germany. This is likely due
to the fact that the products were highly
profitable amid the rapid expansion of thepolyethylene
market.
The
Japanesepetrochemical industry in the 1950s reliedalmost entirely on ethylene products
especially polyethylene, whose market had
begun to grow at fever pitch. The
management style employed at Sumitomo
Chemical’s Oe Plant is considered to be
typical of the Japanese petrochemicalindustry in the 1950s.

Fig. 5.2 Percentage of polyethylene in
ethylene consumption in 1963.

the

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

5.4 The 1960s: Sturm und Drang for
petrochemistry
Due to the rapid development of its
petrochemical industry, Japan started keeping
pace with the United States and Europe by
the 1960s, and these three regions became thethree dominant forces in the global
petrochemical industry. Despite having only
just begun at the end of the 1950s, theJapanese petrochemical industry grew so
rapidly in the 1960s that it overtook many
European countries in ethylene production
capacity (including the United Kingdom,which was the first out of the gate in thisarea). By the end of the 1960s, Japan’s
petrochemical industry was second only to
the United States worldwide.
In the 1960s, not only did remarkabletechnological innovations occur in the field of
petrochemistry, but the industry came to form
the basis for the chemical industry as a whole.
This was truly a period of Sturm und Drangfor petrochemistry. Having kept up with thetimes, Japan was fortunate enough to make its
way into the global arena. The following
sections will primarily discuss the Japanesepetrochemical industry, for which statistics
are readily available.
5.4.1 The Japanese polymer revolution
Polymers gradually permeated the UnitedStates market between the 1930s and the1950s, and spread at an explosive rate inJapan from the mid-1950s into the 1960s.
Thus, Japanese society truly felt the impact ofwhat could be called a polymer revolution.
Supermarkets first appeared in Japan in
the mid-1950s. As in the United States,
supermarkets were an essential driver ofpolymer demand due to the massive amountof films and trays used for wrapping foods
and the plastic daily goods sold. In otherwords, the growth of supermarkets went handin hand with increased polymer consumption.
Plastics were used for beer containers,
fertilizer and rice bags, and flexible
containers used for transporting bulk items.
Plastics were also used in televisions, radio
receivers, refrigerators, washing machines
and other trademark appliances of the

postwar period of rapid economic growth.
Furthermore, plastics were essential as
agricultural materials, such as plastic
greenhouse films, and construction materials,
such as sewer pipes, rain gutters andcorrugated roofing. Furthermore, glue,
coating and other chemical products that werepreviously made from natural polymers or
polymers derived from the oxidation of
unsaturated fats and oils came to becomprised mainly of synthetic polymers. A
lifestyle in which plastics came to becommonplace and were consumed en masse
took root in Japan in the 1960s.
The production of plastics in Japan
topped 100,000 tons in the mid-1950s, before
increasing more than fivefold to nearly
600,000 tons just five years later in 1960. A
further ten years later, production leapt
almost ninefold to 5 million tons, as shown in
Fig. 5.3. Due to its light weight, low cost,water resistance and excellent moldability,
there was a surge in demand for plastic as itcame to replace a wide range of existingmaterials, including paper (e.g. wrapping
paper and boxes), natural rubber (e.g. wire
coatings and hoses), celluloid/cellophane (e.g.
packaging and daily necessities), metal (e.g.
daily necessities and pipes), glass (e.g.
containers and daily necessities) and pottery(e.g. containers and daily necessities). Fromthe 1970s to the present day, the four main
general-purpose resins (polyethylene, PP,
styrene-based resin and PVC) account for
more than 70% of all plastics, as shown in
Fig. 5.3.

Fig. 5.3 Changes in plastic production
volumes in Japan.
Due to the difficulty in using statistics topresent the overall picture of how plastic
permeated the entire realm of existing
Systematic Survey on Petrochemical Technology

109materials, let us outline its permeation into
two fields: rubber, in the form of synthetic
rubber, and textiles, in the form of synthetic
fibers.
In postwar Japan, the domestic
production of synthetic rubber was
significantly delayed, having been banned forseveral years by the United States occupying
forces. In 1959, synthetic rubber production
finally began with Zeon, which was a joint
venture between the American company B. F.
Goodrich Chemicals and the Furukawa
Electric Group. The use of synthetic rubber inJapan dates back to the early 1950s. In 1960,
52,000 tons of the product were imported,
while 23,000 tons were produced.
Accordingly, as Fig. 5.4 shows, the ratio ofsynthetic rubber to new rubber consumption
in 1960 was 27%. In 1965, synthetic rubber
production reached 161,000 tons versus
30,000 tons of exports and 27,000 tons ofimports, bringing the ratio of synthetic rubber
to new rubber consumption to 47%. In 1970,
this ratio increased to 64% on the back of
698,000 tons of synthetic rubber production.
From then until the present day, the ratio has
steadily remained around 60%.

Fig. 5.4 Change of consumption volume of
new rubber in Japanese rubber molding
industry.
Let us turn our attention to textiles. Japan
was a massive producer of rayon before theSecond World War, and the rayon industry
was one of the first to recover after the war.
As Fig. 5.5 shows, by 1965, rayon, acetate
and other chemical fibers containing synthetic
fibers accounted for 48% of all textiles; thesefibers came to rival almost all of the natural
fibers, such as cotton, wool, hemp and silk.
Synthetic fibers accounted for just under halfof all chemical fibers. At that point in time,110

the biggest products were rayon and acetate,
which used natural polymers. However, thelatter half of the 1960s saw a boom in thesynthetic fibers industry. By 1970, the textile
industry was 40% synthetic fibers, 20% rayon
and acetate, and 40% natural fibers: synthetic
fibers had finally usurped the top position in
the market. After that, the ratio of synthetic
fibers continued to increase, and now theyaccount for over 80% of fiber production in
Japan.

Fig. 5.5 Changes in production volumes of
thread in Japan by material.
5.4.2

The shift from coal-based topetroleumbased products
Rayon and coal chemistry saw postwar
production top their prewar peak in thechemical industry, which existed before thepetrochemical industry. As has been alreadymentioned in the previous section, a major
shift from rayon to synthetic fibers occurredin the late 1960s. This section discusses theshift from coal-based to petroleum-based
products.
(1) Aromatic hydrocarbons
The shift from coal-based to petroleum
products began with aromatic hydrocarbons.
Japan
began
producingaromatichydrocarbons from cracked gasoline andreformates in 1958, about five years behind
the United States. In 1958, phenol was
produced by applying the cumene process tobenzene obtained from cracked gasoline.
In the same year, production began on
terephthalic acid (SD process), the raw
material for polyester fiber. This was asuperior process that enabled the one-stage
manufacturing of terephthalic acid by the
direct oxidation of paraxylene. Developed by
Scientific Design (SD) in 1955, this process
was first used in commercial production in

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

1958, after testing by Amoco. Accordingly,
production in Japan began at the same time as
production in the United States. Paraxylene,
the raw material used in this process, wasdifficult to obtain from coal tar, but readily
accessible from cracked gasoline andreformates. Mixed xylenes, paraxylene,
terephthalic acid and polyester fibers were thearomatics
that
came
to
represent
petrochemistry. As Table 5.5 shows, theproduction of paraxylene in Japan began in
1960, just two years after terephthalic acid.
Domestic production of paraxylene did not
begin until the production of terephthalic acidfrom imported paraxylene had properly
commenced.
Table 5.5 First production of petrochemical
products in Japan in the 1960s
Year
1960
1960
1960

Product
Phthalic anhydride(o-xylene method)
2‐Ethylhexanol,
iso-butanol (oxoprocess)
Styrene-butadiene
rubber (SBR)

1960

p-Xylene

1960

Alkylphenol

1961
1961

Polypropylene glycol
Polycarbonate resin

1961

Petroleum resin

1961

AS resin

1962

o-Xylene

1962

Epoxy resin

1962

Polypropylene fiber
Caprolactam(photonitrosation)
process
Polypropylene resin
Acetaldehyde(Hoechst-Wacker
process)
Acetate, butyl acetate(naphtha directoxidation process)

1962
1962
1962
1962
1962

Ethanolamine

1962

Acrylonitrile (Sohio

Company, factory
Nippon Shokubai, Suita
Mitsubishi Chemical
Industries, Yokkaichi
Japan Synthetic Rubber,
Yokkaichi
Maruzen Petroleum,
Matsuyama; Mitsui
Petrochemical Industries,
IwakuniMaruzen Petroleum,
Shimotsu
Sanyo Yushi
Teijin Kasei, Matsuyama
Mitsui Petrochemical
Industries, Iwakuni
Dainippon Celluloid,
Sakai, Mitsubishi
Monsanto Kasei,
Yokkaichi
Maruzen Petroleum,
Matsuyama
Mitsubishi
Petrochemical, Yokkaichi
Toyo Rayon, Shiga
Toyo Rayon, Nagoya
Mitsui Chemicals, Otake
Mitsui Petrochemical
Industries, Iwakuni otake
Dainihonkasei, Otake
Nippon Shokubai,
KawasakiAsahi Kasei, Kawasakiprocess)
1962

Alkylbenzene

1963

Acrylamide (sulfuric
acid hydration process)1963

ABS resin

1963

Methyl isobutyl ketone(MIBK)

Source: Reference [12] and others

Nihon Sekiyu Senzai,
Kawasaki
Mitsubishi Chemical
Industries, Kurosaki
Hamano Seni Kogyo,
Urawa
Mitsui Petrochemical
Industries, Iwakuni otake

The production of phthalic anhydridefrom orthoxylene also began in 1960 (Table
5.5). The demand for phthalic anhydride was
growing rapidly at the time as a raw material
for phthalic ester (polyvinyl chloride
plasticizers). This was a typical coal-based
chemicalproduct.
Naphthalene,anintermediate that was originally obtained
from coal tar at the end of the 19th century
and used as a synthetic dye, was used to
stoichiometrically produce oxidants, such as
fuming sulfuric acid. In the 1910s, a process
was developed to enable the oxidation ofnaphthalene with a solid catalyst (vanadium
pentoxide). In 1945, an o-xylene oxidation
process was put into commercial use in the
United States using the same vanadium
pentoxide catalyst. It took Japan 15 more
years to make the switch from coal-based topetroleum products, despite the fact that thetechnologies were developed proprietarily.
This is because the production of mixed
xylenes and o-xylene did not begin untilmuch later. Consequenly, the first phthalicanhydride produced in Japan used imported
orthoxylene, although production was
domesticated in 1962 following a spike ino-xylene imports.
Ever since the commercial introductionof a process to manufacture nylon from
caprolactam, phenol was used as the raw
material used to make caprolactam. Phenol
had been previously produced from benzene
obtained from coal tar, but when production
via the cumene process began in 1958 it, too,
became a petrochemical product. Meanwhile,
Toyo Rayon developed a proprietary processformanufacturing
caprolactam
fromcyclohexane, which was cheaper than phenol.
This process was called photonitrozation, andit was industrialized in 1962 (Table 5.5). This
cyclohexane was made by hydrogenating
benzene. The production of benzene from
Systematic Survey on Petrochemical Technology

111cracked gasoline and reformates began in thelate 1950s, meaning that the switchover topetrochemicals as raw materials was alreadyin progress. Cyclohexane, a non-aromatic
cyclic hydrocarbon, was also a prototypical
petrochemical. Around this same time,several other processes not involving
photonitrosationfor
manufacturing
caprolactam
fromcyclohexane
weredeveloped in Europe and the United States,
and the transition from phenol to cyclohexane
continued. These Western technologies wereadopted in Japan from the latter half of the
1960s
onward.
Soon,
caprolactam
manufacturers other than Toyo Rayon began
using cyclohexane, and this quickly steppedup the pace at which the transition topetrochemical methods progressed. Between
1963 and 1969, a number of companies
successively started reducing benzene tocreate cyclohexane.
(2) Transition from carbide-acetylene
chemistryIn the 1960s, new petrochemical
technologies based on olefins were developedin rapid succession. These technologies were
almost immediately adopted by Japanesecompanies, and at the same time, domestic
technologies were also developed. This meantthat carbide-acetylene chemistry had all but
disappeared in Japan by the end of the 1960s.
1) Oxo alcohols
As shown in Table 5.5, the conversion ofacetylene from a chemical to a petrochemical
product began with the production of
2-ethylhexanol by the oxo process in 1960.
2-ethylhexanol is the raw material used tocreate the polyvinyl chloride plasticizer called
dioctyl phthalate (DOP). Previously, this had
been synthesized from acetaldehyde, an
important intermediate in acetylene chemistry.
The production of 2-ethylhexanol by the oxo
process
involves
synthesis
frombutyraldehyde, itself obtained from propylene(see Section 3.4.3 (6)). Furthermore, thisprocess was proprietarily developed by
Mitsubishi.Chemical
Industries(now
Mitsubishi Chemical).
2) Acetaldehyde, acetic acid and vinyl

112

acetateIn 1962, the Hoechst-Wacker process forsynthesizing acetaldehyde from ethylene wasintroduced into Japan and put into
commercial use. The Hoechst-Wacker
process was first commercialized in Germany
in 1959, and was later adopted throughout
Europe. In 1962, it was commercialized in the
United States and Canada via technicaltransfer. Mitsui Petrochemical Industries
adopted the technology the same year,
followed by Daikyowa Sekiyu Kagaku in
1963, Kasei Mizushima and Chisso
Petrochemical in 1964 and Tokuyama Sekiyu
Kagaku in 1965. All of these companies
launched ethylene-process plants, which werecapable of achieving much higher capacity
than the conventional acetylene-based plants.
With this shift, companies that had previously
manufactured acetic acid from acetylene andacetaldehyde began either investing in
producers who used the ethylene process to
manufacture acetaldehyde or procuring theiracetaldehyde from these producers. In 1962,
93% of acetaldehyde was manufactured fromacetylene; this had nosedived to 29% by 1965
and 20% by 1967. By 1969, synthetic acetic
acid was no longer being produced fromacetylene at all. In 1962, a process for
producing acetic acid by the direct oxidationof naphtha was commercialized.
Companies that had previously produced
vinyl acetate using acetylene also began
switching technologies en masse in 1967. In
1968, Tokuyama Sekiyu Kagaku andKurashiki Rayon switched to using ethylene
to produce vinyl acetate, followed by The
Nippon Synthetic Chemical Industry andothers in 1969. Between 1970 and 1986, theproduction of vinyl acetate from acetylene
gradually dwindled to zero.
3) Acrylonitrile
Acrylonitrile had been used for many
years in the synthetic rubber called NBR. The
early 1960s saw a spike in demand for thepolymer for use in acrylic fibers and ABS
resins.
The
methodfor
producingacrylonitrile
hadundergoneseveraltransformations; at that time (the end of the
1950s) it was being produced from acetylene
and hydrogen cyanide. Hydrogen cyanide

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

could be made in various ways: fromammonia, methane and air using theAndrussow process, or from methanol,
carbon monoxide and ammonia using theformamide method, to name just two. By
contrast, the Sohio process developed in 1958
was a superior process that enabled the
production of acrylonitrile directly frompropylene, ammonia and air. In 1962, theSohio process for acrylonitrile productions
was put into commercial use in Japan as well.
In the early 1960s, Japan’s acrylonitrile
producers began switching to this process inrapid succession. Japan experienced thequickest penetration of the Sohio process outof any country in the world, and it became avoracious consumer of propylene generated
as a byproduct of naphtha steam cracking.
4) Vinyl chloride
After the Second World War, massive
amounts of acetylene came to be used forvinyl chloride, forming the driving force that
saw acetylene chemistry grow by leaps andbounds, both in Japan and the West.
Compared to the manufacturing of vinyl
chloride from acetylene, manufacturing fromethylene was somewhat more complex, so inJapan, like many other countries, vinyl
chloride was the last compound to make theswitch from acetylene chemistry topetrochemistry. This transition can be seen in
Table 5.6.
Table 5.6 First production of petrochemical
products in Japan in the late 1960s
Year
1964
1964

1964

1964
1964
1964

Product
Vinyl chloride (mixed
gas process)Caprolactam (newInventa process)Vinyl chloride (EDC
process)
Acetic acid (Distiller's
method naphtha
direct oxidation
process
Acetone (Wacker
process)
Butadiene rubber

Company, factory
Kureha Petro Chemical
Industry, Nishiki
Mitsubishi Chemical
Industries, Kurosaki
Central Chemical,
Kawasaki/Zeon
Corporation, Takaoka;
Shunan Petrochemical,
Tokuyama; Mitsui
Chemicals, Nagoya
Dainihonkasei, Otake
Daikyowa Sekiyu Kagaku,
Yokkaichi
Japan Synthetic Rubber,
Yokkaichi; Asahi Kasei,

1965

Perchlorethylene,
trichlorethylene (EDC
process)

1965

Synthetic ethanol

1965
1965
1965
1966
1966
1966
1966
1967
1967
1967
1968
1968
1968
1968
1969
1969

Butadiene(GPBprocess)Higher alcohol (Ugine
Kuhlmann process,France)Ethylene-vinyl acetate
copolymer resin (EVA)
Linear alkylbenzene(LAB)
Acrylic acid ester (ANhydrolysis process)Vinyl chloride(oxychlorination
process)
Epichlorohydrin
Acrolein (propylene
process)
Vinyl chloride (GPA
process)
Vinyl acetate (ethylene
process)n-Paraffin
Polyacetal resin
Butyl rubber
Mixed xylene
isomerization,m-xylene
Solutionpolymerization SBR
Toluenedisproportionation

Kawasaki
Kanto Denka Kogyo,
Mizushima
Japan Synthetic alcohol,
KawasakiZeon Corporation,
Tokuyama
Nissan Petrochemicals,
Chiba
Mitsui Polychemicals,
Otake
Nissan Petrochemicals(Nissan Conoco), Chiba
Mitsubishi Petrochemical,
Yokkaichi
Toyo Soda Manufacturing,
Nanyo
Asahi Glass, Yodogawa
Daicel Chemical
Industries, Otake
Zeon Corporation,
Takaoka
Tokuyama Sekiyu Kagaku,
Nanyo
Nikko Yuka
Polyplastics, Fuji
Japan Butyl, Kawasaki
Japan Gas Chemical,
Mizushima
AA Chemical, Oita
Toyo Rayon, Ukishima

Source: Reference [12] and others

Conventionally, vinyl chloride wasproduced by causing a reaction between
acetylene and hydrogen chloride. When using
ethylene, on the other hand, ethylene has tobe reacted with chlorine to create ethylene
dichloride (EDC), which is then subjected togas-phase cracking to yield vinyl chloride (i.e.
the EDC process). Several companies had put
the EDC process into commercial use.Since
the thermal cracking in the EDC process
yielded large amounts of byproducthydrochloride with the same number of moles
as vinyl chloride, the companies needed tosecure consumers for this hydrochloride.
However, the issue of what to do with thesurplus hydrogen chloride was resolved byrunning this process in parallel with theconventional process involving a reaction
between acetylene and hydrogen chloride.
One mole of acetylene would eventually reactwith ethylene and chlorine to create two
Systematic Survey on Petrochemical Technology

113moles of vinyl chloride (i.e. theacetylene-ethylene combination process).
However, because this method required both
ethylene and acetylene, it was not able to takeadvantage of the merits of the ongoing shift
to petrochemistry. Around 1960, all three
processes – the acetylene process, the EDC
process
andtheacetylene-ethylene
combination process – were being used in the
United States. In Japan, Central Chemical,
Shunan Petrochemical and Mitsubishi
Monsanto Kasei all opened factories using
the acetylene-ethylene combination process
in 1964.
Also in 1964, Kureha Chemical Industry
put a process into commercial use that it had
developed to produce vinyl chloride from a
mixture of acetylene and ethylene gases
obtained through the flame cracking of
naphtha. (This plant remained in operation
until 1982.) In 1967, Zeon opened a plantusing the GPA process, which was based on
the same mixture of acetylene and ethylene
gases. (This plant remained in operation until
1979.) Later, in 1970, Kureha Chemical
Industry opened a plant to produce vinyl
chloride from a mixture of acetylene andethylene gases obtained through thesuperheated steam cracking of crude oil.
(This plant remained in operation until 1978.)As this shows, several ways to manufacture
vinyl chloride were put into use in Japan,
many of which were developed domestically.
In an effort to fundamentally solve theproblem of what to do with the hydrogenchloride byproduct of vinyl chloride
production, oxy-chlorination was developed
and put into commercial use in the UnitedStates in 1965. Oxy-chlorination employs acopper chloride catalyst to generate EDC andwater from a mixture of ethylene, hydrogenchloride and oxygen (or air). When combinedwith the existing EDC process, this process
eventually produces vinyl chloride and waterfrom ethylene, chlorine and air. Since
oxy-chlorination uses absolutely no acetylene,
this process triggered a complete shift toproduction using petrochemical methods.
Oxy-chlorination quickly made its way
around the globe. In Japan, companies suchas Toyo Soda Manufacturing (now Tosoh),Tokuyama Soda (now Tokuyama), Toyo

114

Koatsu Industries (now Mitsui Chemicals),
and Toagosei Chemical Industry (nowToagosei) all developed oxy-chlorination
processes using domestic technology. Until
then, the petrochemical industry had reliedheavily on technical transfers; this was thefirst major example of companies adopting
technologies developed in Japan. Startingwith the adoption of oxy-chlorination at Toyo
Soda’s Shin-nanyo Plant in 1966, a raft ofJapanese companies began putting theprocess into use. With this, the share ofacetylene-based vinyl chloride production fell
sharply from 76% in 1967 to just 18% in1970.
Oxy-chlorination, which uses hydrogenchlorideandoxygentochlorinatehydrocarbons, was originally the first step inthe Raschig process for phenol production,atechnology developed in the 1930s to create
chlorobenzene from benzene. Thirty years
later, the very same process was applied toethylene. Immediately, numerous companies
in Japan and the West could use their own
technologies to develop many related
processes.
5) Chlorinated solvents
Another example of the shift fromacetylene chemistry to petrochemistry was
the adoption of processes to manufacture
perchloroethylene and trichloroethylene from
EDC in 1965.
By the end of the 1960s, the productionof chemical products from acetylene had
declined significantly in Japan, and other thana small handful of exceptions, no major
acetylene products remained in the 1970s. By
the 1980s, the industry based on acetylene
chemistry had all but vanished. In the UnitedStates, the birthplace of petrochemistry,
acetylene chemistry surprisingly held on until
around the year 2000, when the lastacetylene-based vinyl chloride plant was shut
down.
5.4.3

Vigorous technological innovation
and upsizing
As previously mentioned, the productionof alcohols on the petrochemical methods
shifted to the direct hydration from sulfuric

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

acid in the 1950s. During the 1960s, similar
petrochemical processes were developed in
rapid succession, thus spurring an intensive
burst of innovation in which the mainstream
industrial processes changed dramaticallyover a short period of time. Table 5.7 shows
examples of these kinds of manufacturing
processes, including technologies for the
extraction of aromatic hydrocarbons and the
production of acetone, terephthalic acid andcaprolactam. In addition to these, several
other competing technologies were developedin the 1960s, such as those for butadiene
extraction and hydrogenating dealkylation to
obtain benzene from toluene and xylene.
Table 5.7 Cases of intensified competition of
manufacturing methods in the petrochemicalindustry in the 1960s

Fig. 5.6 Ethylene capacity per plant aroundthe 1960s.
Another noticeable facet of the 1960s was
the progressive upsizing of petrochemical
facilities, which is exemplified by the changeover time in per-plant ethylene production
capacity, as shown in Fig. 5.6. Four plants
completed at the end of the 1950s, had an
initial average annual capacity of 20,000 tons.
The average for the 10 plants completed
between 1961 and 1964 jumped to 48,000
tons, while the average for the 10 plants thatcame online between 1965 and 1968 was
118,000 tons. Furthermore, the average forthe five plants opened between 1969 and1970 was 270,000 tons. In around 10 years,
plant capacity had expanded more than
fivefold.

Fig. 5.7 Change in maximum capacity foreach petrochemical plant product in Japan(basic petrochemicals).

Systematic Survey on Petrochemical Technology

115

Fig. 5.8 Change in maximum capacity foreach Japanese petrochemical plant product(industrial organic chemicals).

Fig. 5.9 Change in maximum capacity foreach petrochemical plant product in Japan(polymers).
In pace with the increase in ethylene
plant capacity, the per-plant capacity also
increased at plants for basic petrochemicals,organic industrial products and polymers.
Figure 5.7 shows the change in maximum
capacity for ethylene and butadiene, Fig. 5.8
shows the same for ethylene oxide, styrene,
vinyl chloride and acrylonitrile and Fig. 5.9
shows the same for LDPE, HDPE and PP. In
the 1950s alone, petrochemical plant capacity
had already outstripped the existing capacityof coal-based chemical plants to that point intime. Over the next 10 years, the scale of thisupsizing grew even more massive. The
primary reason for this upsizing was the
pursuit of economies of scale. Since
construction expenses increase by an
exponent factor of 0.6 compared to plant
capacity, the bigger the plant, the cheaper thecost of construction per unit of capacity
would become; accordingly, upsizing helpedto achieve significant cost reduction.
In the latter half of the 1960s, the major
technical factor underlying the successful
upsizing of steam cracking plants was the
adoption of centrifugal compressors. The
same held true for large gas compression
facilities, such as ammonia and methanol
plants. Furthermore, the 1960s saw theincorporation of transfer line heat exchangers(TLEs) into steam cracking plants. Theseexchanged the heat of high-temperature
steam-cracked gas to enable heat recovery
andproductionofhigh-temperature

116(high-pressure) steam, which was used todrive the centrifugal compressors. The
widespread adoption of these devices
contributed to the upsizing of steam-cracking
plants while also decreasing their energy
consumption and operating costs.
5.4.4. Integrated usage of non-ethylene
olefins and aromatic hydrocarbons
Although the petrochemical industry
originated in the United States, there it was
primarily a chemical industry driven by
ethylene. In Europe and Japan, however, theindustry developed based on the steam
cracking of naphtha. Accordingly, thisrequired the integrated usage of non-ethylene
olefins and aromatic hydrocarbons found incracked gasoline. For ethane-based steam
cracking, the mainstream process in the
United States, all that was needed was
ethylene production. If a producer needed
propylene and butylene, they only had torefine the required quantities from FCC waste
gas. Likewise, aromatic hydrocarbons could
be extracted in the necessary quantities fromreformates. The steam cracking of naphtha,
however,
producedvariousothernon-ethylene olefins as well. Even at themodern naphtha steam cracking plants withhigher ethylene yields, the amount of
ethylene generated only amounts to one-third
the amount of the naphtha used. The naphthasteam cracking plants in the 1960s yielded
even lower amounts of ethylene than this.
Accordingly, these plants also produced large
quantities
ofbasic
non-ethylene
petrochemical products. The more thesenaphtha steam cracking facilities wereenlarged, the more important it became toeffectively utilize these non-ethylene
byproducts.
In 1960, the only major consumers ofpropylene were plants that produced
isopropyl alcohol and alkylbenzene (whichused propylene tetramer). Later in the 1960s,
however, more uses for the compound weredeveloped. By 1970, PP, propylene oxide(polyurethane), acrylonitrile, oxo alcohols(butyl alcohol, 2-ethyl hexanol, etc.), cumene
and other compounds had grown to accountfor almost as much propylene consumption as
isopropyl alcohol. Meanwhile, propylene

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

tetramer, the negative aspects of which aredescribed in the next section, experienced a
reduction in production as the demand for it
decreased.
Butadiene, the C4 olefin obtained in thehighest quantity from the steam cracking of
naphtha, had been used to make synthetic
rubber since the 1940s. In the 1960s, various
moreeffective
extractive
distillation
processes were developed to take the place of
conventional extraction. One of those
processes, the GPB process developed by
Japanese company Zeon, is an example of adomestic technology that was exported
around the globe. Nevertheless, there still
remained a lack of demand for C4 butylenes
other than butadiene in the 1960s.
The demand for benzene, paraxylene ando-xylene from cracked gasoline skyrocketed.
Meanwhile, there was little demand form-xylene and toluene, but with thecommercial application of isomerization anddisproportionation,thesearomatichydrocarbons also came to be effectively
utilized within the petrochemical industry.
Thus, the 1960s was a time of significant
growth for propylene, butadiene and aromatichydrocarbons as effective ways weredeveloped and adopted to utilize these
ethylene co-products of naphtha steam
cracking.
5.4.5

Advancements in petrochemistry inthe chemical industry
The petrochemical industry grew into amajor supplier of hydrocarbon solvents,
various industrial organic chemicals andpolymers for the chemical industry.
Accordingly, the chemical industry as awhole came to be closely linked to thepetrochemical industry. Examples of the shift
from chemical to petrochemical methods
have already been mentioned for the rubber
molding and chemical fiber sectors. The
1960s was a time when a wide-range ofsectors in other areas also shifted topetrochemistry.
(1) The shift to petrochemistry in chemicalindustries
using
petrochemical
products
At its onset, the detergent industry
originally used fats and oils as raw materials.

Before the Second World War, higher
alcohols were produced through thehigh-pressure hydrogenation of fats and oils;
these were sulfated to create mild detergents,
such as sulfuric acid ester salts.Having
suffered a soap shortage during First World
War due to a lack of fats and oils, Germany
was one of the first countries to begin
researching coal chemistry-based synthetic
surfactants. By the 1930s, it had begun
producing alkylnaphthalenesulfonic acid soda.
Production of alkylnaphthalenesulfonic acidsoda began in the United States as well,where it was sold as a synthetic detergent. In
1946, after the war, Standard Oil (California)
subsidiary company Oronite developed
alkylbenzenesulfonic acid soda, which wassold and popularized by P&G. In Japan, theproduction of alkylbenzene began in 1958,
and the production of this and other synthetic
detergents soared as electric washingmachines became more commonplace.
Alkylbenzene is produced by causing areaction between tetramerized propylene, also
known as dodecene, and benzene. Meanwhile,
the production of non-ionic surfactants fromdomestically sourced ethylene oxide began in
1959. In the 1960s, the primary product of thedetergent industry shifted from soap tosynthetic detergent, which contributed greatly
to the transition from fats and oils topetrochemical-based methods.
The same trend occurred in the coating
industry. The coating industry originally useddrying and semi-drying oils as raw materials,
including unsaturated fatty acids. Before thewar, the industry had started using alkyd
resins made from drying and semi-drying oils
and phthalic anhydride as resins for coating.
Phthalic anhydride was created by oxidizing
the naphthalene obtained from coal tar. AftertheSecondWorldWar,
coating
manufacturers began using amino-alkyd
resins, polyvinyl chlorides and unsaturated
polyester resins as resins for coating, all ofwhich were products of coal chemistry. In the
1960s, the petrochemical industry began
producing excellent coating resins such as
epoxy, acrylic and polyurethane resins.
Phthalic anhydride also made the jump fromusing a coal-based raw material (naphthalene)
to a petroleum-based raw material
Systematic Survey on Petrochemical Technology

117

(orthoxylene). This meant that alkyd resins
and unsaturated polyester resins were also
now petrochemical products. Thus, thecoating industry also shifted from a fats andoils based industry to a petrochemistry-basedindustry.
The adhesives industry began withnatural polymers such as glue and paste.
Before the war, the industry used phenolic
resin, but shifted to using large quantities ofcoal products after the war until the 1950s,
including urea resin and vinyl acetate resin.
In the 1960s, the petrochemical industry
began producing epoxy resins, polyurethane
resins, acrylic resins, EVA resins andsynthetic rubber. Phenol and vinyl acetate
also made the switchover to being
petroleum-based products; thus, the adhesives
industry also transitioned from a coal-based
to a petrochemistry-based industry.
Several other fine chemical industries,
including the pharmaceutical, pesticide andcosmetic industries, also saw most of theirprimary raw materials, namely, organic
solvents and organic intermediates, switch topetrochemical products.
Thus, in the 1960s, the petrochemicalindustry became a key industry, supplying awide range of chemical industries in Japan
with their raw materials.
(2) The shift to petrochemistry in chemicalindustries
supplyingauxiliarymaterials
tothepetrochemicalindustry
Ammonia, the basic raw material forchemical fertilizers and industrial organic
chemicals, was made from hydrogen obtained
either from the electrolysis of water, fromcoke oven gas or from reactions with coke
synthesis or water gas. Compared to coal, it
was easier to obtain hydrogen from oil,petroleum-based gas and natural gas, sincethese were hydrocarbons. Moreover, while
the large-scale transport of crude oil became
possible, rising wages led to an increase indomestic coal prices, meaning that imported
oil and petroleum-based gases became
cheaper than coal. Furthermore, as thedemand for electricity increased, theerstwhile surplus of hydroelectric power soon
disappeared. Thus, the 1960s played witness118

to the ammonia industry switching over fromcoal to oil and petroleum-based gas. As thesize of the ammonia plants grew, they started
being built inside petrochemical complexes,
where oil and petroleum-based gas werereadily available. This was also convenient
for acrylonitrile and other petrochemicalplants that consumed large quantities ofammonia.
Meanwhile, the world’s caustic soda
plants that produced chlorine and sodiumhydroxide through the electrolysis of brine
were often located in areas where there was arock-salt layer underground, or where
inexpensive power could be obtained byhydroelectricity. Since before the war, mostof these plants in Japan had been located inareas that had hydroelectric power plants,
using the energy of falling water.
The production of carbide and acetylene
was also prevalent in areas where inexpensive
power could be obtained, since it consumed
large amounts of power. However, an
increase in the demand for electricity in Japan
during the 1960s saw power generation
switch from hydroelectric to thermal power
generation using oil. The caustic soda
industry had traditionally been driven by astrong demand for caustic soda, while there
was little demand for the co-produced
chlorine. However, chlorine demand grew
rapidly, starting with polyvinyl chlorides in
the 1950s. In the 1960s, production
skyrocketed of chemical products that usedlarge amounts of chlorine to produce,
although the chlorine did not remain in the
product, (e.g., propylene oxide, isocyanatesand polycarbonate), as did the production ofchlorine-based solvents. For this reason,
high-capacity caustic soda plants also started
being built inside petrochemical complexes.
In contrast to their previous inconvenient
locations near hydroelectric power, chlorine
and other raw materials could now be readilytransported to them by pipes, and large
amounts of thermal power were being
generated nearby. Thus, even the mass
production inorganic chemical industries thatconventionally had no direct connection topetrochemistry started being located inside
petrochemical complexes in greater numbers.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

5.5 The 1970s: The end of Sturm undDrang for petrochemistry and newchallenges
The economic growth experienced inJapan, the United States and Europe during
the 1950s and the 1960s ended in the 1970s,
and a similar fate befell the petrochemicalindustry. As polymer-based materials
continued to become more commonplace, theperiod of explosive demand drew to a close.
Furthermore, massive crude oil price hikes by
OPEC in 1973 and again in 1979 caused theoil crises. The age of cheap crude oil was
over. Consequently, the petrochemicalindustry, which had been using low prices to
its advantage, saw its growth restricted fromthe supply side as well. At the same time,several negative aspects brought about by
rapid economic growth manifested in theform of environmental and safety issues, andthe petrochemical industry was standing in
the firing line. Although new petrochemical
technologies were being actively developed
until the early 1970s, the pace ofdevelopment slowed down to such a point in
the latter half of the 1970s that many started
saying the industry had matured. In addition
to this maturation of the technology,
petrochemistry also made the jump over todeveloping countries, thus the trifecta ofJapan, the United States and Europe began tocollapse.
5.5.1

The end of polymer revolutions inJapan, the United States andEurope
The increase in demand generated byreplacing existing chemical industries, suchas those based on coal chemistry, withpetrochemistry had more or less run its courseby the end of the 1960s. In the 1970s, thespread of polymer-based materials in Japan,
the United States and Europe had alreadyadvanced considerably, thus ending the
rapid-growth era for polymer-based materials.
Furthermore, the two oil crises caused theprice of oil to soar, meaning an increase inboth the cost and the price of petrochemical
products. This increase in cost relative toother materials was one factor that led to theend of the meteoric growth of petrochemical

products.
However, this sea change in the businessenvironment came too quickly for the
petrochemical industries in Japan, the UnitedStates and Europe to immediately respond.
Accordingly, capital investment continued fora little while as it always had, on the back offorecasts for robust demand. Eventually, thisled to excess capacity in all three regions.
Since facilities had been being upsized fromthe end of the 1960s onwards, the decline inoperating rates led to a dramatic increase incosts, and the profitability of thepetrochemical industry suffered as a result.
5.5.2 Manifestation of negative aspects
A lifestyle of mass production, massconsumption and mass disposal spreadquickly in the 1950s and the 1960s in stepwith advancements in petrochemistry. In
addition, the pursuit of substantial cost
reductions in logistics and other areas
propelled the centralization of production,
primarily in coastal complexes. However, theeffects of these changes were not all positive.
Previously unnoticed negative aspects started
surfacing in the 1970s; these can be divided
into three main issues. The first issue wassevere air and water pollution. This was not
limited to the petrochemical industry, butrather was an issue shared by all heavy
chemical industries. The second issue wasplastic waste, which lay squarely with thepetrochemical industry. Finally, the third
issue was the environmental and safetyconcerns stemming from chemical substances.
Again, this was not limited to thepetrochemical industry, but involved a wide
range of chemical industries. In the latter halfof the 1970s, petrochemical companies inJapan, the United States and Europe were
fully immersed in finding solutions to theseissues.
(1) Air and water pollution
Air and water pollution were particularly
severe issues faced by large complexes inwhich petrochemical facilities, oil refineries
and thermal power generations wereconcentrated.
Complexes
regulatedconcentrations of the air pollutants emitted,
such as sulfur dioxide, nitrogen oxide, soot
Systematic Survey on Petrochemical Technology

119and dust, and water-polluting substances,such as BOD and COD. Regions whereemissions were particularly high also madeuse of total pollution load control schemes.
To reduce pollutants, companies converted to
low-sulfur fuels, installed flue gas
desulfurization equipment, installed dust
collectors,
modifiedboileroperatingconditions, installed denitration equipment
and introduced primary wastewater treatment
processes, such as coagulating sedimentationand oil separators, and secondary wastewater
treatment processes, such as activated sludge
systems. These technologies were applied inevery industry, not just the petrochemicalindustry. Investment in such pollution
prevention rapidly increased in the 1970s; in1975, it accounted for 22% of all investmentin the Japanese petrochemical industry.
In Japan, measures to mitigate air andwater pollution in the petrochemical industry
were intensively carried out in the early
1970s, after which the proportion of funds
invested in pollution prevention fell away
dramatically. Nevertheless, the developmentof low-pollution production methods that
aimed to decrease the amount of byproducts
came to form the core of technologicaldevelopment in the petrochemical industry
from that time onwards.
(2) Plastic waste
Coinciding with the development ofdisposable containers, plastic waste became asevere issue for the entire petrochemicalindustry; the same was true for for old tires aswell. However, this problem did not manifest
until petrochemical products that were soldand processed were disposed of after being
consumed, meaning it could not be solved by
the petrochemical industry alone. Since thisinvolved local governments as well as several
other related industries and also consumers,
measures could not be enacted immediately.
In Japan, the Plastic Management Research
Association (which was reorganized into the
Plastic Waste Management Institute (PWMI)
the following year) was established in 1971,
and long-term initiatives were commenced
with regard to the processing of plastic waste,
recycling
research,technologicaldevelopment, public relations and the120

nurturing of a recycling industry.
Steady efforts such as these graduallycame to produce results in Japan over the
next 40 years or so. As Fig. 5.10 shows, thevolume of plastic waste continued to increase
until it peaked in 2000, and has followed agradual downward trend since then.
By contrast, the treatment of plastic waste
is a different story. In the 1970s, most waste
was either buried in landfills or simply
incinerated. However, as Fig. 5.11 shows,thermal recycling at municipal waste
incinerators had come to be the primary
treatment method by the 2000s. Strides werealso being made in cooperation with otherindustries, including the cement and steel
industries. In 2000, the utilization rate was
48%; by 2013, this had jumped to 88%. Thus,
efforts to tackle the plastic waste problem inJapan are showing signs of success after yearsof hard work. Notwithstanding, the problem
continues to grow across the globe and still
remains a major challenge.

Fig. 5.10 Change in plastic gross discharge inJapan.

Fig. 5.11 Progress of plastic recycling inJapan.
(3) Environmental

andsafetyNational Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

issuesstemming from chemical substances
As shown in Table 5.8, four major
environmental and safety issues stemmingfrom chemical substances have occurred in
the field of petrochemistry, namely, issues
with synthetic detergents, issues with organic
chlorine compounds, issues with gasoline
additives (tetraethyl lead, MTBE) and issues
with chemical substances in relation to global
environmental problems.
1) Synthetic detergents
By the mid-1960s, rivers were alreadystarting to become polluted by foam fromalkylbenzenesulfonic acid soda, widely usedin synthetic detergents. Alkylbenzenesulfonicacid soda used dodecene made fromtetramerized propylene as a raw material andpossessed strong cleaning power. In Japan, its
use as the primary ingredient in synthetic
detergent rapidly spread from the late 1950s
onwards.
However,
most
of
the
alkylbenzenesulfonic acid soda derived fromdodecene contained branched-chain alkyl
groups. Due to its poor biodegradability, thecompound remained in the environment andcaused foam pollution in rivers. In contrast,
the alkylbenzenesulfonic acid soda containing
straight-chain alkyl groups were found to bebiodegradable. Straight-chain alkyl groups
can be obtained from higher alcohols, whichthemselves are obtained through the highpressure hydrogenation of fats and oils.
Consequently, producers switched to using
fats and oils to make these. Within
petrochemistry as well, various techniques for
producing straight-chain α-olefins weredeveloped, thus establishing the infrastructureneeded to supply straight-chain alkyl groups.

This issue was a major blow to the Japaneseand European petrochemical industries,
which traced their origins to the steam
cracking of naphtha, because it meant the lossof a key consumer for propylene, for which
demand
was
still
low.
However,manufacturers in both the synthetic detergent
and petrochemical industries were quick to
respond to this issue.
2) Organic chlorine compounds
In 1968, the Kanemi Yusho Incident
occurred in Japan. This was a case of mass
polychlorinated biphenyl (PCB) poisoning,but the problem was much bigger, involving
dioxins as well as many other chlorinatedorganic products and their waste products andbyproducts. It was then linked to the issue ofchlorine-based pesticides, which had been
pointed out as problematic in the early 1960s.
PCBs were inexpensive, stable in thepresence of heat and chemicals, highly
insulating, and highly incombustible, so they
were widely used as heat transfer mediums,
insulating oils for transformers and capacitors
and plasticizers, as well as in carbonlesspaper. The production of PCBs began in the
United States in the late 1920s and in Japan in
the mid-1950s. The Kanemi Yusho Incident
happened when PCBs, which were being used
as a heat transfer medium for the heat
treatment of food oil, contaminated food oil
due to the inadequate maintenance of a heatexchanger. The production and use of PCBs
was prohibited, and PCB-containing products,
such as carbonless paper, were widely
recalled; however, the problem did not stop
there.

Systematic Survey on Petrochemical Technology

121

Table 5.8 Safety and Environmental issues on chemical substances
related to petrochemistry

Organic chlorine compounds, like PCBs,
do not break down very readily in theenvironment, and, since they accumulate inbody fat, they are perpetuated in highconcentrations along the food chain. In the
1960s, it had already been pointed out thatchlorine-based pesticides were causing
environmental pollution. Furthermore, it was
discovered that dioxins, a byproductgenerated in the process of producing variousorganic chlorine products, could potentiallycontaminate the primary products. Moreover,it was also found that dioxins could be
generated when organic chlorine products
were incinerated. Like PCBs, dioxins areorganic chlorine compounds that are
non-degradable, accumulative and toxic.
Efforts were undertaken in Japan, theUnited States and Europe to tackle thisproblem, and as a result, management
techniques were adopted for all existing andnew chemical substances, not just organic
chlorine compounds, from the standpoints ofdegradability, accumulativeness and toxicity.
Laws that were enacted in Japan around thistime include the Act on the Evaluation ofChemical Substances and Regulation of Their
Manufacture and the Law concerning
Pollutant Release and Transfer Register.
3) Gasoline additives
The third problem was tetraethyl lead. In

122

the late 1960s, questions began to arise
surrounding tetraethyl lead, which had been
added to gasoline to enhance its octane
number. Tetraethyl lead was used in
combination with ethylene dibromide toprevent the accumulation of lead oxide in theengine when gasoline was burned. Tetraethyl
lead went into commercial production in the
United States in the 1920s and was one of thefirst products of the country’s nascentpetrochemical industry. During the Second
World War, it was used in large quantities as
an octane enhancer for aviation fuel. In Japan
as well, it went into commercial production
before the war, and was imported en masseeven after the war since domestic production
was not achieved until much later.
Since tetraethyl lead is itself highly toxic,
sufficient attention must be given whenhandling gasoline containing the substance;
this had been fully known since the 1920s. In
the late 1960s, air pollution caused by leadcompounds emitted as automotive exhaustand chronic lead poisoning among roadsideresidents became significant issues. Therefore,
efforts were undertaken to make the switch tounleaded gasoline. Japan had alreadyachieved this transition by the mid-1970s, but
in the United States it took until the
mid-1990s for leaded gasoline to finally beoutlawed. For the petrochemical industry, thisNational Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)meant that demand dissipated for ethylene in
the form of tetraethyl lead and ethylene
dibromide. To propel the transition tounleaded gasoline, manufacturers either had
to produce gasoline containing high quantities
of high-octane alkylates or aromatichydrocarbons or add different additives togasoline. In the United States, gasoline
producers began using MTBE as an additivein the 1980s. MTBE is made by reacting
methanol with t-butyl alcohol derived from
isobutylene. The production of MTBE
increased rapidly in the United States
between the 1980s and the 1990s; productionin Japan began in 1992. By the end of the
1990s, worldwide MTBE production had
reached 18 million tons. With such a large
production volume, isobutylene from thesteam-cracking of naphtha and FCC waste
gas went into short supply. Consequently,
half of the required amount of isobutylene
had to be produced by dehydrogenating
isobutane. Incidentally, MTBE-contaminatedgroundwater became an issue in the UnitedStates in the 2000s. The underlying cause ofthis was leakage from tiny cracks inunderground storage tanks at gasoline stations.
MTBE is slightly more soluble than gasoline
in water, so it ended up contaminating
groundwater. Furthermore, even small
amounts of MTBE can dissolve in water,
resulting in the water being no longer able tobe used for drinking due to the odor and taste.
In 2002, the State of California banned theuse of MTBE as a gasoline additive, and theremaining states followed suit. By themid-2000s, petroleum companies stopped
adding MTBE to their gasoline. The logicalsolution would have been to inspect theunderground tanks at gasoline stations toprevent leaks, but a government policy wasput in place instead, reflecting the growing
tendency to regulate chemical substances
without much thought. After that, gasoline
manufacturers in the United States replaced
MTBE
with
fermentation
ethanol.
Fermentation ethanol is much more watersoluble than MTBE, so the fundamental
problem of cracks in underground tanks at
gasoline stations has still not been dealt with.
As mentioned in Section 4.2.1 (4), theproduction of fermentation ethanol from cornin the United States skyrocketed between the
mid-2000s and the 2010s, reaching 25 million
tons of ethylene equivalent. Since corn
farmers are subsidized, the use of synthetic
ethanol additives made from petrochemicals
is prohibited. With this, the petrochemicalindustry has lost a major consumer of its
products, and it has yet to recover. As thisshows, the issue of using additives to enhancethe octane number of gasoline that started in
the 1970s has affected and continues to affectthe petrochemical industry in many ways.
4) Chemical substances related to global
environmental problems
The fourth category of environmental andsafety problems caused by chemicals consistsof global environmental problems. This issue
began with the ozone layer depletion byfluorocarbons, which contain chlorine andbromine. In the past, fluorocarbons were
widely used as refrigerants, safe solvents andpropellants. Production in the United States
started in the 1930s, while manufacture in
Japan began in 1942. Fluorocarbons areproduced through a reaction betweenhydrogen fluoride and chloroform, methyl
chloroform and trichloroethylene.
In the mid-1970s, chlorofluorocarbons(CFCs, also known as Freon) andbromofluorocarbons (Halon) were identified
as primary causes of ozone layer depletion,and global production and imports of thesecompounds were banned by the Montreal
Protocol in 1985. This resulted in an easing of
the ozone depletion trend from the mid-1990s,
but
norecoverywasobserved.
Hydrofluorocarbons (including hydrogen)and perfluorocarbons (excluding chlorine andbromine) were supplied as new CFC
substitutes. However, emissions of thesecompounds later became subject torestrictions designed to further curb global
warming. As a result, it became necessary todevelop safer products.
The Kyoto Protocol that was adopted in
1997 for the purpose of reducing global
warming set reduction targets for six types ofgreenhouse gases, including carbon dioxide.
In addition to the above-mentionedhydrofluorocarbons and perfluorocarbons,another chemical compound linked to
Systematic Survey on Petrochemical Technology

123petrochemistry is nitrous oxide (N2O).
Nitrous oxide is a byproduct of the nitric acidoxidation process in the production of adipic
acid, a raw material for nylon. The volume of
nitrous oxide released in the production of
adipic acid was roughly equivalent to 10% of
the nitrous oxide produced through humanactivity; many adipic acid producers havealready introduced facilities at their plants todecompose nitrous oxide byproduct.
5.5.3

Maturing petrochemical technology
and expansion into developing
countries
As illustrated in Table 5.9, the intense
technological revolution observed in the
1960s continued in the early 1970s.
Japan commercially manufactured EPDM
and IR as new polymers throughZiegler-Natta catalytic reactions, and also
introduced the first production of styrene-type
thermoplastic elastomers (a major type ofthermoplastic elastomers) by leveraging
living polymerization. Moreover, theutilization of olefins other than ethylene
derived from the steam cracking of naphtha
paved the way for the commercial productionof acrylic acid ester derived from the directoxidation of propylene, maleic anhydride
made from n-butylene or n-butane feedstock,
1,4-butanediol (PBT resin material) madefrom butadiene feedstock and THF. The
commercial production of high-purity
terephthalic acid enabled direct reactions
betweendimethyl
terephthalate(DMT)-independent terephthalic acid and EG,
leading to the commercial adoption of
manufacturing technologies for polyester
filaments (long fibers). This laid the platform
to allow polyester fiber to rise far above
nylon fiber and acrylic fiber from the 1980s.
At the same time, the technology to separate
paraxylene, a raw material for terephthalicacid, from mixed xylene was also further
developed in the form of Toray’s Aromax
process and UOP’s Parex process, both ofwhich meant substantial cost reductions. The
long-desired production alternative to the
propylene oxide chlorohydrin method
emerged in the form of the styrene
co-production
method,which
wasincorporated into commercial production. In

124Europe and the United States, tert-butyl
alcohol and propylene oxide co-production
methods were also employed in commercial
production on a large scale.
Table 5.9 First production of petrochemical
products in Japan in the 1970s
Year

Product

1970

EPDM

1970

Acrylic acid ester (directoxidation of propylene)

1970

Maleic unhydrate (B‐Bfraction)

1970
1971
1971

Styrene-type thermoplastic
elastomer
Isoprene (GPI process),
isoprene rubber
Butanediol, THF
co-production (butadiene
process)

1971

Polyacrylamide

1972

PBT resin

1972

High purity telephthalic acid

1972
1972
1972
1973
1973
1975
1976

Isopropyl alcohol (direct
hydration process)
Ethylene-vinyl alcohol
copolymer (EVOH)
Direct polymerization
process for polyester
filament
PAN process for carbon
fiber
Adsorptive separation of
p-xylene (Aromax)
Styrene monomer,
propylene oxide
co-production

Kuraray, Okayama
Kanebo Polyester,
Hokuriku
Toray Industries,
Shiga
Toray Industries,
KawasakiNihon Oxirane, Chiba
Toray Industries,
Mishima

PET resin for bottles

1978

No decalcification process
for polypropylene by thehigh activity catalyst
Superabsorbent polymer

1978

Ionomer resin

1979

Modified polyphenylene
ether

1977

Company, factory
Sumitomo Chiba
Chemical, Chiba;
Nippon EP Rubber,
Yokkaichi; Mitsui
Petrochemical
Industries, Chiba
Nippon Shokubai,
Himeji
Kasei Mizushima,
Mizushima; Nippon
Shokubai, Himeji
Asahi Kasei,
KawasakiZeon Isoprene,
Mizushima
Toyo Soda
Manufacturing,
Nanyo
Mitsubishi Chemical
Industries, Kurosaki
Mitsubishi Rayon,
Toyohashi
Matsuyama Sekiyu
Kagaku, Matsuyama
Tokuyama Soda,
Tokuyama-higashi

Mitsui Petrochemical
Industries, Chiba
Sanyo Chemical
Mitsui
Polychemicals, Otake
Asahi Dow, Chiba

Source: Prepared with Reference [10]From the late 1970s, however, thenumber of new products and technologies
used in commercial production fell rapidly,

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)leading to the view that petrochemical
technology had matured. The 1970s saw theestablishment of state-operated ethylene
production companies first in South Korea
and Taiwan, and later in the so-called newly
industrialized countries (NICs) (or newly
industrialized economies [NIEs]), marking
the launch of the petrochemical industry inthose countries. Unlike Japan and Europe,
these nations had no prior track record incoal-based chemical industry. They usedpolymers such as polyethylene andpolystyrene and synthetic fiber feedstock
imported from the three major supply regions,to start production of synthetic fiber as well
as molded polymer products. Thanks to theemergence of the textile industry and thehousehold items and home appliancemanufacturing sectors, which relied onsynthetic fiber and molded polymer products,
domestic demand for petrochemical products
increased in these countries. Consequently,
the relevant governments instituted policies topromote the petrochemical industry with theaim of superceding foreign imports. Since the1980s, this pattern has governed the rise of
the petrochemical industry throughout theASEAN region, China and India, and it hascontinued to be repeated to the present day.
As petrochemical technology continued
to mature, the driving force behindtechnology
transfer
shiftedfrompetrochemical companies developing newtechnologies to plant engineering companies.
As a result, it became easier forstate-operated companies and large privatecompanies in developing countries to enter
the petrochemical sector. From the 1980s,
global demand for petrochemicals fluctuatednotably in tandem with an increase in thenumber of market players.

5.6 Birth of the Middle Eastern
petrochemical
1980s

industryintheThe event that had the most profound
impact on the petrochemical ndustry in the
1980s was the emergence of a large-scale
petrochemical industry in the Middle East.
This development was symbolic of thematuring state of petrochemical technology

and put an end to the dominance of the threemajor regions that had presided from the
1950s to the 1970s.
At the same time, the petrochemicalindustry in developed countries witnessed
several trends to cope with maturing demand,
environmental problems and soaring raw
material prices in the 1970s. The first of thesetrends was the shift toward polymer-based
structural materials. Another trend was thedevelopmentofenergy-saving
andlow-pollution technologies.
5.6.1

Emergence of the petrochemicalindustry in Middle East
As a result of the steep rise in oil prices
during the 1970s, the oil-producing nations of
the Middle East had amassed large amountsof capital. Leveraging these funds, therespective governments formulated plans topromote non-oil industries. One such areathat was focused on was associated petroleum
gas, which had previously been largely
neglected. After collection and separation,
associated petroleum gas yielded methane(C1), which was used domestically as a fueland as a raw material for syngas. It also
contained ethane (C2), which served as apetrochemical raw material. The remaining
propane and butane (C3 and C4, respectively)
were exported as LPG, while the condensate
was exported as a light petroleum productequivalent to naphtha. While it was possible
to also use propane and butane (C3 and C4,
respectively)
andcondensate
aspetrochemical raw materials, initially only
ethane was used as a steam cracking raw
material due to problems with long-distancetransport.
Accordingly,
petrochemical
production in Middle Eastern oil-producing
nations started with a small number ofindustrial organic chemicals and polymers
that were directly derived from ethylene, suchas polyethylene, EG, EDC, styrene andsynthetic ethanol. The Middle Eastern
petrochemical industry was very large inscale, but simple in structure.
The bulk of the petrochemical productmanufacturers were joint ventures between
state-operated companies in oil-producing
nations and European and American oil
capital. The technology was entirely supplied
Systematic Survey on Petrochemical Technology

125

by developed nations, with construction
subcontracted to plant engineering companies
from the West. Middle Eastern oil-producing
nations had very little domestic demand for
petrochemical products; therefore, virtually
all production was geared toward exports.
Manufactured products were sold separatelyby the state-run companies and their
European and American capital partners.
As associated petroleum gas had thus far
been burned and discarded, these products
were supplied to petrochemical producers atexceedingly low (near-zero) costs that werecheaper than energy prices as natural gas.
This was one of the reasons why the Middle
Eastern petrochemical industry became
highly competitive on the global market. Thatbeing said, the developed nations tacitly
approved such dumping policies as a means
to develop new industries in developing
nations. The reason for this was that thevolume of associated petroleum gas was
proportional to the volume of oil production
and, in the absence of a sharp increase in thelatter, it was believed there would be certain
limits on associated petroleum gas volume.
Estimates in the 1980s put Saudi Arabia’s
production volume of ethylene from ethane
included in associated petroleum gas as highas roughly 6 million tons. This was
equivalent to roughly 1.5 times the ethylene
output of Japan at the time. Based on theprevailing global ethylene demand, it wasestimated that this additional supply could be
sufficiently absorbed. Existing petrochemical
powerhouses such as Europe and Japan were
alarmed before Saudi Arabian petrochemical
operations began; however, given the
concurrent emergence of, and sharp growth in,
Asian demand for petrochemical products,
the bulk of the exports were redirected toAsia.
In the mid-1980s, the Middle Eastern oil
producers began Phase 1 of theirPetrochemical Plan, and product sales madesteady progress. Around the same time,
however, the global supply-demand balancefor oil slackened and oil prices declined
considerably, resulting in funding issues thatdelayed the start of Phase 2 of the plan.
Thereafter, oil prices resumed an upward
trajectory, allowing Middle Eastern oil

126

producers to secure ample funds and reinvest
these into large-scale expansion of
petrochemical facilities. This pattern has been
repeated several times to the present day.
5.6.2

Transition to polymer structural
materials
In the 1970s, petrochemical companies inJapan, the United States and Europe faced amaturing demand for petrochemical products,
resulting in overcapacity issues. In response,
sectorplayers
moved
away
from
polymer-based packaging materials and otherdisposable applications in the 1980s, andinstead looked at expanding into applications
that could be used over the long term, such asmechanical parts and construction materials.
Relative to other materials, plastics offered
the benefits of being light and easy to process,and the objective shifted towards maximizingthese advantages. The much-anticipated large
new market that emerged was the automotive
sector. The surge in oil prices at the time had
increased demand for fuel-efficient vehicles.
One way to improve fuel efficiency was toreduce vehicle weight, and plastics played arole in this respect. Meanwhile, the market
for electrical appliances experienced amaturing demand for household appliances as
the driving force of growth shifted toelectronic products. To meet the needs ofboth of these markets, plastics required
precision molding and heat-resistence.
These new requirements for plastics weremet by the field of engineering plastics.
Engineering plastics had already beencommercially manufactured from the 1950s
through the 1960s in the form ofpolycarbonate, polyamide (nylon), glass fiber
filled PET and other compounds, but they had
garnered little attention amidst a period of
sharp growth in general-purpose resins. Fromthe late 1960s through the 1970s, theso-called
general-purpose
engineering
plastics had made a cursory appearance withthe commercial production of polyacetal,
PBT
andmodified-polyphenyleneether.
These general-purpose engineering plastics
became a springboard for subsequent
expansion into the automotive and electronics
fields. Thereafter, polymers that undercut
engineering plastics on price also came to be

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

used. Some examples include polyurethane,
ABS resin, fiberglass reinforced unsaturated
polyester and epoxy resin.
As plastics came to be more widelyadopted in automobiles, automakers started
calling for low-cost plastics. The polymer that
addressed those demands was PP. Produced
through a block copolymer with ethylene, PP
is a plastic that is not only light and easy toprocess, but also offers superior shock
resistance and other mechanical strength
properties. Consequently, PP met the needs ofthe automakers and started graduallyreplacing the other types of plastic that hadoriginally been introduced in the automotive
sector. PP came to account for a dominant
share of the plastics used in large molded
automotive parts, such as bumpers.
Meanwhile, super engineering plastics
such as polyimide, PPS, polyether ether
ketone (PEEK) and polyether sulphone (PES)
were also successively brought into
commercial production in the 1980s,
followed by liquid crystal polymers and otherplastics. Super engineering plastics were able
to withstand temperatures of 150°C andabove, which allowed for precision molding
and thus paved the way for the further
expansion of plastics into the electronics
field.
5.6.3

Energy-saving and low-pollution
technologies
Following the steep rise in oil prices andthe emergence of environmental and safety
problems in the 1970s, a number ofenergy-saving and low-pollution technologies
were
successively
incorporated
intocommercial production in the 1980s.
(1) Energy-saving technologies
The 1970s had already seen thedevelopment of highly active catalysts with
HDPE; the technology had progressed to thestage where there was no need to remove thecatalyst after polymerization. Consequently,
slurry polymerization methods that did not
require decalcification and gas-phase
polymerization were also adopted incommercial production. Due to its highmolecular weight, HDPE facilitated thedevelopment of high strength products andproduction of ultra-thin film with reasonable

strength. This enabled resource savings interms of product usage. The film provided analternative
infieldsrelyingon
medium-quality packaging paper, and was
widely used in disposable shopping bags andother applications. In the field of synthetic
fiber, several energy-saving technologies thatshortened
production
processes
wereachieved through continuous polymerizing
and spinning and high-speed spinning andfalse twisting (partially oriented yarn partially textured yarn [POY-PTY]).
The PP highly active catalyst developedby Mitsui Petrochemical Industries (nowMitsui Chemicals) also greatly contributed toenergy savings in the 1970s. The prevailing
Ziegler-Natta catalyst at the time produced
PP with low stereoregularity, which had to becorrected with a solvent. Since large
quantitiesofcatalysts
were
used,
decalcification was necessary to subsequently
remove catalyst residue from the PP. This
made the original PP production process
more complex than the method producing
HDPE. By contrast, the use of a highly active
catalyst yielded little PP with low
stereoregularity and also eliminated the needfor various catalyst removal tasks because thevolume of PP generated was dramaticallylarger per catalyst volume unit. Further
advances in the 1980s led to the commercial
production of PP via the gas-phase
polymerization method.
A key development in energy-saving
petrochemical technology in the 1980s was
the commercial production of L-LDPE. As
shown in Table 5.10, Japan already used
HDPE facilities and commercially produced
L-LDPE in 1980, while Union Carbide(UCC) set up a new plant with gas-phase
polymerization technology in 1983. Ever
since ICI first engaged in commercial
production of LDPE in 1930, the polymer had
been produced under a high pressure of 2,000
atmospheres and at high temperatures. By
contrast, L-LDPE could be produced using
medium-to-low-pressure HDPE production
technology through the copolymerization of
ethylene and lower α-olefins such as
1-butylene (see Section 3.4.2 (1)).
Table 5.10 First production of petrochemical
Systematic Survey on Petrochemical Technology

127

products in Japan in the 1980s
Year
1980
1980
1983

Product
Methanol process for
acetic acidLinear low-density
polyethylene by HDPE
facility
UNIPOL process linear
low-density polyethylene

1981

Dimethyl ether

1982

1-Butylene

1983

Butane process for maleic
anhydride
Polyimide resin

1983
1985

Isobutylene directoxidation process for MMA

1984

Methacrylonitrile (MAN)process for MMA

1984

Bio-process for acrylamide

1982

1986

Gas phase process forpolypropylene
PPS

1987

PEEK

1985

Source: Prepared with Reference [10]Company, factory
Kyoudo Sakusan,
AboshiShowa Denko K.K.,
Oita
Nippon Unicar,
Kawasaki
Mitsubishi Gas
Chemical Company,
NiigataNisseki Jushi Kagaku,
Kawasaki
Mitsui Petrochemical
Industries, Chiba
Nichiyu Kagaku
Kogyo, Oita
Ube Industries, Ube
Mitsubishi Rayon,
Otake
Nihon MMA, Ehime
Asahi Kasei, Kawasaki
Nitto Chemical
Industry, Yokohama
Sumitomo Chemical,
Chiba
Tosoh (SUSTEEL)
Sumitomo Chemical,
Chiba(2) Low-pollution technologies
Low-pollution
technologies
were
successively introduced into commercial
production during the 1980s. As alreadynoted, new chlorine-free production methods
for propylene oxide were employed incommercial production in the 1970s. There
are other petrochemical products that do notcontain chlorine in the final product, althoughchlorine is used in the production process.
Chlorine is created through electrolysis andthus requires a heavy energy investment.
Since it is ultimately discarded as chlorides,
this is a waste of energy. Consequently,
proactive research was conducted into
chlorine-free production methods in the
1980s. At the time, commercial production of
isocyanate had only been partially successful
for aliphatic isocyanate. Even today, newproduction methods for aromatic isocyanate
with large output volumes have yet to be
adopted commercially. On the polycarbonate
front, many production methods weredeveloped that shifted from traditional128

phosgene and BPA reactions to diphenyl
carbonate and BPA reactions; these foundtheir way into commercial production.
In the 1980s, Japanese companies
developed several variations on the MMA
process and integrated these into commercial
production, as shown in Table 5.10. For over
50 years, MMA had been produced throughthe acetone cyanohydrin process, which
utilized a reaction between acetone andhydrogen cyanide. The major drawbacks ofthis method were the reliance on hydrogencyanide, a highly poisonous compound, andthe generation of byproduct ammoniumhydrogen sulfate in volumes that exceeded
the resulting MMA by 50%. In contrast,
Mitsubishi Gas Chemical developed aground-breaking process that generated noammonium hydrogen sulfate even when using
the acetone cyanohydrin method, and adopted
this into commercial production. Other
companies such as Mitsubishi Rayon andNippon Shokubai developed production
methods to manufacture MMA throughoxygen oxidation reactions, with isobutylene
or tert-butyl alcohol serving as raw materials.
These were low-pollution processes that
required no use of hydrogen cyanide and did
not generate ammonium hydrogen sulfate as a
byproduct. They were also effectively
leveraged for isobutylene (C4) derived
through naphtha steam cracking.

5.7 The1990s:Ashift
frompetrochemistry
tofunctional
chemistry

Global demand for petrochemical
products continued to rise, supported by
low-cost polyethylene and other products
supplied by oil-producing nations. China inparticular went through a polymer revolution
driven by imported petrochemical products in
the 1990s, and started building full-scale
petrochemical complexes through joint
ventures funded by European and Americancompanies in the 2000s. In the 2010s, thecenter of global petrochemical demand
shifted to Asia. During the same period, theUnited States underwent a shale gas
revolution and moved forward with an
ethylene expansion plan targeting a 40%

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)increase in ethylene capacity from the 2010
level. However, since there is relatively little
prospect of growth in domestic demand, thisplan has triggered fears of substantial
disruption to the global petrochemical
supply-demand balance.
As the petrochemical industry in Japan,
Europe and the Unites States grappled with aprotracted
slump,
thepetrochemicalcompanies in these nations adopted two
distinct strategies: the first was to move awayfrom petrochemistry altogether; the other was
to keep petrochemistry as the foundation ofoperations while attempting to migrate tofunctional chemistry.
Petrochemical technology is generally
thought to have matured in the 1970s, but the
1990s witnessed unprecedented new trends
that were reflective of changes in the sector’s
supply-demand environment and otherfactors.
5.7.1

Emergence of the petrochemicalindustry in China and the changing
face of the Middle Eastern
petrochemical industry
The emergence of the petrochemicalindustry in China followed the same
trajectory as it had in South Korea, Taiwan
and the ASEAN region. The Chinese polymer
revolution started in the 1990s, whenpetrochemical companies in Middle Easternoil-producing nations began large-scale
exports of low-cost ethylene products. The
largest importer of these products was China,
which also imported other products that could
not be sourced from the Middle East fromJapan, South Korea and Taiwan.
The first petrochemical product to be
manufactured in China was synthetic fiber,with production volumes increasing up
rapidly from the 1990s. To support this effort,
several raw materials for synthetic fiber were
imported, such as EG, PTA and acrylonitrile.
The Chinese textile industry came todominate the world, firstly in thelabor-intensive sewing field, and later inwoven, knit and spun materials. Building on
its textile industry foundations, China looked
to expand into the production of synthetic
fiber in the 1990s. Its entry into this market
drove a contraction in the corresponding

markets in Japan, the United States andEurope. Moving into the 2000s, China rapidly
expanded its facilities. This forced countries
such as Taiwan and South Korea, which had
emerged as synthetic fiber manufacturers in
the 1970s, to scale back production. In the2010s, China’s synthetic fiber production
grew to account for nearly 70% of the global
supply.
In similar fashion, China’s expansion into
plastic processed goods also began throughthe importing of plastics as raw materials. In
the 2000s, its imports of petrochemical
products
ballooned,
promptingtheconstruction of large-scale petrochemicalcomplexes centered on naphtha steam
cracking in the mid-2000s. These projects
were driven by joint ventures with Europeanand American oil and petrochemicalcompanies, which supplied most of thetechnology. China continued to add newcapacity thereafter, but it was unable toimmediately replace imports due to the highgrowth in domestic demand. The expansion
has continued since the 2010s, with Asia
(including China, South Korea, Taiwan and
the ASEAN regions) and the Middle Eastdeveloping into the largest markets for
petrochemical products, both in terms of
demand and production volume.
However, the shift of the petrochemicalindustry to Asia and the Middle East was notnecessarily a favorable trend. In several ways,
this development significantly skewed theinternational character of the global
petrochemical industry. The first problem isthat
ChineseandMiddleEasternpetrochemical companies have grown into
giant organizations that rank among the five
top chemical companies in the world. In
countries such as South Korea, Taiwan andSingapore, petrochemical companies started
out under government control, but wereprivatized once business took off. Conversely,state-operated companies in the Middle East
and China have shown no sign ofprivatization and have become giant
enterprises. Another issue was the absence ofinternational influence in raw material prices.
Chinesestate-owned
petrochemicalcompanies were essentially giant oil
refineries, and petrochemistry only accounted
Systematic Survey on Petrochemical Technology

129for a fraction of their operations. Major oilcompanies in Europe and the United States
withdrew from the petrochemistry businessacross the board and redirected their attention
to their refinery businesses. This left Chinesestate-controlled companies as the only players
pursuing broad-based petrochemical business,a field in which they gained an alarmingly
large presence. Meanwhile, around 2000,
repeated rounds of capacity expansion in the
Middle East had virtually exhausted theregional supply of ethane derived fromassociated petroleum gas (APG). Thereafter,
local companies were forced to use LPG andcondensate, both originally export products,
as petrochemical feedstock. However, rawmaterials prices were set considerably lower
than export prices. Since petrochemistry had
started out with APG-derived ethane set at a
far lower price than the international price,
there was no choice but to reduce the price ofraw materials for secondary plants relying on
LPG and naphtha as feedstock, out ofconsideration for domestic circumstances.
Although the Middle Eastern countries had
long since grown beyond the phase ofcultivating new industries, their original
policies were left
unchanged. The
petrochemical industry in the oil-producing
nations of the region had pursued growth asits primary objective, and as part of thisprocess had gradually broadened its range
from an exclusive focus on American-styleethylene products to later also include all
Japanese and European olefin-based andaromatic-based products. Faced with poor
domestic demand and an inescapable relianceon exports, the Middle Eastern petrochemicalindustry entered a difficult phase ofoperations.
European and American oil
companies attempt to break awayfrom petrochemistryThematuringofpetrochemical
technology that started in the 1970s and thesubsequent technology transfer to developing
countries led to an emergence of new rivals.
Against this backdrop, Japanese, Americanand European oil petrochemical companies
started struggling with chronically excessive
capacity and poor earnings. As illustrated inTable 5.11, many of these companies
abandoned all future prospects for theirpetrochemical businesses and exited thepetrochemistry field, focusing instead on new
growth areas within the chemical sector, suchas pharmaceuticals. The transformations were
not always successful and several reputablecompanies, such as Hoechst (Germany) andICI (United Kingdom), did not survive theprocess as standalone entities. Others, such as
DuPont and Bayer, sold off theirpetrochemical businesses and looked for newopportunities in the agribusiness andpharmaceuticalsectors,but
were
subsequently unable to regain their former
luster. Among the oil giants that had once
invested aggressively in the petrochemical
field as downstream oil businesses, there wasalso a growing trend to significantly
downsize their petrochemical businesses intandem with a deterioration in earnings.
Meanwhile, investment funds proactively
acquired petrochemical businesses andrapidly grew into major global petrochemical
enterprises. As petrochemical businesses
were being bought and sold based oncomparatively
short-term
outlooks,
technology development and other long-term
activities lost further steam in Europe and theUnites States.
Table 5.11 Trends of expansion beyond
petrochemistry by major Western chemicalcompanies

5.7.2

130

5.7.3

From petrochemistry to functional
chemistry
Not all Western petrochemical companies
chose to move away from petrochemicals. A
large number of companies streamlined theirpetrochemical businesses to a certain degree,

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

but kept them as the foundation of theiroperations while pivoting into functional
chemistry. BASF and Dow Chemical are
typical examples of this. Many Japanesepetrochemical companies also followed thispath. Examples of success include the world’s
first commercial production of polyacrylicacid superabsorbent resin by Sanyo Chemical
in 1978, and the commercialization of COP
for optical resin by Zeon in 1990. The
development of such technologies could nothave taken place without a foundation inpetrochemical technology.
However, functional chemistry extended
beyondthescopeofconventional
petrochemical operations. It entailed not only
developing functional polymers, but also
concurrent molding technologies, and led tothe introduction of functional polymer
molded products on the market. This made it
more difficult for rivals to enter the sector,
and also lifted profitability. Even plantengineering companies with strengths inchemical engineering technology were unable
to easily make the leap to molding
technologies leveraging the performance offunctional polymers. Reflecting this shift
toward functional chemistry, the plastics
molding industries became the center ofJapan’s chemical industry in terms of added
value. As shown in Fig. 5.12, petrochemistry,
plastics molding and pharmaceuticals
followed similar growth trajectories as threeindustries that have supported the Japanesechemical industry from the 1970s to the1990s. Thereafter, the added value growth inpetrochemistry turned from flat to negative,
while plastics molding and pharmaceuticals
both remained on an uptrend. Rather than theend of growth in petrochemistry, thisdevelopment should be interpreted as theoutcome of an expansion in the scope ofbusiness by petrochemical companies toinclude plastics molding, in order to address
new business opportunities. Functional
chemistry has since outgrown its traditionalclassification under petrochemistry, and now
also includes polymer molding.

Fig. 5.12 Changes in the three largest added
values in the Japanese chemical industry.
5.7.4

New trends in petrochemical
technologies
Petrochemical technologies are said tohave matured in the 1970s. However, theJapanese petrochemical industry continued toincorporate remarkable technologies into
commercial production even after the 1990s,
as illustrated in Table 5.12. The bulk of thesewere developed by Japanese chemicalcompanies. Examples in Table 5.12 include
cyclohexanol derived from a cyclohexene
process, optical resin COP, dimethylcarbonate derived from a low-pressure
gas-phase process, MMAs derived from a
new acetone cyanohydrin (ACH) process,acetic acid derived from a direct ethane
oxidation process, polycarbonates derived
from a non-phosgene process, caprolactam
derived from an ammonium-sulfate-free
co-production process and acrylonitrile
derived from a propane method. The Japanesepetrochemical industry continues to work on
the frontlines of the global development of
petrochemical technology today. In addition,
the unprecedented technological trends
observed in the 1990s increased more andmore in the 2000s. In this section, we have
only reviewed the circumstances that gave
rise to these new technology trends. For
details on the technologies in question, refer
to Section 6.2.
Table 5.12 First production of petrochemical
products in Japan from the 1990s to 2008
Year
1990

Product
Cyclohexanone process
for cyclohexanol

1990

Optical resin COP

1992
1992

MTBE
Low-pressure

Company, factory
Asahi Kasei, Mizushima
Zeon Corporation,
Mizushika
Kashima Oil, Kashima
Ube Industries, Ube

Systematic Survey on Petrochemical Technology131gas-phase process for
dimethyl carbonate
1994
1995
1996
1997
2002
2003
2004

PES
Metallocene gas-phaseprocess for linear
low-density
polyethylene
New ACH process for
MMA
Ethylene directoxidation process for
acetic acidNon-phosgene process
for polycarbonate
Ammonium sulfate-free
co-production process
for caprolactam
Metathesis process for
propylene

Sumitomo Chemical,
Ehime
Ube Industries, Chiba
Mitsubishi Gas Chemical
Company, Niigata
Showa Denko K.K., Oita
Asahi Kasei, Chimei－
Asahi Corporation in
Taiwan*Sumitomo Chemical,
Ehime
Mitsui Chemicals, Osaka

Asahi Kasei Chemicals,
Tongsuh Petrochemical
Corporation in Korea*
Note: The asterisk (*) denotes a technique that a chemicalcompany of Japan has developed, but was produced first at
the joint venture overseas.
2007

Propane process foracrylonitrile

Source: Prepared with Reference [12](1) Technologies aiding the shift fromethylene to propylene
From the 1980s onwards, propylene
demand increased steadily on the back of thegrowth of PP. Around 1970, PP competedwith IPA, propylene oxide, acrylonitrile andother compounds, and only accounted forsome 15% of propylene demand. By 2010,
however, that percentage had increased toover 60%. This shows the remarkably strong
growth PP has enjoyed among propylene
derivatives.
Meanwhile,followingcommercial production of acetic acid using
the methanol process in the late 1970s, theproduction volume of acetaldehyde dropped
considerably from the 1980s, while thedemand for ethylene in developed countries
declined compared with propylene. Still,
petrochemical companies that focused
exclusively on ethylene production emerged
and expanded in the Middle East, and theyflooded global export markets with ethylene
products, further narrowing the scope fordeveloped countries to establish naphthasteam
cracking
plants.
Accordingly,
propylene shortages became apparent fromthe 1990s. The price of propylene rose
gradually compared with that of ethylene.
While it had once hovered at around half of132

the ethylene price, the price of propylene rose
to parity with ethylene by around 2010.
To address these changes in theenvironment,
severalnew
propylene
production methods were developed andsuccessively commercialized.
(2) Shift to monomer direct synthesis
technology from paraffin
From its onset, petrochemistry has been
built on two foundations: olefin chemistryandaromatic
chemistry.
Saturatedhydrocarbons (alkane or paraffin) such as
methane, ethane and propane have poor
reactivity and extremely limited direct
applications. Paraffin is mainly used as a raw
material for steam cracking. However,acrylonitrile gave rise to the development oftechnology to create double-bond industrialorganic chemicals from paraffin, and several
other potential technologies also came into
being as a result. The ongoing developmentof technologies using paraffin as a raw
material could alter the face of traditional
petrochemical complexes.
(3) Metallocene and post-metallocene
catalysts
The polyolefin field saw the emergenceof metallocene catalysts in the 1980s, which
attracted attention by virtue of their highly
superior performance compared with thetraditional Ziegler-Natta catalysts. The newcatalysts were first deployed in the field ofpolyethylene. However, they were unable toexert a profound impact on the petrochemicalmarket in the way the Ziegler-Natta catalysts
had in the 1950s and the commercial
production of L-LDPE had in the 1980s.
Demand for petrochemical products had
matured, and minor improvements in
productivity and performance proved unable
to easily outdo existing product markets.
However, this was not the end of themetallocene catalyst technology story. A
series of post-metallocene catalysts that
surpassed the original metallocene catalysts
have been successively announced since thelate 1990s.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

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Industry Association, 1971.
[10] “Twenty-year
historyofthepetrochemicalindustry,”
Japan
Petrochemical Industry Association, ed.,Japan Petrochemical Industry Association,
1981.
[11] “Thirty-year
historyofthepetrochemicalindustry,”
Japan
Petrochemical Industry Association, ed.,Japan Petrochemical Industry Association,
1989.
[12] “Fifty years of petrochemistry—The
half-century
timeline,”Japan
Petrochemical Industry Association, ed.,Japan Petrochemical Industry Association,
2008.
[13] “Plastic production, waste, recycling,
and disposal statistics for 2013,” Plastic
Waste Management Institute.
[14] “History of high pressure polyethylene”
Japan
Petrochemical
Industry
Association, ed., Japan Petrochemical
Industry Association, 1998.

Systematic Survey on Petrochemical Technology133

6 Technological system and systematization of
petrochemistryWe
havealreadyoutlinedthepetrochemical products by the number ofcarbon atoms in Chapter 3, as well as briefly
touching on some of the production
technologies for each product. In this chapter,
we shall discuss the modern petrochemical
technology system, taking a cross-sectionalview of the technology. We shall also
examine new trends in petrochemical
technology that have emerged in the 1990s
and since, as well as discussing the history of
petrochemical technology on the basis of thetechnology system, examine the essence of
petrochemical technology amidst the large
numberofmass-producing
chemicaltechnologies that predated petrochemistry,
and introduce epoch-making technologies.
Finally, we shall systematize petrochemical
technology and discussed its future prospects.

6.1 Technologicalsystemandcharacteristics of petrochemistryThe
technologicalsystemofpetrochemistry as well as the categories of
petrochemical products can roughly beclassified
into
three
areas:
basic
petrochemicals, industrial organic chemicals
and polymers (Fig. 6.1). A great variety of
petrochemical processes are available,
because processes developed before thecreation of petrochemistry and petroleum
refining processes have flowed over into
petrochemistry and been developed. Thissection summarizes the technological systemof current petrochemistry.

6.1.1

Technological system of basic
petrochemicals
As shown in Fig. 6.2, the technologicalsystem of basic petrochemicals from natural
gas and petroleum is classified into
manufacturing technologies for syngas, olefin
and aromatic hydrocarbon.

Fig. 6.2 Technology system of basic
petrochemicals.
As shown in Fig. 6.3, the manufacturing
technologies for olefin are classified into
technologies for lower and higher olefins.
The former technologies are further classified
into technologies for C2 olefin, C3 propylene,
C4 butadiene having a conjugated doublebond and C4 butylenes having one doublebond. Many of these technologies wereoriginally petroleum refining technologies
that subsequently flowed over into
petrochemistry and were further developed.
The latter processes are further classified into
technologies for higher linear olefins andbranched-chain higher olefins.

Fig. 6.3 Olefin production technology system.
Fig. 6.1 Technology system of
petrochemistry.

134(1) Ethylene manufacturing technologies
As described in Chapter 4, industrialorganic chemicals and polymers were alreadybeing manufactured all around the world

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before the creation of petrochemistry, using
raw materials that were available nearby.
Figure 6.4 summarizes the technologies for
manufacturing ethylene prior to theestablishment of petrochemistry. A method ofcollecting ethylene as a byproduct involved
separating ethylene from coke oven gas at
low temperature. This method was commonlyused in Germany. Another method involved
obtaining small quantities of ethylene as a
byproduct during the manufacture ofacetylene from natural gas using the arc
process. Catalytic technologies were also
used for the production of ethylene. Ethylene
was produced from fermentation ethanol by
gas phase dehydration in the presence of acidclay or other catalyst at various places aroundthe world. This technology was essential forearly polyethylene production, because it
yielded ethylene with higher purity moreeasily than other technologies. Ethylene wasproduced by partial hydrogenation ofacetylene during the Second World War inGermany. The development of catalysts was
the key to the success of this process. Thus,
ethylene production technology had its rootsin the forests of coal chemistry and evenfermentation chemistry.
Meanwhile,
ethylene
production
technology was the first of the lower olefin
manufacturing technologies using petroleum
as raw materials to be developed, in the formof thermal cracking of heavy oil (Fig 6.5).
Heavy oil was thermally cracked to give
waste gas containing ethylene and otherlower olefins, from which the ethylene andpropylene were collected. To obtain gasoline
fractions, heavy oil is thermally cracked athigh temperature and high pressure in theabsence of a catalyst. This is purely apetroleum refining technology. The Burton
process developed in 1913 was the firstthermal cracking technology for petroleum. It
was industrialized by Standard Oil (Indiana)
in 1913. The Dubbs process developed in1914 involved the cracking of petroleum bypartial combustion of heavy oil. Subsequently,
manypetroleum
thermalcracking
technologies were developed from the 1910s
to the 1920s. However, because these were
petroleum refining technologies rather thanpetrochemical technologies to obtain gasoline,

they are not detailed here.

Fig. 6.4 Ethylene production technology
predating petrochemistry.
Steam cracking was developed as anextension of thermal cracking of petroleum.
This started with the production of ethylene
by steam cracking of ethane by U.S. Carbide& Carbon Chemical in 1920. Subsequently,
U.S. Standard Oil (NJ) industrialized
production of ethylene by steam cracking of
propane in the first half of the 1920s and by
steam cracking of naphtha in 1941. An
outline of steam cracking is given in Section
3.3.3. Steam was added in order to improvethe conversion rate by lowering the partialpressure of naphtha or ethane as a raw
material to make the thermal cracking
equilibrium reaction progress towards thecracking side, to reduce the accumulation ofcarbon on the internal wall of the reaction
tube
and
to
controlathermalcracking-induced temperature fall through theheat of the steam.
As shown in Table 5.3, in addition to
tube-type steam cracking that was developed
as an extension of thermal cracking of
petroleum in the United States, various
ethylene manufacturing technologies weresuddenly developed and industrialized after
the Second World War, competing with eachother from the late 1940s to around the 1960s.
These technologies included the Catarole
process using a copper-iron catalyst (Shell
Chemicals 1947), the moving bed cracking
process using sand as a medium (TPC process,Socony-Vacuum 1947, sand-cracking process,Lurgi 1955) and high-temperature steam
cracking aimed at the co-production ofacetylene (BASF process, 1960, Hoechst
process, 1960).
Ultimately, only exothermic tube type steam
cracking survived the competition in the
Systematic Survey on Petrochemical Technology

135

1970s. Various exothermic tube type steam
cracking processes have been developed,
depending on the type of cracking furnaceand the method of separating/refining basic
petrochemicals, and have been competingwith each other. At present, the Stone &Webster process and the Lummus process,among others, are widely used all around theworld. Exothermic tube type steam cracking
has gone through the following technologicaldevelopments and improvements. In the firsthalf of the 1960s, the retention time in the
tube was shortened from 0.7–1.5 seconds to
0.2–0.4 seconds. This was due to thediscovery of the mechanism underlying theadherence of coke to the pipe wall. As aresult, the yield of ethylene increased. In the
1960s, the installation of the tube waschanged from horizontal to vertical. In the
1960s, a quench heat exchanger (TLE) and acentrifugal compressor were introduced,
resulting in energy saving as well as anincrease in the size of the equipment.

From the 1950s to the 1960s, of all theolefins made by steam cracking of naphtha,
propylene tended to be being produced inexcess. Therefore, the triolefin process
producing ethylene and n-butylene bydisproportionation in the presence of a solid
catalyst was developed by Philips in 1960.
This process was only industrialized in
Canada in 1966. However, because asubsequent expansion in the demand for
propylene solved the problem of excessive
propylene, the use of this process was
discontinued within less than 10 years.
Although the mechanism of the reaction was
unclear at the time, it was subsequently foundto be metathesis reaction via a carbene metal
complex. As mentioned in Section 6.2, due toa change in the propylene supply-demandenvironment, the reverse reaction was revived
as a process for manufacturing propylene by
the metathesis reaction in the 1990s.

Fig. 6.5 Ethylene production technology system.
(2) Propylene manufacturing technologies
Figure 6.6 summarizes the system of
propylene
manufacturing
technologies.
Propylene as well as ethylene is made fromwaste gas obtained by the thermal cracking ofheavy oil. However, petroleum refining
technologies to obtain gasoline fractions fromheavy oil did not develop towards
non-catalytic thermal cracking, but towards

136

catalytic
cracking.
Houdry(France)developed the fixed-bed cracking processusing a silica-alumina catalyst in 1927 andthe U.S. Sun Oil industrialized it in 1938. In
1938, Kellogge developed the catalytic
cracking process using a fluidized bed
catalyst. Standard Oil (NJ) further developed
the process by joint studies with Kellogge. It
developed the fluidized catalytic cracking

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(FCC) process in 1940 and industrialized it in1942.
Meanwhile,
Socony-Vacuum
developed moving bed TCC as a modificationof the Houdry process and industrialized it in1943.
Waste gas is obtained in larger quantities
by the catalytic cracking of heavy oil than by
the thermal cracking of heavy oil. Since it
contains small amounts of ethylene and large
amounts of propylene and butylenes, it
became a large-scale supply source of
propylene. This is because thermal cracking
is a radical reaction, while catalytic cracking
is an ionic reaction.
When gaseous raw materials with C3 or
C4 and liquid raw materials such as naphtha
are steam cracked to obtain ethylene,
propylene is also produced in approximately
half the amount of ethylene. This process is amajor propylene supply source. Especially inJapan, Asia, Europe, etc. where ethylene isproduced from naphtha by steam cracking,the steam cracking process is the mostimportant propylene supply source, while
waste gas from FCC plants is no more than asecondary supply source and classified ascomplementary. However, the steam crackingof ethane produces ethylene and only verysmall quantities of propylene. Therefore, theFCC plants are important propylene supply
sources in the United States where ethane isused in larger quantities as a material for
ethylene.
Meanwhile, in the 1990s, the supply of
propylene from the above two byproducttechnologies (steam cracking of naphtha andthe FCC process) became insufficient.
Therefore, technologies for producing
propylene as the main product, such as thereinforced fluidized catalytic cracking
process, propane dehydrogenation and themetathesis process, were developed andindustrialized. These technologies aredescribed in Section 6.2, “New trends inpetrochemical technology.”
Unlike ethylene, propylene has neverbeen synthesized from raw materials otherthan petroleum to give propylene products
since the creation of petrochemistry.

Fig. 6.6 Propylene production technology system.
(No propylene production technology predating petrochemistry)(3) Butadiene manufacturing technologies
Since the production of synthetic rubber
was a very important national issue in
Western countries during the Second World
War, importance was attached to the
production of butadiene. However, because it
was not until after the Second World War thatsteam cracking of naphtha became widelyused in Europe and Japan, during the war

butadiene was produced in these countries by
the processes shown in Fig. 6.7. These werecoal chemistry and fermentation chemistry
technologies.

Systematic Survey on Petrochemical Technology

137

Fig. 6.7 Butadiene production technology
predating petrochemistry in Europe andJapan.
The first process is condensation of
acetaldehyde. Acetaldehyde was produced
from acetylene or fermentation ethanol.
Acetaldehyde is condensed and thenhydrogenated to give 1,3-butanediol, which isthen dehydrated to give butadiene.
The second process is dimerization ofacetylene. Under atmospheric pressure,acetylene is dimerized into monovinyl
acetylene, which is then hydrogenated to give
butadiene.
The third process is ethynylation ofacetylene. It is one of the Reppe reactions.
Under pressure, acetylene is reacted withformaldehyde to give butadiene via
1,4-butynediol and 1,4-butanediol. However,
because the third process was developed at
the end of the Second World War, it was only
industrialized on a very small scale.
Thefourthprocessisdehydration/dehydrogenation of ethanol. In
1928, it was developed and industrialized in
the Soviet Union. During the Second World
War, it was also industrialized in the UnitedStates. According to a modification of thisprocess, ethanol is oxidized to acetaldehyde,
and butadiene is obtained by the dehydration
reaction of acetaldehyde with ethanol. This
process is described above in Section 5.2.5.
At present, as shown in Fig. 6.8 the mostimportant butadiene supply source is a
byproduct of ethylene production by steam
cracking of naphtha. However, in this case, ahydrocarbon having more carbon atoms thanbutane must be used as a raw material,
because butadiene cannot be obtained by thesteam cracking of ethane or propane.
On the other hand, in the United States
where butane and butylene could be obtainedinlarge
quantities,
thebutylene138

dehydrogenation process shown in Fig. 6.8
was developed and industrialized on a large
scale during the Second World War. The raw
material for butylene was obtained fromwaste gas produced from the catalytic
cracking of heavy oil. Although this process
is not as competitive as the byproduct processfrom steam cracking, it is still presently used
to cover a shortage of butadiene in the UnitedStates.

Fig. 6.8 Butadiene production technology
system.
Butadieneis
also
obtainedbydehydrogenation of n-butane from waste gas
produced by catalytic cracking of heavy oil or
natural gas (Houdry process). This process
was used during the Second World War, but
has not been used since then due to its highcost.
(4) Butylenes manufacturing technologies
As with propylene, butylenes have neverproduced from raw materials other thanpetroleum
beforethecreationofpetrochemistry. Butylene manufacturing
technologies were established only throughpetrochemistry.
As shown in Fig. 6.9, butylenes aremainly produced from the C4 fraction
produced by steam cracking of naphtha or
waste gas produced by catalytic cracking of
petroleum. Butylenes are obtained as
byproducts in both processes. To obtainspecific butylenes, Sasol in South Africa
separates
1-butylene
fromsynthetic
petroleum by the Fisher-Tropsch process.
1-Butylene is used as an ethylene comonomerin manufacture of L-LDPE.
Due to the fact that the demand forbutylenes is generally not as strong as that for
propylene, processes to produce butylenes as
the main product are not widely used. Some
examples are as follows. In reinforced
fluidized bed catalytic cracking to produce

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propylene as the main product, butylenes arealso produced together with propylene. In
Saudi Arabia, 1-butylene is produced bydimerization of ethylene. It is used as an
auxiliary raw material for L-LDPE. In Saudi
Arabia, n-butylene is produced to obtainpropylene by the metathesis reaction of
ethylene with n-butylene obtained bydimerization of ethylene. In the 1990s, thedemand for MTBE rapidly increased in the
United States due to its use as an additive togasoline. Isobutylene is needed for the

production of MTBE. Since isobutylene
could not be adequately supplied from the
byproducts of steam cracking of naphtha andcatalytic cracking of petroleum, it was
producedinlarge
quantities
bydehydrogenation of isobutane. However,from the 2000s onwards, the addition of
MTBE to gasoline was prohibited and as aresult, the dehydrogenation of isobutane
declined.

Fig. 6.9 Butylene production technology system.
(5) Higher
linearolefinmanufacturing technologiesHigher linear
olefin manufacturing technologies originatedin oleochemistry before the dawn of
petrochemistry. These technologies are used
to produce fatty alcohols by the methyl
esterification and high-pressure reduction offats and oils, and then dehydrate the alcohol
to produce α-olefins (Section 4.3.2). Once it
becamepossibletoproducealkylbenzenesulfonic
acid
soda
from
dodecene by the tetramerization of propylene,
it was then possible to produce higher olefinsin large quantities. However, this dodecene
was often branched rather than linear,
resulting in issues of foam pollution (Section
5.5.2 (3) 1). Accordingly, technologies tomanufacture higher linear olefins from fats
and oils have come to be utilized again.
Meanwhile, several technologies have beendeveloped to produce higher linear olefinsusing petrochemistry, as shown in Fig. 6.10.
Once n-paraffin has been adsorption
separated using a zeolite from the kerosene
fraction, the n-paraffin can be steam cracked

to produce a higher linear olefin mixture withinternal or terminal double bonds. Other
α-olefin producing technologies include
separation from synthetic oil using the
Fisher-Tropsch
process,
Ziegleroligomerization of ethylene, SHOP-method
oligomerization of ethylene and catalytic
dehydrogenation of n-paraffin.

Fig. 6.10 Higher linear olefins production
technology system.
(6) Aromatic hydrocarbon manufacturing
technologies
Systematic Survey on Petrochemical Technology

139

Manufacturing processes for aromatichydrocarbons as well as those for olefins arevery important manufacturing processes forbasic petrochemicals. Since before thecreation of petrochemistry, benzene, toluene,
naphthalene, anthracene, etc. were produced
by distillation/separation of coal tar obtainedby retorting phase of coal. Even now, this is asignificant process for the manufacture ofnaphthalene. However, it is difficult to obtain
xylene from coal tar.
The main supply sources for aromatichydrocarbons from petroleum are cracked
gasoline obtained by steam cracking of
naphtha for the production of ethylene and areformate obtained by catalytic reforming of
petroleum for the production of high octane
gasoline. Since cracked gasoline contains
many aromatic hydrocarbons, benzene can be
refined by azeotropic distillation. It is also
possible to refine benzene, toluene, etc. after
further increasing the concentration ofaromatichydrocarbons
byextractive
distillation. As the concentration of aromatichydrocarbon is lower in a reformate than in
cracked gasoline, first only the aromatichydrocarbons are extracted from thereformate by solvent extraction. After

extraction, paraffin and cycloparaffin withmany branched chains are left in thereformate. These paraffins are useful gasoline
ingredients. For solvent extraction, various
polar solvents such as ethylene glycols/water,
sulfolane,
N-methylpyrrolidone/water,
Dimethyl sulfoxide (DMSO)/water andN-formylmorpholine/water have been used
and many processes such as the Udex process
have been developed and industrialized.
As shown in Fig. 6.11, benzene isrefined/separated from the above aromatichydrocarbon
fractionsbyazeotropic
distillation and extractive distillation. Apartfrom that, hydrogenating dealkylation of
toluene and disproportionation of toluene aremainly used for producing benzene. Benzene
and methane are obtained using the former
reaction, while benzene and xylene are
obtained using the latter reaction.
Although toluene is useful as a gasoline
fraction, there is little chemical demand for it.
Therefore, it is rare for toluene to be obtained
from a reformate. It is exclusively obtained fromcracked gasoline produced by steam cracking(Fig. 6.12).

Fig. 6.11 Benzene production technology system.

140

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Fig. 6.12 Toluene production technology system.
Xylene has three isomers, namely, ortho-,metha- and para-xylenes. Ethylbenzene isalso a C8 aromatic hydrocarbon. Since theboiling points of these four aromatichydrocarbons are similar, it is difficult toseparate them by distillation. A mixture ofthese three xylene isomers, or a mixture of C8
aromatic hydrocarbons with ethylbenzene
added, is called mixed xylene. Meanwhile,
there is greater demand for o-xylene andp-xylene. Ethylbenzene is used as a raw
material for styrene. However, in this case, it
is not refined/separated from mixed xylene,
because high purity ethylbenzene issynthesized by the reaction of ethylene withbenzene.
As shown in Fig. 6.13, mixed xylene ismainly obtained by naphtha steam cracking
and reforming. Both processes are byproductprocesses. One process that is used primarily
fortheproductionofxyleneisdisproportionation of toluene. Benzene is also
produced in this process.

Fig. 6.13 Xylene production technology
system.

Crystallization has long been performed
for the manufacture of p-xylene, which has
the greatest demand (Fig. 6.14). The boilingpoint of each component of mixed xylene issimilar, while the melting point is different,
being -95°C, -48°C, -25°C, and 13°C for
ethylbenzene, m-xylene, o-xylene andp-xylene,
respectively.
Consequently,
p-xylene can be obtained if mixed xylene iscooled and crystallized. However, thecrystallization process consumes muchenergy. Therefore, once the adsorption
process using solid adsorbents such as zeoliteand molecular sieves (Aromax process by
Toray, Parex process by UOP) was developed,
it completely replaced the existing processfrom the 1970s onwards.
M-xylene has the smallest demand of thethree xylene isomers; it is the resulting
product once an equilibrium mixture of
mixed xylene has been made byisomerization and then o-xylene and p-xylene
have been separated from the mixture. As
industrial processes, the octafining process(Arco/Engelhard) was developed in the 1960s,
followed by the isomer process (UOP), the
LTI process (Mobil Chemical), etc. In the
1990s, the HTI process (Mobil), in which
ZSM-5 zeolite was partially replaced byplatinum, was developed and widely used.
This process makes use of the phenomenon
whereby the equilibrium reaction is further
progressed by the remaining m-xylene ando-xylene because they cannot escape through
Systematic Survey on Petrochemical Technology

141the empty holes in the zeolite as easily as
p-xylene, making the yield of p-xylene higher
than the equilibrium concentration.

Fig. 6.14 p-Xylene production technology
system.
(7) Syngas manufacturing technologies
Syngas was originally manufactured fromcoke. It was at first manufactured for
production of city gas in the latter half of the
19th century and for ammonia, methanol andsynthetic petroleum in the first half of the20th century. It is a very old process. Since it
became possible to obtain large amounts ofpetroleum and natural gas after the Second
World War, syngas then began to be
manufactured from these materials. As shownin Fig. 6.2, there are two manufacturing
technologies. One is exothermic steam
reforming in the presence of a nickel catalyst.
It is often applied to natural gas. The other issteam reforming by non-catalytic partial
combustion. A great variety of raw materials
ranging from natural gas to heavy oil can be
used.
(8) Summary
The system of technologies for basic
petrochemicals has been described for eachproduct in subsections (1) to (7). Further, as
shown in Fig. 6.15, these technologies may
be cross-sectionally classified into reaction
technologies
andseparation/refining
technologies. It is characteristic that the
separation/refining technologies are just as

142

significant as the reaction technologies forbasic petrochemicals, while the reaction
technologies are very significant for theindustrial organic chemicals and polymers
mentioned below.
In
terms
of
separation/refining
technologies, in addition to distillation that is
generally performed in chemical technologies,
solvent extraction and extractive distillation
are performed for the separation of butadiene
and aromatics, while adsorption is performed
for the separation of n-paraffin and p-xylene.
Recrystallization was performed for the
separation of p-xylene, but was later replacedby adsorption because it was expensive.
Furthermore, in case of difficulty inseparation by physical procedures, separation
can also be done using differences inreactivity. Some examples are the separationof isobutylene by utilizing differences inhydration reactivity in the presence of a solidacid catalyst and the separation of
cyclopentadiene from C5 fraction by using
differences in dimerization reactivity.
Meanwhile, the reaction system isbroadly classified into non-catalytic andcatalytic technologies. Steam cracking as a
non-catalytic technologies and catalytic
cracking of heavy oil and catalytic reformingof naphtha as catalytic technologies supply
far greater amounts of basic petrochemicals.
There are many other catalytic technologies,
primarily for producing specific basic
petrochemicals
other
than
ethylene(propylene by dehydrogenation of propane,butadiene by dehydrogenation of butylene,
α-olefin by oligomerization of ethylene,
benzene by dealkylation of toluene, benzene
and xylene by disproportionation of toluene,p-xylene by isomerization of m-xylene, etc.).

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Fig. 6.15 Technology system of basic petrochemicals (summary)chemistry, fermentation acetone/butanol
chemistry and other fields that developed
6.1.2 Technological system of industrial
before the creation of petrochemistry.
organic chemicals
Furthermore, there are no derivatives with the
There are a great number of industrial
potential to progress to the next stage oforganic chemicals and their intermediates;industrialorganic
chemicals,
likethere are also a great number of processes for
acetaldehydeinacetylene
chemistry.
Inmanufacturing these products. As shown inacetylene chemistry, not only C2 products,
Fig. 6.16, the technological system of thesesuch as acetic acid, but also various
chemicals is made up of C1 chemistrycompounds, such as C3 acetone, C4 butyl[Footnote 1], olefin chemistry, aromatic
alcohol and butadiene, were obtained fromhydrocarbon
chemistry,
cycloparaffin
C2 acetaldehyde. This was because C2
chemistry and other synthetic organic
acetylene was the only basic chemical inchemistry.
acetylene chemistry. In petrochemistry, as
mentioned in Chapter 3, ethylene oxide,
acetone, acrylonitrile, acrolein, phenol, etc.
are important derivatives from which further
development of various products is
expectable, but none of them have as yetgrown to a key material comparable toacetaldehyde in acetylene chemistry. In
Fig. 6.16 Technology system of industrial
petrochemistry,
derivatives
withorganic chemicals.
corresponding carbon number atoms are often
manufactured from the starting materials of
The reactivity of olefins is not as strong as
various olefins and aromatic hydrocarbons
that of acetylene but not as weak as that of
obtained as basic petrochemicals. Moreover,paraffin (alkane). Moreover, olefin chemistry
importance is often attached not to thehas also developed in many areas due to thedevelopment of processes for production offact that not only ethylene but also various
expected industrial organic chemicals via
other olefins, such as propylene, butylenes
several industrial organic chemicals, but toand butadiene, are simultaneously produced
the development of processes that canby the steam cracking of naphtha, one of the
produce
expectedindustrialorganic
olefin manufacturing processes. On this point,chemicals from basic petrochemicals, either
olefin chemistry is clearly different fromdirectly or in as few steps as possible.
acetylene chemistry, fermentation ethanol
Furthermore, rather than stoichiometric
reactions, petrochemistry often aims at[Footnote 1] The system of processes for manufacturing C1 or morecatalytic reactions, using the cheapest
industrial organic chemicals from C1 methane and syngas and thecategories of such products are called C1 chemistry.
Systematic Survey on Petrochemical Technology

143possible secondary raw materials, such as
oxygen, ammonia or water. In particular, it
often aims at reactions that can replace
reactions that use elements that are notcontained in the final expected product (forexample, addition of hypochlorous acid andoxidation by nitric acid). In green chemistryterms, these are reactions with good atom
utilization efficiency.
(1)
Olefin chemistry: addition to
double bonds
As shown in Fig. 6.17, olefin chemistry isclassified as addition reactions to the doublebond of olefins, reactions to places other thanthe double bond, and special reactions. Of
these, special reactions are further classified
into the oxychlorination process and olefin
metathesis reactions. Oxychlorination andmetathesis reactions are described in (3) ofthis section and in Section 6.2.1, respectively.

Fig. 6.17 System of olefin chemistry.
The addition reaction to the double bondof olefins is the core of olefin chemistry. It issimilar to addition reactions to the triple bondin acetylene chemistry. However, as shown in
Fig. 6.18, olefin chemistry is much morediverse than acetylene chemistry.
1) Addition of sulfuric acid, water andalcohol
The addition of sulfuric acid to the
double bond of olefins is the oldest
petrochemical process. As described in
Chapter 5, History of petrochemistry, in 1920,
Standard Oil (NJ) produced isopropyl sulfuric

144

acid by the stoichiometric reaction of
propylene with sulfuric acid and thenhydrolyzed it to make IPA and started
industrial production. This process triggered
off petrochemistry. Similarly, in 1923,
Sharpless Solvent produced amyl alcohol by
the reaction of isopentene with sulfuric acid,followed by hydrolysis. In 1930, Carbide &Carbon Chemical produced ethyl sulfuric acidfrom ethylene and sulfuric acid and thenhydrolyzed it to make synthetic ethanol andstarted industrial production. In the same year,
Shell Chemicals started industrial productionof sec-butyl alcohol from n-butylene using
the sulfuric acid process. However, since
production of alcohol by the sulfuric acidprocess is associated with production of large
amounts of dilute sulfuric acid, it must beconcentrated for reuse. Consequently, oncethe catalytic process for directly producing
alcohols by adding water (direct hydration) tothe double bond of olefins was developed,
this method soon replaced the sulfuric acidprocess. In 1947, Shell Chemicals developed
a process for directly synthesizing ethanolfrom ethylene and steam in the presence of aphosphoric acid catalyst and industrialized it
the following year. In 1951, ICI started
industrial production of IPA by direct
hydration of propylene in the presence of atungsten oxide-titanium oxide-iron oxide
catalyst at 250 atm and 270˚C. Ether isdirectly manufactured by this process if
alcohol is added to the double bond in placeof water. This process was used for
production of diethyl ether. The MTBE
developed in the late 1970s was the first ether
to be produced on a large scale. MTBE wasproduced from isobutylene and methanol in
the presence of a solid acid catalyst, such asacid ion exchange resin. At present,
ethyl-t-butyl ether (ETBE) is produced from
isobutylene and ethanol.

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Fig. 6.18 Olefin chemistry; System of technology on addition to double bond.
2) Addition of hypochlorous acid andoxygenThe addition of hypochlorous acid to the
double bond of olefins is one of the oldest
stoichiometric reactions, along with theaddition of sulfuric acid. In 1920, Carbide &CarbonChemicalproduced
ethylenechlorohydrin by the reaction of ethylene withhypochlorous acid. This process also
triggered off petrochemistry. Ethylene oxide
is obtained when ethylene chlorohydrin is
dehydrochlorinated with sodium hydroxide or
calcium hydroxide. Since this reaction is
stoichiometric, large amounts of sodium
chloride and calcium chloride are produced as
byproducts.
Ethylene oxide is reacted with water togive EG, diethylene glycol and triethylene
glycol. In the 1930s, ethylene cyanohydrin
was made from ethylene oxide and hydrogencyanide and then thermally cracked to giveacrylonitrile. EG can also be made byhydrolysis of ethylene chlorohydrin withsodium hydroxide solution (BASF, 1919).
However, the chlorohydrin processwastes chlorine and sodium hydroxide. In
1937, UCC industrialized a process for
directly producing ethylene oxide byepoxidizing ethylene by air oxidation (10–30
atm, 230–325°C) in the presence of a silver
catalyst. After the development of thiscatalytic process, the ethylene chlorohydrin
process declined.
It is worth noting that ethylene oxidechemistry developed early in the 1930s
because a process was developed for
manufacturing ethylene oxide at a low price.
In 1937, IG Farben released polyoxyethylene
ether of alkyl phenol as a nonionic surfactant.
In addition, fatty acid, fatty acid amide andfatty alcohol polyoxyethylene ether wereindustrialized. In 1944, U.S. company Atlas
Powder released an ester of sorbit and fatty
acid and its polyoxyethylene compound asnonionic surfactants named Span and Tween,
respectively. Ethylene oxide chemistryalready started before petrochemistry had
fully flourished.
As with ethylene, propylene chlorohydrin
is produced by the stoichiometric reaction of
propylene with hypochlorous acid and thendehydrogenated with calcium hydroxide togive propylene oxide. In 1929, UCC
industrialized this process. However, unlike
the case with ethylene, catalytic technologies
for directly epoxidizing propylene withoxygen have not yet been developed andtherefore, the propylene chlorohydrin process
is still used as the main manufacturing
process for propylene oxide.
Oxirane Chemical developed the Halcon
process in 1968 and industrialized it in 1970.
According to this process, a peroxide(hydroperoxide) is made from isobutane,
ethylbenzene, cumene, etc. and is thenreacted with propylene in the presence of acatalyst to give propylene oxide (see Section
3.4.3 (4)). In the 2000s, it became possible to
Systematic Survey on Petrochemical Technology

145

produce hydrogen peroxide cheaply on alarge scale, resulting in the industrializationof a process for producing propylene oxide by
the reaction of propylene with hydrogen
peroxide. Since only water is produced as a
byproduct in this case, the production of
propylene oxide is not influenced by thedemand for byproducts.
3) Addition of chlorine
The addition of chlorine to the doublebond is also an old process. In 1925, Carbide& Carbon Chemical added chlorine toethylene to give ethylene dichloride (EDC)
and started production of it. EDC was
dehydrochlorinated to give vinyl chloride.
However, in 1932, Griesheim Electron inGermany developed a new process for
directly synthesizing vinyl chloride fromacetylene and hydrogen chloride in thepresence of a mercuric chloride-impregnatedsilica gel catalyst; as a result, the EDC
process was not widely used for the
production of vinyl chloride.
After the Second World War, as ethylene
became supplied cheaply in large quantities
by steam cracking, the EDC process revived.
Initially, the dehydrochlorination reaction to
produce vinyl chloride from EDC was aliquid-phase stoichiometric reaction using an
alkaline solution. However, in this case, halfof the chlorine was wasted as alkali salt. After
that, gas phase cracking in the presence of a
pumice stone or activated charcoal catalyst
was developed. In this case, half of thechlorine could be collected as hydrogenchloride. However, this had the disadvantage
in that the life time of each catalyst was short;as a result, the noncatalytic thermal cracking
process was widely used, in which EDC was
passed at high speed through a hightemperature and pressure pipe. Since the EDC
was thermally cracked to give vinyl chloride
and equimolar hydrogen chloride, thecombined ethylene-acetylene process wasdeveloped for producing vinyl chloride by thereaction of hydrogen chloride thus obtainedwith acetylene. However, after the ethylene
oxychlorination process was developed in
1965, the acetylene process and the combined
acetylene-ethylene process both declined
rapidly,while
thecombined146

EDC-oxychlorination
process
becameexclusively used (see Section 5.4.2 (2) 4)).
According to the ethylene oxychlorination
process, ethylene, hydrogen chloride andoxygen (or air) are reacted to give EDC in thepresence of a copper chloride/potassium
chloride catalyst. The key point of thisprocess is that hydrogen chloride obtained asa byproduct of thermal cracking of EDC isreacted with ethylene to give EDC.
The development of industrial processes
for manufacturing chlorine from hydrogenchloride started a long time ago. In the 1820s,
the Leblanc process as the first method of
manufacturing soda (patented in 1791 in
France) was actively used in the United
Kingdom. However, the hydrogen chloride
byproduct of this process was released into
the air and rivers, leading to the enactment of
the Alkali Act in the United Kingdom in 1863.
Investigations were conducted to collecthydrogen chloride and make it into chlorine
and then into bleaching powder. As a result,
the Weldon process (a liquid-phase processusing a manganese dioxide catalyst) and the
Deacon process (a gas phase process using acuprous chloride-impregnated brick catalyst,
the world’s first heterogeneous gas phaseprocess) were developed in 1866 and 1868,
respectively. Since the Weldon process
produced thick gas, it was industrialized
immediately. Meanwhile, since the Deacon
process produced dilute gas, it was not until
the 1880s that the process came into wide use,after Hurter conducted fundamental studies
on the absorption of hydrogen chloride. In
1932, Raschig developed an oxychlorination
process for producing chlorobenzene frombenzene, hydrogen chloride and oxygen in thepresence of a copper oxide-cobalt
oxide-alumina catalyst or a copper oxide-ironoxide-alumina catalyst. This process was animportant constituent of the Raschig process(formation of phenol and hydrogen chloride
from chlorobenzene and water) by gas phasehydrolysis of chlorobenzene, industrialized in1935 (see Section 4.6.1). This Raschig
process became a model for the ethylene
oxychlorination process.
A process in which hydrogen chloride as
a byproduct of thermal cracking of EDC was
made into chlorine using a method similar to

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

the Deacon process and reused was also
developed and industrialized. However, the
EDC production process by reproduction ofchlorine was short-lived. This was because
the ethylene oxychlorination process wasindustrialized
immediately
after
the
development of this process. Chlorine is notproduced by the ethylene oxychlorination
process, because ethylene is chlorinated in thepresence of a copper oxide catalyst and the
reduced catalyst is reproduced by air andhydrogen chloride.
The application of the oxychlorination
process has not yet been extended tocompounds
other
than
EDC
and
chlorobenzene. In 1975, a process for
manufacturing chloromethane from methane,hydrogen chloride and oxygen in the presenceof a copper chloride/potassium chloride fusedsalt catalyst was industrialized. However, thisprocess did not create any major applications
for oxychlorination.
4) Addition of aromatic hydrocarbon,
isobutane and olefins
The addition of aromatic hydrocarbons[Footnote 2], isobutane and olefins to double
bonds is a petroleum refining technology thatdeveloped in the 1930s. Petroleum waste gas
containing olefins is reacted with benzene in
the presence of an aluminum chloride catalyst
to give ethylbenzene and cumene. Polymer
gasoline is obtained by dimerization or
trimerization of olefins in the presence of aphosphoric acid catalyst, while alkylate
gasoline is obtained by the reaction of olefinswith isobutane.
Of these compounds, ethylbenzene andcumene obtained by the addition reaction ofaromatic hydrocarbons to double bonds areimportant raw materials for petrochemical
products. Ethylbenzene is dehydrogenated togive styrene. In 1930, styrene wasindustrialized by IG Farben. Ethylbenzene
was produced by the liquid-phase process inthe presence of an aluminum chloride catalyst[Footnote 3]. In 1953, Koppers Chemical[Footnote 2] This reaction is usually classified as an alkyl-group
substituention reaction into aromatic hydrocarbons (alkylation).
However, it is described here, because it can formally be considered
an aromatic hydrocarbon addition reactionfrom the olefin
perspective.
[Footnote 3] Ethyl chloride that is made by the reaction of
fermentation ethanol with hydrogen chloride is reacted with benzene

started production of ethylbenzene using thegas phase process in the presence of aphosphoric acid-silica/alumina catalyst. In
1958, UOP developed a gas phase processusing a boron trifluoride-hydrogen fluoride
catalyst. This was followed by thedevelopment and industrialization of the
Mobil-Badger process, which uses a zeolite
ZSM-5 catalyst, in 1980. It was subsequently
widely used around the world. To improve
manufacturing processes for ethylbenzene,
attempts have been made to control higher
order alkylated substances, to improve theconversion rate, to decrease the corrosivenessof catalysts and to prolong the life time ofcatalysts.
Benzene is added to the double-bond of
propylene to give cumene. Cumene is
exclusively used for the production of phenol
and acetone by the oxidation/cleavage
reaction. This phenol/acetone co-production
process using the cumene process wasdeveloped by Hock and Lang in 1944 andwas then industrialized by Hercules (UnitedStates) and Distillers (United Kingdom) in
1953. Cumene is synthesized in the presenceofasulfuric
acid/aluminum
chloride/hydrogen fluoride catalyst in theliquid-phase process, while it is synthesized
by addition of steam in the presence of aphosphoric acid-silica catalyst in the gas
phase process. Subsequent improvement of
catalysts resulted in the use of a zeolite
catalyst, as was used for ethylbenzene. Use of
the zeolite catalyst has spread rapidly since its
industrialization in 1996.
The third most important addition
reaction of aromatic hydrocarbons to the
double bond of olefins is the production ofhigher alkylbenzene from higher olefins andbenzene.
Thesulfonateof
higheralkylbenzene is an important anionicsurfactant and is used in large quantities fordetergents. The addition of benzene to higher
olefins is often performed by liquid-phaseprocess in the presence of hydrogen fluoride,aluminum chloride, etc. as a catalyst.
5) Hydroformylation (oxo process)in the presence of an aluminum chloride catalyst to give
ethylbenzene without going through ethylene. This route wasselected in countries where fermentation ethanol could be obtained
more easily than ethylene. This is a typical Friedel-Crafts reaction.
Systematic Survey on Petrochemical Technology147

In the hydroformylation of olefins,hydrogen and a formyl group (-CHO) areadded to the double bond to give aldehydewith one more carbon atom than the original
olefin. Aldehyde is made into various
derivatives by reduction (alcohol), oxidation(carboxylic acid) and aldol condensation. In
1938, Roelen (Ruhr-Chemie) discovered thatpropionaldehyde is produced when ethylene
is reacted with carbon monoxide andhydrogen in the presence of a cobalt catalyst(HCo(CO)4). When propylene is reacted in
the above manner, the main product isn-butyraldehyde, although isobutyraldehyde
is also obtained. n-butyraldehyde ishydrogenated as it is to give n-butanol, orhydrogenated after aldol condensation to give2-ethylhexanol. These alcohols were reactedwith phthalic anhydride to give phthalate
esters, which were used as plasticizers forpolyvinyl chloride. Since 2-ethylhexanol inparticular is used in large quantities even now,
n-butyraldehyde is in great demand, although
there is an excess of isobutyraldehyde.
In 1975, UCC and other companies
succeeded in the industrialization of thehydroformylation
processusing
theWilkinson
catalyst(triphenyl
phosphine-coordinated rhodium catalyst).
This process can makes a significantly higher
n-aldehyde/isoaldehyde ratio than the cobalt
catalyst process. Hydroformylation is applied
not only to ethylene and propylene, but also
to C7–C12 olefin oligomers, such as
isoheptene, diisobutylene and tripropylene.
C8–C13 oxoalcohols produced by thisreaction are made into phthalate esters andthen used as plasticizers. C11–C18 α-olefins
undergo hydroformylation to give C12–C19
linear higher alcohols. These are used for the
production of surfactants and fiber
auxiliaries.
6) Addition of hydrogen cyanide
The addition reaction of hydrogencyanide to double bonds is important for the
production of adiponitrile in petrochemistry.
Among several presently available methodsof manufacturing adiponitrile, the mostcommon is the addition of two hydrogencyanide molecules in two stages to butadienein the presence of a nickel-triallyl phosphite

148

catalyst. Adiponitrile is hydrogen reduced togive hexamethylenediamine, which is thenused as a raw material for 6,6-nylon.
(2) Olefin chemistry: Reaction to places
other than double bonds
Like ethynylation (reaction acetylene ofto hydrogen) as one of the Reppe reactions inacetylene chemistry, the reaction to hydrogenadjacent to the double bond and the reaction
to hydrogen in the methyl group adjacent to
the double bond (hydrogen at the allylic
position) were successively developed in
olefin chemistry from the latter half of the
1950s onwards (Fig. 6.19). As a result, thedemand for olefin chemistry using propylene
and butylene as starting materials expanded
dramatically, despite it once having a lower
demand than ethylene.

Fig. 6.19 Olefin chemistry; System ofreactions to places other than double bonds.
1) Direct synthesis of acetaldehyde fromethylene
In acetylene chemistry, acetaldehyde wasmade by the addition of water to acetylene,
from which important derivatives such as
acetic acid, acetone and butadiene were
produced. However, the process for
producing acetaldehyde from ethylene istime-consuming, because ethanol must be
synthesized first and then oxidized to giveacetaldehyde. In 1930, UCC industrialized
this process using ethylene from petroleum
waste gas as a raw material; many U.S.
chemicalcompanies
later
producedacetaldehyde by this process.
In 1894, F.C.Phillips found out that
ethylene was stoichiometrically oxidized bypalladium metal salt to give acetaldehyde.
This reaction is very unique in that hydrogenof ethylene is replaced by the palladium metalsalt hydroxy group derived from water. The
resulting vinyl alcohol becomes acetaldehyde
as a tautomer. More than 60 years later, thisNational Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)reaction was converted to a catalytic reaction
and used as a petrochemical process. In 1956,
Schimidt (Wacker Chemie) discovered areaction to synthesize acetaldehyde fromethylene and oxygen in the presence of aredox catalyst that was an aqueous solution ofcopper chloride containing a small amount of
palladium chloride [Footnote 4]. In 1959,
Wacker Chemical, jointly with Hoechst,
completed an industrial process using thisreaction. In the one-stage process (Hoechst
process), the oxidation of ethylene andreproduction of palladium salt take place atthe same time in the same reactor. Since theconversion rate of ethylene is 35–45% underconditions of 3 atm, 120–130°C andliquid-phase reaction, it requires thecirculation of unreacted gas. Therefore,highly purified ethylene and oxygen are used.
In contrast, in the two-stage process (Wacker
process), oxidation of ethylene andreproduction of palladium are performed
separately. As the conversion rate of ethylene
is nearly 100% under conditions of 10–12
atm, 100°C and liquid-phase reaction,
circulation of unreacted gas is not needed andreproduction of palladium can be performed
with air. The idea of the redox catalyst as anaqueous copper solution containing palladiumchloride was truly epoch-making.
As mentioned in Section 5.3.2 (3), one of
the two core products in acetylene chemistry(acetaldehyde and vinyl chloride) declined
due to the development of this reaction earlyin the 1960s. This prompted rapid progress inpetrochemistry.
2) Acetoxylation of ethylene
When ethylene and air are passed throughan acetic acid solution in the presence of
sodiumacetateusing
apalladium
chloride-cupric chloride solution catalyst,
acetoxylation of ethylene occurs to give vinyl
acetate. In the 1960s, ICI and Celaneseindustrialized this process by liquid-phasereaction.
However,both
companies
discontinued it within a few years, because
corrosion occurred. Bayer and Hoechst
succeeded in the industrialization of this[Footnote 4] The mechanism of this reaction has been investigated indetail, showing that the oxygen of acetaldehyde is not from air, butfrom water used as a solvent.

process by gas phase reaction in the presenceof a solid catalyst composed ofsilica-impregnated palladium salt. This
process also replaced the method of
manufacturing vinyl acetate from acetylene
and acetic acid.
3) Ammoxidation of propylene
In the 1930s, the demand for acrylonitrile
as a raw material for synthetic rubber (NBR)
expanded; as a result, an ethylene
cyanohydrin process was developed using the
stoichiometric reaction of ethylene oxide withhydrogen cyanide, and production ofacrylonitrile started. Around the 1950s,
production of acrylic fiber also started in the
United States, resulting in a rapid increase in
the demand for acrylonitrile. To increase thesupply, American Cyanamid developed aprocess for adding hydrogen cyanide toacetylene and industrialized it in 1955. In
1957, Knapsack-Griesheim developed aprocess for manufacturing acrylonitrile, inwhich lactonitrile made by the reaction of
acetaldehyde with hydrogen cyanide wasdehydrated to give acrylonitrile. Due to thefact that a process for directly synthesizing
acetaldehyde from ethylene (Hoechst-Wacker
process mentioned above) was developed
simultaneously, acrylonitrile production was
expected to become a large-scale consumer ofacetaldehyde.
However, in 1958, the U.S. Sohio
developed a propylene ammoxidation process.
According to this process, propylene,ammonia and air are reacted in the presenceof a bismuth molybdate catalyst in a fluidized
bed at 450˚C. At almost the same time,Distillers (the United Kingdom) also
developed a manufacturing process using a
bismuth molybdate catalyst. In theammoxidation of propylene, it is the methylgroup (hydrogen at the allylic position) rather
than the double bond of propylene that reacts
to give a nitrile group. This was quite anepoch-making reaction that had previously
been unknown. The development of thisprocess meant a decline in the hydrogencyanide addition process using acetylene as araw material as well as the acetaldehyde
process using ethylene as a raw material, andpropylene became a raw material foracrylonitrile.
Systematic Survey on Petrochemical Technology

149

Catalysts for ammoxidation were
subsequently improved by the addition ofvarious promoters to bismuth-molybdenum
complex oxides. In addition, various
industrial catalysts were developed, such as a
bismuthic acid-uranium catalyst containing
depleted uranium. In the Sohio process, theyield of acrylonitrile was initially not so highdue to the production of hydrogen cyanide,acetonitrile and other byproducts. Catalysts
have subsequently continuously been
improved to increase the yield of acrylonitrile
and to decrease the formation of byproducts.
4) Partial oxidation of the methyl groupadjacent to the double bond of olefins
Following the ammoxidation process,production of acrolein by partial oxidation of
the methyl group of propylene to aldehyde
was industrialized using a bismuth molybdate
or bismuth phosphomolybdate catalyst that
was also used for acrylonitrile. Acrolein isfurther oxidized to give acrylic acid, which isthen esterified to give acrylic acid esters.
Acrolein was also used as a starting material
for synthetic glycerin.
Production of acrolein began with theindustrialization of a gas phase condensation
reaction of acetaldehyde with formaldehyde
by Degussa in the early 1940s, in the periodof coal chemistry. In 1958, Shell Chemicalindustrialized a process for manufacturing
acrolein by the oxidation of propylene in thepresence of a cuprous oxide catalyst, while
Distillers developed a propylene oxidation
process using a copper oxide-silica catalyst.
However, once the above bismuth molybdate
catalyst was developed, it was the mainprocess used.
When n-butylene is air oxidized in thepresence of a vanadium oxide catalyst, bothof the methyl groups are oxidized to give
maleic anhydride and maleic acid. In 1962,
the U.S. Petro-Tex Chem industrialized thisprocess. In 1970, Mitsubishi Chemicalindustrialized a fluidized bed process using a
vanadium pentoxide-phosphoric acid catalyst.
This method was outstanding in terms of heatremoval.
The method of manufacturing MMA
from isobutylene developed by many
Japanese companies is a significant,150

world-first process. Only one of the methylgroups of isobutylene is oxidized. In 1982,
Nippon Shokubai became the first in theworld to industrialize it. The following year,
Mitsubishi Rayon also industrialized it using
its own technology. Isobutylene is at firstmade into t-butyl alcohol in the presence ofan acid catalyst, such as ion exchange resin,
and then into methacrolein by oxygen
oxidation/dehydration in the presence of amolybdenum/iron/nickel-based
catalyst.
Therefore, while the double bond of
isobutylene is retained, the methyl group is
not necessarily partially oxidized. A
heteropolyacid catalyst is used for oxygen
oxidation of methacrolein into methacrylicacid.
MMA has been produced by the acetone
cyanohydrin process, in which acetone is
stoichiometrically reacted with hydrogencyanide, since the 1930s. The isobutylene
process developed by several Japanesecompanies is now replacing the acetone
cyanohydrin process all around the world.
5) Chlorination of propylene at the allylic
position
While the addition of chlorine topropylene
is
easy,
the
resultingdichloropropane is not industrially important,unlike EDC, because it is not in demand. On
the other hand, at 300°C or higher,
substitution reaction of chlorine to hydrogenat the allylic position of propylene occurs inplace of addition reaction. By using thisreaction, Shell Chemical developed a methodof manufacturing allyl chloride in 1937 (seeSection 3.4.3 (9)).
(3) Aromatic hydrocarbon chemistry
In the middle of the 19th century,
aromatic hydrocarbon chemistry bore fruit in
the synthetic dye industry using coal tar as araw material. In particular, substitution
reactions of aromatic rings, such as
chlorination (e.g. chlorobenzene), nitration(nitrobenzene)
andsulfonation(benzenesulfonic acid), and reactions of theirfunctional groups to introduce various
substituents, such as amine (aniline), diazoand hydroxyl (phenol) groups, were almost
all completed in the latter half of the 19th

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

century. Furthermore, the chlorination ofside-chain methyl groups, the synthesis ofderivatives of the resulting chlorinatedsubstances, such as benzyl alcohol andbenzoic acid, and the production of phthalicanhydride, maleic anhydride, etc. by partial
oxidation of naphthalene and benzene rings
were also completed under the umbrella ofaromatic hydrocarbon chemistry before thecreation of petrochemistry. In 1941, IG
Farben started production of polyurethane
foam composed of TDI. In 1958, DuPont
started production of MDI. TDI and MDI
were manufactured by the process forsynthesizing aromatic isocyanate using thereaction of aromatic amine with phosgene.
As mentioned above, the technologicalsystem of large-scale aromatic industrialorganic chemicals was already nearlycompleted under coal tar chemistry.
Meanwhile, dehydroalkylation of toluene,
disproportionation of toluene, isomerizationofxylene,alkylationofaromatichydrocarbons, etc. were developed inpetroleum refining chemistry in the 1930s.
Aromatic hydrocarbon chemistry, whichdeveloped in the fields of coal tar chemistry
and petroleum refining chemistry flowed over
into petrochemistry. Accordingly, as shownin Fig. 6.20, the direct oxidation of side chain
methyl groups and the oxidation of hydrogenat the α-position of side chain alkyl groups
are the only processes of aromatichydrocarbon chemistry that were developed
as new petrochemical processes after
petrochemistry began to fully develop in the
1950s.

Fig. 6.20 System of of aromatic hydrocarbon
chemistry.
1) Direct oxidation of side chain methylgroupsIn 1969, BASF developed a process for
manufacturing phthalic anhydride by air

oxidation of o-xylene in the presence of a
vanadium oxide-based catalyst. In coal tar
chemistry, a method of manufacturing
phthalic anhydride from naphthalene by air
oxidation of naphthalene in the presence of a
vanadium oxide-based catalyst had beenindustrialized in 1916 (see Section 4.6.2).
Therefore, it may be said that air oxidation ofo-xylene was developed as an extension ofcoal tar chemistry.
Meanwhile, terephthalic acid as a raw
material for polyester developed together
with petrochemistry, since production ofpolyester started around 1950. In air
oxidation of p-xylene, one of the two methylgroups can be oxidized to give paratoluic acid,but the second methyl group cannot beoxidized as readily as in o-xylene. In 1951,
DuPont industrialized a stoichiometric
process for oxidizing p-xylene with nitricacid in two stages, and started producing
terephthalic acid. Oxidation with nitric acid ismore costly than air oxidation and oxygen
oxidation. Subsequently, aiming at cost
reduction, ICI developed a manufacturing
process in which air oxidation and nitric acidoxidation were performed in the first andsecond stages, respectively.
In 1952, Henkel developed the firstHenkel process, in which potassium
orthophthalate that could be manufactured byair oxidation of o-xylene was isomerized witha cadmium catalyst in carbon dioxide underconditions of 1–8 atm and approximately
400°C to give potassium terephthalate. In
1958, this process was industrialized for the
first time in the world by Kawasaki Kasei
Chemicals in Japan. Henkel developed thesecond Henkel process for producing
potassium terephthalate and benzene bydisproportionation of potassium benzoate. In
1963, this process was industrialized for the
first time in the world by Mitsubishi Kasei inJapan. In this case, benzoic acid was
produced by air oxidation of toluene (directoxidation of the side chain methyl group in
the presence of a cobalt salt catalyst), a
process that was not available in the period ofcoal tar chemistry (toluene side-chain
chlorination process).
In 1950, Imhausen in Germany developedaverysophisticatedprocessfor
Systematic Survey on Petrochemical Technology

151manufacturing DMT. According to thisprocess, one of the methyl groups of p-xylene
is air oxidized into p-toluic acid in thepresence of a cobalt naphtenate catalyst; after
it is methylesterified, another methyl group is
air oxidized and the resulting substance ismethylesterified again. This DMT process
was industrialized by Hercules in the UnitedStates and many other companies around theworld. It has the advantage that the purity of
DMT, unlike that of terephthalic acid, can beincreased by distillation. In polymerization, it
is also advantageous that the reaction
proceeds by transesterification between DMT
and EG. However, because methanol is
produced as a byproduct, it must be returned
to DMT plants for reuse.
In 1955, Scientific Design developed aprocess for manufacturing terephthalic acidby oxidizing p-xylene in an acetic acidsolvent in the presence of a cobalt acetate ormanganese acetate catalyst and a bromine
compound promotor. This process was tested
for industrialization at Amoco Chemical andwasthenindustrializedbyMitsuiPetrochemical Industries and Maruzen
Petrochemical in 1958 and 1960, respectively.
It was subsequently widely used all aroundthe world.
Following the Amoco process, a process
for manufacturing chloromethylbenzene fromtoluene, formaldehyde and hydrogen chloride
andaprocessformanufacturing
diisopropylbenzene from benzene andpropylene were developed in 1960.
As mentioned above, the method of
manufacturing terephthalic acid went throughvarious changes, but the Amoco process
finally gained global precedence as the meansof direct oxidation of p-xylene. According tothis process, terephthalic acid is polymerizedwith EG to give polyester. Because water isthe only byproduct, unlike the DMT process,it does not require the collection of methanol.
The Amoco process developed to a process
for manufacturing highly purified terephthalicacid in the 1970s and the production scale ofthis process increased further from the 1990s
onwards.
Oxidation of the second methyl group of
m-xylene was as difficult as it was for
p-xylene. However, m-xylene was air

152

oxidized by the same process as was used forp-xylene to give isophthalic acid. Isophthalicacid industrialized by Oronite Chemical in1955 was used as an auxiliary raw material
for alkyd resin and unsaturated polyester.
2) Oxidation of hydrogen at the
α-position of side chain alkyl groups
Hydrogen at the α-position of the side
chain alkyl group of ethylbenzene or cumene
is oxidized to give a peroxide. This process isimportant for manufacturing intermediates ofstyrene and phenol.
Phenol is an important raw material, notonly for fine chemicals, such as dyes,
pharmaceuticals, pesticides and explosives, butalso for phenol resin. As an industrial organic
chemical, it has been produced on a large
scale since the period of coal tar chemistry. In
petrochemistry, it was initially used as a raw
material for nylon. It then became
increasingly important as a raw material forsynthetic detergents, bisphenol A (epoxy
resin, polycarbonate resin), etc.
In 1890, phenol was industrialized bysulfonation process of benzene. As mentioned
in Section 4.6.1, the chlorobenzene andRaschig processes were subsequently
industrialized in 1925 and 1935, respectively.
The process for manufacturing cumene is
described in Section 6.1.2 (1) 4). When
cumene is air oxidized at 130°C in thepresence of an aqueous alkali solution,hydrogen at the α-position is oxidized to givecumene hydroperoxide. After unreacted
cumene is removed by distillation, cumenehydroperoxide is concentrated and theconcentrate is then treated with 10% sulfuric
acid at 50°C to give phenol and acetone.
Production of phenol by the cumene process
has the advantage that the reaction conditions
are much milder than for the existingprocesses and moreover, there are no wasted
auxiliary raw materials. Meanwhile, synthesisof phenol by direct oxidation of benzene still
remains one of the dreams of chemical
researchers. Although many attempts havebeen made to realize this dream, none of them
have have had the driving success of thecumene process in industrialization.
When ethylbenzene is air oxidized,hydrogen at the α-position is oxidized to give

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

ethylbenzene hydroperoxide. This substanceis reacted with propylene to give propyleneoxide and α-phenylethyl alcohol. Styrene is
obtained by dehydration of the lattercompound. This method co-produces
propylene oxide and styrene.
(4) Cycloparaffin chemistry
Throughout the technology system ofindustrial organic chemicals as shown in Fig
6.16, cycloparaffin chemistry has flourishedlittle.
Adipic acid and ε-caprolactam are theonly industrial organic chemicals that are
produced on a large scale from cyclohexane.
Both of them are C6 compounds. The
reactivity of cycloparaffin is lower than thatof olefins, but is higher than that of paraffin.
Cyclohexane produced by the hydrogen
reduction of benzene is the only cycloparaffinthat is easily obtained in large quantities. It isvery costly to synthesize other cycloparaffins
or to separate them from petroleum.
Adipic acid and caprolactam wereindustrialized by DuPont and IG Farben in1938 and 1940, respectively, during the coaltar chemistry era. Phenol was used as a raw
material in both cases. Phenol is reduced withhydrogen to give cyclohexanol, which isoxidized with nitric acid to give adipic acid.
Caprolactam was produced by Beckmann
rearrangement from cyclohexanol via
cyclohexanone and cyclohexanone oxime.
The process from hexanol onwards was a
combination of stoichiometric reactions foradipic acid and caprolactam, which
subsequently remained unchanged for a long
period of time.
At the beginning of the 1960s, it became
possible to make large quantities ofcyclohexane from benzene, and cycloparaffinchemistry started bearing fruit. As shown in
Fig. 6.16, air oxidation and photonitrosationof cyclohexanone were industrialized on alarge scale in the area of cycloparaffinchemistry.
As a result, the raw material changed
from phenol to cyclohexane. Since a mixtureof cyclohexanol and cyclohexanone is
obtained by air oxidation of cyclohexane,
adipic acid and caprolactam are bothproduced from the mixture.

The
processformanufacturing
caprolactam can be roughly divided into two
halves. In the first half, cyclohexanone oxime
is produced. In the second half,
cyclohexanone oxime is allowed to undergo
Beckmann rearrangement to give caprolactam.
This process yields approximately 4.5 times
more ammonium sulfate than caprolactam,
because ammonium sulfate is obtained as a
byproduct in the stages of manufacturinghydroxylamine, manufacturing oxime andBeckmann rearrangement. This is a serious
disadvantage with this process. Accordingly,
various methods have been developed tocontrol the amount of ammonium sulfate
byproduct. However, there are few processes
that are still used to counter the oxime
process. One of them is photonitrosation
developed by Toray. It is a unique process inwhich cyclohexane, nitrosyl chloride andhydrogen chloride are reacted underphotoirradiation to give cyclohexanone oximehydrochloride. This is one of the rareexamples in which a photochemical reaction
is used for large-scale production of industrialorganic chemicals. Since hydroxylamine is
not used in this process, the amountof
ammonium sulfate byproduct can be
decreased. However, it is still obtained as a
byproduct of the Beckmann rearrangement
process.
In 1994, Enichem developed a process inwhich cyclohexanone oxime is directly
produced from ammonia and cyclohexanone
using hydrogen peroxide without usinghydroxylamine in the presence of an
MFI-type zeolite titanosilicate (TS-1 zeolite)
catalyst (ammoximation process). Water isthe only byproduct of this process.
Meanwhile, Sumitomo Chemical developed
high-silica MFI zeolite, a heterogeneous
catalyst causing Beckmann rearrangement in
the gas phase; the company industrialized amanufacturing
processinwhichammoxidation was combined with gas phase
Beckmann rearrangement in 2003. Sumitomo
Chemical became the first in the world in the
60-year history of caprolactam production to
successfully produce caprolactam without
any ammonium sulfate byproduct.
Meanwhile, Asahi Kasei developed an
outstanding process for manufacturing
Systematic Survey on Petrochemical Technology

153cyclohexene by partial hydrogenation ofbenzene. Cyclohexanol is easily produced by
the addition reaction of water to the doublebond of cyclohexene. The addition reaction ofwater is a classic petrochemical process foralcohol production, mentioned in Section
6.1.2 (1). Asahi Kasei industrialized it in
1990.
(5) C1 chemistry
Chemistry stemming from C1 methaneand syngas is called C1 chemistry. Following
the oil crises, much attention was focused on
potential oil depletion in the future. C1chemistry has been actively studied sincethen. Figure 6.21 shows the current
technology system. Many of thesetechnologies have been available since before
the creation of C1 chemistry.

Fig. 6.21 System of C1 chemistry.
1) C1 chemistry from syngas
C1 chemistry from syngas includes many
processes that have been available since
before the creation of petrochemistry. In 1925,
BASF industrialized production of methanolfrom carbon monoxide and hydrogen by
high-pressure reaction (approximately 300atm) in the presence of a zincoxide-chromium oxide catalyst. Subsequently,
it was also industrialized in the United
Kingdom and the United States in the 1920s.
In Japan, it was industrialized in 1932 basedon studies by the Temporary Nitrogen
Research Institute (formerly the Tokyo
Industrial Research Institute, now the
National Institute of Advanced Science andTechnology) at the Hikoshima Factory of
Gosei Kogyo (now Mitsui Chemicals). Afterthe Second World War, methanol was
produced by fundamentally the same process,but on a much larger scale owing to the154

introduction of centrifugal compressors.
However, in the 1960s, ICI developed alow-pressure process (50–100 atm) using acopper-zinc-aluminum oxide catalyst andindustrialized it on a large scale of 310,000
tons in 1972. Furthermore, Lurgi developed aprocess for manufacturing methanol by using
a multitubular reactor in the presence of acopper oxide-zinc oxide catalyst. At present,
large methanol plants are being built that arecapable of producing 2 million tons annually.
The
industrial
productionofformaldehyde from methanol by air oxidationin the presence of a copper or silver catalyst
was already being performed at the end of the
19th century. Hydroformylation is describedabove in Section 6.1.2 (1) 5). The industrial
manufacture of phosgene from carbon oxide
and chlorine in the presence of an activatedcharcoal catalyst was already established in
the 19th century. The manufacture of
isocyanate from phosgene and amine wasalso already performed in the coal chemistryera, having started when the manufacture ofpolyurethane foam from TDI began in 1941.
Since C1 phosgene is a bi-functional
compound, it is reacted with different
bi-functional compounds to give polymers.
The industrialization of polycarbonate bycondensation polymerization of phosgene and
BPA was performed by Bayer and GE in
1957.
However, phosgene is toxic. Furthermore,neither isocyanate nor polycarbonate contains
chlorine in the final product, as it iseliminated during production. As a result,
expensive chlorine obtained by electrolysis iswasted. Accordingly, one of the mostpressing goals for green chemistry from the
1990s onwards was the technologicaldevelopment of non-phosgene processes. The
subsequent course of events is described in
Section 5.6.3(2).
In acetylene chemistry, carbonylation
using carbon monoxide as one of the Reppe
reactions under high pressure was important
for the synthesis of acrylic acid, acrylic acid
ester, acrylamide, acrylic acid amide, etc. In
olefin chemistry (see Section 4.5.2 (5)),
BASF industrialized the synthesis ofpropionic acid from ethylene, carbon
monoxide and water in 1952. However, it was

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

not a large-scale product. BASF has
continued studies on the method of
manufacturing acetic acid by carbonylation of
methanol since the company industrialized
methanol in the 1920s. BASF developed
molybdenum-nickel
alloy(Hastelloy)
resistant to corrosion and an industrial
process using cobalt iodine as a catalyst in the
1960s. Meanwhile, Monsanto developed ametal carbonyl catalyst composed of rhodium
and iodine in the 1960s and built the first
150,000 ton class plant in 1970. After that,
the Monsanto process became the mainprocess for manufacturing acetic acid bycarbonylation of methanol. This process is thegreatest successful example of C1 chemistrydeveloped after the Second World War.
2) C1 chemistry from hydrogen cyanide
One large-scale petrochemical processusing hydrogen cyanide is the synthesis ofacetone cyanhydrin by adding hydrogencyanide to the carbonyl group of acetone. It is
the first process for manufacturing MMA;ithas long been used and is widely used evennow. However, because the production of
MMA by the acetone cyanhydrin process isclassified as (6) “Other organic synthetic
chemistry,” it is not detailed here. Also, theaddition of hydrogen cyanide to butadiene is
an important process for synthesizing
adiponitrile. It has already been described in
Section 6.1.2 (1) 6).
3) C1 Chemistry from chloromethanes
Methyl chloride is used as a methylating
agent for the synthesis of methyl cellulose,
etc. It is also used for the synthesis ofmethylchlorosilanes by reaction with siliconin the presence of a copper catalyst. This
process was developed by Rochow in 1941.
Methylchlorosilanes are important raw
materials for silicone. However, thesepolymers are not synthesized by C1
chemistry, because the methyl group ofsilicone is a side chain and its skeleton iscomposed of silicon and oxygen.
Fluorocarbons are synthesized fromchloromethanes and hydrogen fluoride.
However, the production of fluorocarbons has
decreased as the number of substances
regulated by the Ozone Protection Law has

increased.
(6) Other organic synthetic chemistry(reactions of derivatives)
In addition to the above products directly
produced from basic petrochemicals in olefinchemistry, aromatic hydrocarbon chemistry,
cycloparaffin chemistry and C1 chemistry,
petrochemistry also involves the productionof many industrial organic chemicals byorganic synthesis from primary derivatives
made from basic petrochemicals. For
example, there are many industrial organic
chemicals made from ethylene oxide,
ethylene dichloride/vinyl chloride, acetone,
butyraldehyde, acrylonitrile, acrolein, phenol,
nitrobenzene,
cyclohexanone,etc.
Technologies used for the synthesis of thesechemicals should not simply be classified as
petrochemical technologies, but as morecomprehensive organic synthetic technologies.
Detailed
descriptionsofthese
technologieshave been omitted here, because
they are much older than petrochemical
technologies, dating back to the creation oforganic chemistry in the 18th century.
6.1.3 Technological system of polymers
As shown in Fig. 6.22, the system ofpolymer manufacturing processes can beroughly classified into chain polymerizationand sequential polymerization. In chain
polymerization, it is actually impossible toremove a substance that is changing to apolymer in the process of polymerization.
Once chain polymerization starts in a
low-molecular-weight raw material, only the
unreacted monomer and the resulting polymer
can be obtained, even if the polymerization
process is discontinued partway through.

Fig. 6.22 System of polymer production
technology.
Chain polymerization is classified into
radicalpolymerization
and
ionic
Systematic Survey on Petrochemical Technology

155polymerization. In radical polymerization,polymerization is performed using aradical-generating polymerization initiator.
The radical initiator is partially bound to theend of the resulting polymer. In ionicpolymerization, polymerization is started byions. It is further classified into cationicpolymerization, anionic polymerization,
coordination anionic (metal complex)
polymerization
and
metal
oxide
polymerization. Chain polymerization isapplicable to compounds containing double
bonds, such as olefins and vinyl compounds,
heterocyclic compounds, such as ethyleneoxide [Footnote 5], and aldehydes, such asformaldehyde.
By contrast, in sequential polymerization,a low-molecular-weight raw material reacts
as a whole to give a substance of a slightly
higher molecular weight, which then further
reacts to finally give a polymer. If sequential
polymerization is discontinued partway
through, a substance of molecular weight in
the intermediate stage of polymerization is
obtained as an intermediate. Like reactions
between low-molecular-weight substanceswith functional groups (such as esterification
and amidation), sequential polymerization
starts between monomers with at least twofunctional groups in a molecule and thenintermediates continue reacting with eachother. However, as the reaction proceeds, it
becomes necessary for molecules with higher
molecular weight to react with each other. As
a result, viscosity is increased, thereby
disturbing thesmooth progression of thereaction. Various modifications are needed
for the industrial production of polymers.
As shown in Table 6.1, theindustrialization of synthetic polymers started
with phenol resin in 1909. Synthetic polymers
were industrialized later than industrialorganic chemicals. Although new synthetic
polymers were industrialized from the 1910s
to the 1920s, the concept of polymer had not
yet been established. In 1920, based on the
results of studies on natural rubber, etc., H.
Staudinger insisted that a great number ofsmall molecules are combined to form a large
molecule; he advanced the concept of a giant[Footnote 5] Cyclic compounds containing atoms other than carbon
in the ring.

156

molecule (macromolecule) in 1922. This
theory was not accepted by the academic
societies the day, giving rise to hot
discussions. However, the idea rapidly
penetrated into the academic societies in theearly 1930s as a result of studies based on
X-ray diffraction in the late 1920s, theproposal of a viscosity formula for polymer
solutions by Staudinger-Ryusaburo Nozu in
1930, etc.
In 1928, supporting the macromoleculetheory, W.H. Carothers started fundamental
studies on the synthesis and physicalproperties of condensation polymers at
DuPont. In 1934, P.J. Flory and Carothers
independently advanced a theory ofpolycondensation. In 1937, Flory and G.V.
Schulz independently advanced “a theoreticalsystem of radical polymerization.” In the
1930s, the concept of polymers wasestablished and the theoretical system ofpolymerization
wascompleted.
Thebackground of polymerization processes wascompleted.
Table 6.1 Typical synthetic polymers
industrialized before and during the Second
World War

Carothers not only advanced a theory, but
alsocarriedout
synthesis
andindustrialization of polymers. In 1931,
Carothers developed chloroprene rubber. This
became the first monumental product to beindustrialized based on the theory ofmacromolecules.
Furthermore,
DuPontannounced the invention of 6,6-nylon in 1938
and industrialized it in the following year.
An interesting anecdote exists about thedevelopment of 6,6-nylon. In 1934, Carothers
synthesized 5,10-nylon and suggested to his
company superior that it would be a practicalsynthetic fiber. 5,10-Nylon is a polyamide in

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

which C5 aliphatic diamine and C10 aliphatic
dicarboxylic acid are polymerized. The raw
material for C10 aliphatic dicarboxylic acidwas castor oil. The company superior rejected
his suggestion, because he considered that
there could be a shortage of raw materials ifnylon fiber were to meet with success in the
future. Therefore, Carothers synthesized
many other polyamides in which diamine wascombined with carboxylic acid and fromamong these polyamides, he selected
6,6-nylon made from coal (phenol in thosedays). Obviously, he selected it based on theidea that molecular design not only includes
methods of polymerization and performanceof polymers, but also their profitability.
Nylon was an epoch-making polymer,
because the idea of molecular design wasapplied ahead of not only wholly aromaticpolyamides, but also super engineering
plastics and thermoplastic elastomers thatwere developed later.
After the Second World War, theconsumption of polymers as materials forfibers, packages and daily necessities for
consumer use showed a dramatic increase,starting in the United States (see Section 5.3.1(4)). In particular, LDPE and polystyrene
were supplied in large quantities by
petrochemistry. In the 1950s, the trend
towarddomestic
productionofpetrochemicals and the polymer revolution
spread to Europe and Japan. At that time,polymer science also spread to the industrial
world, and full scale technologicaldevelopment based on scientific theories
commenced. As shown in Table 6.2,
large-scale polymers such as ABS resin,
acrylic fiber, polyester fiber, PET resin,
HDPE, PP, polycarbonate, polyacetal, BR
and EPDM emerged one after another over a
period of 15 years between the late 1940s andthe 1960s, resulting in an acceleration of thedevelopment of the petrochemical industry.

Table 6.2 Typical synthetic polymers
industrialized before and during the Second
World WarA great variety of polymer-manufacturing
technologies, including those industrialized
before the creation of petrochemistry, form asubstantial
pillarofpetrochemical
technology.
(1) Chain polymerization
Engineering technologies for chain
polymerization are described first, following
by explanations of radical polymerization andionic polymerization reaction forms.
1) Manipulation technologies for chain
polymerization
Polymerization is generally a large-scale
exothermic reaction. Removal of the reaction
heat is important especially in chain
polymerization, because once polymerization
has been initiated, the reaction will rapidly
progress while generating heat. As shown in
Fig. 6.23, manipulation technologies forchain polymerization are classified as bulk
polymerization, solution polymerization,
slurrypolymerization,suspension
polymerization and emulsion polymerization.

Fig. 6.23 System of manipulation
technologies for chain polymerization.
Bulk polymerization is performed using a
monomer alone in the absence of a solvent.
This process is used for both radical
Systematic Survey on Petrochemical Technology

157

polymerization and ionic polymerization. Asa matter of course, removal of heat is
important. Various processes have beendeveloped, such as the bulk process, in whicha monomer is used in large quantities as asolvent, and the fluidized bed process, inwhich a catalyst, etc. is added to an air streamof a monomer so that polymer particles areformed in the gas phase. HDPE, L-LDPE andPP have been actively manufactured by thegas phase process since the 1980s, chiefly
because high performance catalysts for
coordination anionic polymerization weredeveloped.
In solution polymerization, the heat canbe removed with a solvent and viscosity canbe made lower than in bulk polymerization.
However, the solvent must be separated fromthe polymer after polymerization. In the caseof solution products such as adhesives, thesolution after polymerization is used as it is.
This process can be used for both radical
polymerization and ionic polymerization.
Slurry polymerization is often used forionic polymerization. Since a catalyst issuspended in a solvent and the resulting
polymer is also suspended in it, the reaction
solution as a whole becomes slurry. Due tothe fact that the heat is removed by thesolvent, the viscosity can be made lower thanin solution polymerization.
Suspension polymerization is often used
for radical polymerization. Water is usuallyused as a solvent. A monomer is suspended ina solvent and polymerization is started bydissolving a polymerization initiator in thesuspended monomer. Heat can easily beremoved, because polymerization proceeds
while the monomer is suspended. This
process is often used for the industrial
production of vinyl polychloride.
Emulsion polymerization is also often used
for radical polymerization. Since water isused as a solvent and since a monomer isemulsified with a surfactant, droplets are atleast 1 unit smaller in size and heat can beremoved more easily than in suspension
polymerization. An initiator and a catalyst forpolymerization are dissolved in a solvent andmade to enter the emulsified micelles toinitiate polymerization. After polymerization,anemulsionisformed.
Emulsion158

polymerization is often used for the
production of synthetic rubber, resin forcoatings (emulsion coatings) and adhesives.
None
of
these
polymerization
manipulation technologies can be deemed as
the best, because it varies with each polymer.
For example, LDPE has always been
manufactured by bulk polymerization since
this process was developed. The method of
manufacturing polyvinyl chloride changed
from emulsion polymerization to suspension
polymerization. HDPE and PP were initially
produced by solution polymerization andslurry polymerization, but as catalysts
improved, these processes were subsequently
replaced by bulk polymerization using a
monomer as a solvent and then by bulk
polymerization using a gas phase fluidized
bed. However, slurry polymerization, etc. areused even now for convenience in making
some grades. SBR is produced by emulsion
polymerization in radical polymerization, but
by solution polymerization in anionicpolymerization.
Simply,manipulation
technologies vary with each type ofpolymerization. As a result, the performanceof the product also varies accordingly.
2) Radical polymerization
Radical polymerization has a long history.
At first, it was used for the production ofvinyl acetate resin, polyvinyl chloride andother such products that were developed in
the 1920s. It can be very widely applicable toboth polar and nonpolar monomers.
High-pressure polymerization of ethylene(formation of LDPE), discovered in the 1930s,
is also radial polymerization. The widelydistributed molecular weight and large
branched structure of LDPE represent well
the characteristics of radical polymerization.
As shown in Table 6.1 and 6.2, most of thetypical polymers produced by radical
polymerization, such as polyvinyl chloride,
vinyl acetate resin, polystyrene, AS resin,
ABS resin, LDPE, polymethyl methacrylate,chloroprene rubber, SBR, NBR, fluororesin
and acrylic fiber, were already available
before 1950. These polymers did muchtowards the full-scale development of
petrochemistry from the 1950s onwards.
However, prior to that, the development of

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

the
basic
technology
forradicalpolymerization had already been advanced bymonomers made using coal chemistry.
Peroxides and azo compounds are often
used as polymerization initiators. Since thesecompounds can generate radicals in responseto heat, light (including ultraviolet rays andelectron beams) and a combination ofoxidation and reduction (redox initiator), they
can initiate polymerization under various
conditions. These initiators are used not only
for the manufacture of polymers at plants, butalso for the formation of photosensitive
polymers for dental use, etc., for whichpolymerization at the site of use is preferred.
The termination of radical polymerization
used to be uncontrollable, because it occurs
due to radical transfer (chain transfer) or
recombination. For this reason, polymers
produced by radical polymerization werecharacterized by wide molecular weight
distribution.
However,livingradicalpolymerization developed in the 1990s,
unlike in existing technologies using
polymerization initiators, made it possible togenerate all polymer terminals at the sameprobability owing to radical generation froma stable covalent species (dormant species);
moreover, radical concentrations can be kept
low to control termination. Living radical
polymerization began to be used in the 2000s,
but it has only been applied to a relatively
small amount of functional polymers. No newlarge-scale polymers have been developed
using this method.
3) Ionic polymerization
As shown in Fig. 6.24, ionicpolymerization is classified into cationicpolymerization, anionic polymerization,
metal oxide polymerization and coordination
anionic polymerization. The molecularweight distribution range is narrower forionic polymerization than for radical
polymerization.
In cationic polymerization, the growthterminal of the polymer is a cation. Catalysts
for cationic polymerization include Lewis
acids, such as boron fluoride and aluminum
chloride, protonic acids, such as sulfuric acidand phosphoric acid, Lewis acids combinedwith a halogenated alkyl or water as a

cocatalyst, etc.. Monomers that undergo
cationic polymerization are generally
double-bondcompounds
withanelectron-donating group. The polymerizationof isobutylene is a typical industrial exampleof this type of polymerization.

Fig. 6.24 System of ion polymerization.
In anionic polymerization, the growthterminal of the polymer is an anion. Catalysts
for anionic polymerization include alkali
metals, such as metal potassium and sodium,
metal alkyls, such as butyl lithium, alkali
amides, such as sodium amide, Grignard
reagents, etc. Monomers that undergo anionicpolymerization are generally double-bondcompounds with an electron attractive group.
Polymerization of styrene, butadiene,
acrylonitrile, etc. can be performed byanionic polymerization. Since cyanoacrylicacid esters used for instant adhesives have astrong electron-attractive group, anionicpolymerization is initiated by airborne
moisture, resulting in solidification andadhesion. In this case, polymerizationcommences with water acting as a base.
Ring-opening
polymerizationofheterocyclic compounds, such as ethyleneoxide, is also one type of ionicpolymerization. Formation of polyacetal bypolymerization of formaldehyde and by
copolymerization of formaldehyde andethylene oxide are also ionic polymerization
processes.
Unlike in radical polymerization, no
termination reaction due to recombination
occurs in ionic polymerization, because thepolymer growth terminals with the same
electric charge repel each other. Also,
because there are counter ions at the growthterminals, termination reaction due to chaintransfer is unlikely to occur. Therefore, living
polymerization can be performed. For
example,oncompletionofionicpolymerization of styrene, a block copolymer
can be made by polymerization of isoprenefrom the growth terminal of polystyrene.
Styrene- and olefin-based thermoplastic
Systematic Survey on Petrochemical Technology

159

elastomers are made using this technology.
Metal oxide polymerization is used forpolymerization of ethylene under medium
pressure. In 1950, Standard Oil (Indiana)
discovered the formation of HDPE whentrying to perform oligomerization of ethylene
under moderate conditions in the presence ofa silica-supported molybdenum oxide catalyst.
At the same time, Phillips also obtained
HDPE
by
using
a
silicaor
alumina-supported chromium oxide catalyst.
This process of polymerization can produce
polyethylene under milder conditions than theexisting high-pressure radical polymerization
process for LDPE. It was industrialized in1957 and has been used as a method of
manufacturing HDPE ever since. However,metal oxide polymerization had no uses otherthan ethylene. When it is applied to propylene,
approximately 10% solid PP is obtained, but
the remainder is a liquid polymer that isuseless.
4) Coordination anionic polymerization
Coordination anionic polymerization is
one type of ionic polymerization. This
process is described separately because it isparticularly important in petrochemistry. In
coordination anionic polymerization, thegrowth terminal of a polymer (anion) is
coordinated with a catalyst to form a complex.
In 1953, this polymerization process beganwith Ziegler’s successful polymerization of
ethylene at ordinary temperature andatmospheric pressure in the presence of atriethyl aluminum-titanium tetrachloride
catalyst. Like polyethylene obtained in thepresence of a metal oxide catalyst, theresulting polymer was HDPE. In 1955, Nattasucceeded in the formation of stereoregularpolymers from α-olefins such as propylene
and styrene in the presence of triethyl
aluminum combined with titanium trichloride.
Ziegler-Natta catalysts, shown in Table 6.2,
were subsequently widely usedtoindustrialize HDPE in 1955, PP in 1957,
cis-1,4-polybutadiene(BR)andcis-1,4-polyisoprene (IR) in 1960 and EPDM
in 1961.
Coordination anionic polymerization is a
representative petrochemical technology
because it has been used to produce numerous

160

products and moreover, it has done muchtowards the technological development of
petrochemistry since the 1960s (Fig. 6.25). In
1968, Mitsui Petrochemical Industries
developed an alkyl aluminum-magnesium
chloride-supported titanium chloride catalyst.
The activity of this catalyst was more than
100 times higher than the first-generation
Ziegler-Natta catalyst. As a result of thisdevelopment, decalcification, which had been
essential for reactions with Ziegler-Nattacatalysts, became unnecessary. Furthermore,in 1975, Mitsui Petrochemical Industries andMontedison jointly succeeded in selectively
making highly stereospecific active sites byletting an electron donor, such as ethyl
benzoate, act on a catalyst. Since theZiegler-Natta catalyst is a solid, its catalytic
activity varies with each crystal surface(multisite). The active sites of this catalyst
were selectively specified by using additives.
As a result, it became unnecessary to remove
nonstereoregularPP
formedduringpolymerization in the presence of theZiegler-Natta catalyst. This highly active andhighly stereoregular catalyst is called thesecond-generation Ziegler-Natta catalyst. As
a result of this development, the ranges ofmolecular weight distribution of HDPE andPP have been dramatically narrowed,
resulting in marked improvements in quality(see Section 5.6.3 (1)).

Fig. 6.25 Change of coordination anionicpolymerization catalyst.
Manufacture of L-LDPE similar to LDPE
by copolymerization of ethylene with α-olefin
was industrialized by DuPont Canada in 1960.
However, the quality of the product was
lower than existing LDPE. In contrast,
L-LDPE
manufactured
using
the
second-generation Ziegler-Natta catalyst wassuperior to LDPE in uniformity ofcomposition distribution and also in
performance. In 1979, UCC developed a

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

method of manufacturing L-LDPE by the gas
phase fluidized bed process. In the 1980s,
L-LDPE achieved rapid growth, taking over aconsiderable part of the LDPE market. Also,
because construction costs and operation
costs were both lower than for high-pressure
LDPE facilities, the L-LDPE process was
exclusively adopted by new petrochemicalindustries in the Middle East and Asia. Due tothe second-generation Ziegler-Natta catalyst,
it became possible to further increase theamounts of comonomers; consequently,
VLDPE and ULDPE with much lower
density than LDPE were industrialized as
new types of polyethylene.
Table 6.3 Typical synthetic polymers
industrialized from the 1960s

In 1980, Kaminsky found out that thepolymerization activity of a catalyst in whicha reactant of triethyl aluminum with water(Methylalumoxane [MAO]) was combinedwith metallocene (cyclopentadienyl complex
of zirconium, titanium, etc.) was more than 1
unit higher than the second-generation
Ziegler-Natta catalyst. This became known asa metallocene catalyst (Kaminsky catalyst)(see Section 5.7.4 (3)). The metallocene
catalyst is a single-structure metal complex
having a single active site (single site).
Accordingly, the range of molecular weight
distributionisnarrowerthanthesecond-generation Ziegler-Natta catalyst.
However, because improvements were also
being made to the second-generation
Ziegler-Natta catalyst, the metallocene
catalyst was not used in the industrializationof polyethylene until 1991. Due to its
superior merits, the metallocene catalyst is
used in the production of elastomers, such as
EPR and EPDM.

Organometallic
complexcatalysts
foreshadowed by the Ziegler-Natta catalyst
began to attract much more attention after thedevelopment of the metallocene catalyst.
Many improvements and modifications arebeing made to these catalysts even now. A
constrained geometry catalyst aimed at
improving stereoregularity by controlling thestructure around the active site has beendevelopedandindustrializedasamodification of the metallocene catalyst.
Figure 6.25 summarizes the status of
catalysts
forcoordination
anionic
polymerization. It can be expected that thesecatalysts will develop further in the future. As
an indication of future development,
post-metallocene catalysts have alreadybegun to develop. These are mentioned in
Section 6.2.
(2) Sequential polymerization
As shown in Fig. 6.22, sequential
polymerization is classified into condensation
polymerization, polyaddition and addition
condensation. The most typical reaction formof sequential polymerization is condensation
polymerization(polycondensation).
Condensation polymerization proceeds while
polyfunctional monomers are performing
condensation on each other by releasing asimple low-molecular-weight substance, suchas water or hydrogen chloride. Formation ofpolyurethane by the reaction of polyol with apolyisocyanate compound is a modificationof condensation polymerization. This reactionis also called polyaddition, because no simple
low-molecular-weight substance is eliminatedand a urethane bond is formed by the reaction
between the hydroxyl and isocyanate groups.
Meanwhile, if phenol resin, urea resin ormelamine resin is formed, the reaction iscalled addition condensation. In this case,polymerization
proceeds
asfollows:
formaldehyde is added to active hydrogen at
the ortho or para position of phenol or toactive hydrogen of the amino group of urea ormelamine to give a methylol group (-CH2OH),
which is then reacted with active hydrogenand then dehydrated (condensed) to give amethylene bond (-CH2-). It also proceeds if
the methylol groups dehydrate (condense)
each other to give an ether bond
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161

(-CH2OCH2-). If addition and condensation
are repeated, a two-dimensional prepolymer
will be formed depending on the conditions,followed by theformationof athree-dimensional crosslinked polymer byheating or pH change.
As shown in Table 6.1, addition
condensation is the oldest method ofpolymerization, created before the period of
petrochemistry. By this process, phenol resin- the first synthetic polymer, urea resin andmelamine resin were industrialized in 1909,
1928 and 1935, respectively. Phenol resin
was probably the first synthetic polymer tofamiliarize people with plastics, during thecoal chemistry period before the creation of
petrochemistry. Since phenol resin had thedrawback of turning brown, it was colored
black and used mainly for black telephones
and bulb sockets. As urea resin showed nosuch discoloration, it was used in large
quantities for white or colored tableware,
buttons and electrical parts. In Japan, phenol
resin and celluloid resin were typical plasticsof the time before the Second World War.
Urea resin became a typical plastic after theSecond World War until the mid-1950s (seeSection 5.3.3 (1)). Transparent andheat-resistant melamine resin was often used
for decorating the surfaces of laminatedplates made of phenol resin. However, it was
time-consuming to mold phenol, urea andmelamine resins to thermosetting resins byaddition condensation; accordingly, thepractice of using these resins as raw materials
for molding daily necessaries and electricalparts was discontinued in the 1950s, whenthermoplastic resins, such as polyethylene
and polystyrene, began to be supplied in large
quantities. However, even now these resin
products still play an important role inmanufacture of adhesives for plywood andlaminates.
Nylon (polyamide), industrialized in
1939, was the first polymer made bycondensation
polymerizationandpolyaddition. As described above, nylon
played a significant role in verifying andestablishing the concept of polymers. Tables
6.1 and 6.2 show the polymers made by theindustrializationofcondensation
polymerization and polyaddition, following

162

on from nylon, unsaturated polyester,polyurethane, silicone and epoxy resin, whichwere developed before the full-scale
development of petrochemistry. Since the1950s when petrochemistry started coming
into fruition, large-scale polymers have also
been developed, such as polyester (PET),
which is at present comparable in production
to the four major general-purpose resins (PE,PP, PVC and PS), and polycarbonate, used asa more general application of an engineering
plastic from the 1990s onwards. From the
1960s onwards, to meet the needs of themarket for strong, heat-resistant polymers, as
shown in Fig. 6.26, engineering plastics, suchas polyphenylene oxide (PPO) and PBT,
super engineering plastics, such as polyimide,
PES, PEEK, polyether imide, and liquid
crystal polymers and metha- and para-based
aramidfibersweredevelopedbycondensation polymerization. In particular,
super engineering plastics are polymers
whose molecules are designed so that they
have both high strength/high heat resistanceand high forming processability required forthermoplastics. Condensation polymerization
has the advantage of easy molecular design.

Fig. 6.26 Technology system of high-strengthand high-heat resistance condensation
polymerization polymers.
In terms of manipulation technology forcondensation polymerization, the monomer
and resulting polymer are usually heated
above their melting points to performpolymerization in a molten state. This process
corresponds to bulk polymerization in chain
polymerization. Since condensation reaction
is reversible, it is important to immediately
removetheresultingcondensed
low-molecular-weight substance, such as
water, from the reaction system. For thisreason, polymerization is often carried out
under reduced pressure. The molecularweight of PET may be insufficient for many
uses if it is produced by normal condensation

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polymerization in a molten state under
reduced pressure. Therefore, its molecularweight is further increased by solid-phase
polymerization. In the case of polyester,condensation
polymerization
may beperformed by transesterification between a
diester monomer and polyol. Since
low-molecular-weight monool is eliminated,
it must be removed.
Meanwhile, aromatic polyamide fibers
are made by low-temperature solution
polycondensation in the presence of a polar
solvent,
such
as
DMF
and
N-methylpyrrolidone.
This
technology
corresponds to solution polymerization inchain polymerization. In this case, it isimportant to increase the degree ofpolymerization as much as possible bydissolving the resulting polymer. Afterpolymerization, spinning can also be carriedout. Interfacial polymerization is also
performed,in
which
condensation
polymerization is carried out on theintersurface of two solvents that are insolublein each other. For example, BPA is dissolved
in sodium hydroxide solution, whilephosgene is dissolved in methylene chloride.
Since methylene chloride and water are
insoluble in each other, two phases areformed.
Condensation
polymerization
proceeds on the intersurface of the two phases
to give polycarbonate.

6.2 New

technologicalpetrochemistry

trendsin

As mentioned in Section 5.5, it is said
that petrochemistry technologically matured
in the late 1970s. The superiority of steam
cracking was established in the manufactureofolefins.
Subsequently,
becauseimprovements were only made to increase thescale of production, investigations in pursuitoftechnologicalvarieties
decreasedsignificantly in number. Since coal andfermentation chemicals were completely
replaced by industrial organic chemicals, it
became difficult to develop new technologies
leading to any dramatic increase in the scaleof productivity. However, from the 1970s
onwards, technologies for manufacturingindustrial organic chemicals showed steadydevelopment, although not so strikingly as
was observed in the 1950s and 1960s. One
such technology was olefin chemistry fromC4 and C5 compounds that were notpreviously in demand. Another example wasenergy-saving low-pollution manufacturing
technologies(see
Section
5.6.3).
Technological innovations continued inpolymer technology as follows: thesecond-generation Ziegler-Natta catalyst wasindustrialized in the 1970s, L-LDPE as alarge-scale new product in the 1980s and themetallocene catalyst in the 1990s; many superengineering plastics, high performance fibers
and functional resins were developed.
Meanwhile, due to the steady accumulation oftechnological modifications, such as living
polymerization and block polymerization, PP
achieved marked growth in the 1980s and as
a result, the demand for olefins was correctedfrom monopolar concentration on ethylenethat had continued up until the 1960s. The
demand for isobutylene (a raw material for
MMA and MTBE) and the demand for
1-butylene (an auxiliary raw material for
L-LDPE) also increased. The use of olefins
overallwas
accelerated,andthepetrochemicalindustry
becamevery
comprehensive, as discussed in Chapter 3.
Meanwhile, the two oil crises in the
1970s meant that subsequent attention was
focused on the need to develop technology tocounter the depletion of petroleum resources.
While coal is reserved in large quantities
under ground, its handling is difficult.
Therefore, studies have been conducted todevelopchemical
reactionsdirectly
producing industrial organic chemicals frommethane or other alkanes as natural gas,
which have the second greatest reserve after
coal and are easy to handle. Under thesecircumstances,many
technologicalinnovations
haveoccurredinthepetrochemical industry since the 1990s,
although their historical value has not yet
been established. This technology has thepotential to create new types of
petrochemistry with product categories andforms of production that differ from existing
petrochemistry that has been prevalent aroundthe world since the 1950s, that is, technology
in which basic petrochemicals are produced
Systematic Survey on Petrochemical Technology

163

by steam cracking and then transported bypipelinetopetrochemicalcomplexes
manufacturing industrial organic chemicals
and polymers.
6.2.1 Metathesis reaction of olefins
The metathesis reaction of olefins wasfound and developed as a triolefin processduring the Sturm und Drang period of
petrochemistry in the 1960s, but its value was
unknown. Subsequently, the mechanism of
the reaction was elucidated. It was found to
be a reaction of double bonds, although theform of the reaction was unknown (seeSection 6.1.2 (1)). Recombination of bonds
occurs between two kinds of olefins. It is
induced by a transition metal alkylidene
complex catalyst (carbene complex). In 1967,
Calderon et al. confirmed that a double-bond
was cleaved to give a new double bond in thepresence of a catalyst composed of WCl6 and
EtAlCl2. This confirmation made themetathesis reaction well known. In 1971,
Chauvin suggested a mechanism for thisreaction. Around that time, the reaction began
to be utilized as a petrochemical process inthe presence of a Ziegler-type catalyst
composed of tungsten or molybdenum
combined with alkyl aluminum, etc. In the
1990s, Schrock and Grubbs et al. developed ahighly active alkylidene complex catalyst ofmolybdenum and ruthenium that could
tolerate functional groups with high polarity.
Since then, this catalyst has been widely used,
not only for petrochemistry, but also fororganic synthetic reactions.
As shown in Fig. 6.27, there are threesuccessful examples of the application ofmetathesis reactions in petrochemistry.

Fig. 6.27 Examples of metathesis reactions utilized in petrochemistry.
(1) Synthesis of propylene
The production of propylene by themetathesis reaction of ethylene with
2-butylene was industrialized for the firsttime in 1970. However, it was not until the
mid-1980s that this reaction became used ona fully-fledged scale. In the 1990s, thisprocess was used for the large-scale
production of propylene. Due to the increased
demand for propylene, propylene also began
to be actively manufactured at petrochemicalcomplexes in Japan by steam cracking of
naphtha from 2-butylene, for which there waslittle demand. Several plants producing
150,000 tons of propylene a year by the164

metathesis process have been built in Japan.
The production of propylene at these plants issignificant, comparable to the amount ofpropylene obtainable from plants producing
300,000 tons of ethylene by steam crackingof naphtha. In the Middle East, where
propylene cannot be obtained because ethane
is used as a raw material, plants have been
built at which ethylene is dimerized to given-butylene, which is then subjected tometathesis reaction with ethylene to give
propylene.
(2) Metathesis polymerization
The second typical example of metathesis

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)reaction application in petrochemistry is
metathesis polymerization. Cyclic olefin issubjected
toring-opening
metathesis
polymerization (ROMP) in the presence of a
Ziegler-type catalyst to give a polymer, whichis then hydrogenated to give an opticalmaterial outstanding in transparency, heat
resistance and size stability. Many chemicalcompanies have been actively seeking a newmarket for this area. If a Grubbs catalyst thatis highly resistant to polar functional groups
is used, various functional groups can be
introduced and living polymerization can also
be performed. Accordingly, attempts havebeen made to make use of this process for thesynthesis of functional polymers.
(3) Efficient synthesis of α-olefins
Metathesis reaction was also applied to amethod of efficiently synthesizing α-olefins(see Section 3.4.2 (7)). This is the synthetic
higher olefin process (SHOP) developed by
Shell. Ethylene is oligomerized to give
α-olefins with various numbers of carbon
atoms. There are limited higher alcohols withcarbon numbers that are useful for surfactants,
lubricants, etc. In contrast, the SHOP is asophisticated process in which metathesis
reaction and isomerization/hydroformylationin the presence of a cobalt catalyst take place
repeatedly to avoid the formation of useless
α-olefins. After an α-olefin with a usefulcarbon number atom is removed, theremaining olefins with longer and shorter
carbon chains are isomerized (into internal
olefins). Reorganization is then performed bymetathesis reaction in such a way so that theolefin carbon atoms are added and thendivided by two. From this, internal olefinswith useful numbers of carbon atoms are
separated again. The resulting internal olefin
is hydroformylated in the presence of a cobalt
catalyst to give terminal aldehyde. This is
reduced to give alcohol, which is thendehydrated to give an α-olefin with a usefulnumber of carbon atoms. If this procedure isrepeated, only α-olefins with necessary
carbon numbers are obtained.
It is also expected that metathesis
reaction will be further applied topetrochemical processes, such as thesynthesis of styrene by metathesis reaction of

stilbene formed by dimerization of toluene byoxidative dehydrogenation with ethylene.
Monoolefins and dienes with slightly
complicated molecular structures have been
produced by metathesis reaction and havealready been industrialized as intermediates
for fine chemicals.
6.2.2

Propylene-targeted production
technology
As mentioned in Section 5.7.4 (1), thedemand for propylene increased relative tothat for ethylene in the 1980s. A shortage of
propylene became apparent in the UnitedStates, where it was obtained as a byproductof the fluidized catalytic cracking (FCC)
process mainly for producing gasoline, andalso in countries where propylene wasobtained as a byproduct of ethylene
production by steam cracking of naphtha.
Accordingly, the 1990s saw the start oflarge-scale production of propylene bymetathesis reaction, as mentioned in thepreceding section. In the 1990s, production of
propylene by catalytic dehydrogenation of
propane also started. Although this process
was at first not considered to be able to rival
thebyproduct
processes,
steadyimprovements have been made with respect
to catalysts and processes.
In contrast to FCC, deep catalytic
cracking (DCC), which aims at increasing theyield of propylene rather than decreasing theyield of gasoline, was developed andindustrialized in China. Subsequently, thisprocess has also been developed in many
countries other than China. It is also known
as reinforced fluidized catalytic cracking.
In China, the petrochemical industry
experienced a sudden rise due to technology
imports and capital injection from othercountries from the 1990s onwards. To prevent
an increase in the dependence on othercountries for petroleum, China planned tobuild plants for industrial chemical products
from coal, mainly in inland areas such as
Inner Mongolia. One example was the MTP
process for manufacturing propylene frommethanol derived from coal. In 2010, a
500,000-ton class MTP plant was built using
imported
technology andusedfor
manufacturing PP. However, because it was
Systematic Survey on Petrochemical Technology

165

built as part of the economical security
policies of China, there is little likelihood of
this
plant
immediately
realizing
competitiveness. Since oil refining companies
and plant engineering companies indeveloped
countries
originallymadestrenuous efforts to develop the MTP process,its industrialization in the inland areas ofChina should be regarded as experimental ina special market with only a few rival
companies. However, because methanol canbe produced much more cheaply and on amuch larger scale from natural gas than fromcoal in natural gas-producing countries, thedevelopment of the MTP process to use cheap
methanol as a raw material is, in itself, aninteresting part of C1 chemistry, mentioned
below.
6.2.3 C1 chemistry
Before the Second World War, syngas
was exclusively made from coal. Since theend of the war, it has been made frompetroleum and natural gas. Unlike petroleum,
natural gas is produced at remote places far
from consumption areas; accordingly, its
development is often difficult due todifficulty in transportation. To solve thisproblem, there has been a growing trend to
manufacture syngas and produce methanol
and ammonia on a large scale at production
sites for natural gas.
As already mentioned in Section 6.1.2 (5)1), one of the consumers of cheap methanol
produced as described above was a processformanufacturing
aceticacidbycarbonylation of methanol, industrialized in
1970. Due to the major success of thisprocess, and due to the petroleum crises of
the 1970s, research and development of C1
chemistry were actively conducted from the1970s to the 1980s. However, for the time
being, the only outcome has been to prove
thedifficulty of C1 chemistry.
Meanwhile, attention has been focused on
the synthesis of dimethyl oxalate by oxidative
carbonylation of carbon monoxide, methanol
and oxygen (Section 3.4.1 (3)), developed by
Ube Industries in the 1970s as a method ofsynthesizing C2 compounds by couplingcarbon monoxide. Dimethyl oxalate ishydrogen reduced to give EG and methanol.

166

This process was industrialized in 1978.
Recently, many plants producing EG by thisprocess have been built in China. These
Chinese plants use carbon monoxide fromcoal. Ube Industries also synthesized
dimethyl carbonate by the same process. The
importance of dimethyl carbonate has been
increasing as an electrolyte for lithium ion
secondary batteries and also as an alternative
for phosgene (a starting material for
manufacturing
polycarbonate
bythenonphosgene process).
6.2.4 Paraffin chemistry
Paraffins (alkanes) other than methane,such as ethane, propane and butane, havebeen converted to olefins by steam cracking,etc. before use due to their markedly low
reactivity. However, because paraffin ischeaper than olefins, attempts have been
made to develop a method of directly
manufacturing industrial organic chemicals
from paraffin.
The first successful example of paraffinchemistry was the synthesis of acetic acid byliquid-phase oxidation of propane, butane andpentane, developed by Celanese in 1952.
According to this process, acetic acid is
manufactured by dissolving a catalyst, suchas cobalt acetate or chromium acetate, in an
acetic acid solvent and then blowing raw
material gas and air into the solution. In
addition to acetic acid, byproducts obtained
include acetaldehyde, acetone, MEK, ethyl
acetate, formic acid and propionic acid. Morebyproducts are obtained in paraffin chemistry
than in olefin chemistry, because theconditions for reaction are severer forparaffin chemistry.
In
1962,
Distillers
industrialized
processes for synthesizing acetic acid fromlight naphtha in the presence of a manganese
naphthenate catalyst. However, theseprocesses for manufacturing acetic acidcompeted with oxidation of acetaldehyde
from ethylene in the 1960s and were
overwhelmed by carbonylation of methanolfrom the 1970s onwards.
The second successful example was the
production of maleic anhydride by oxidationof n-butane. Maleic anhydride is a mid-scaleindustrial organic chemical that is used as a

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

raw material for unsaturated polyester andalso for synthesis of fumaric acid and malic
acid. In the coal chemistry period, it was
already produced in small quantities
exclusively by air oxidation of benzene in thepresence of a vanadium pentoxide catalyst.
This reaction was similar to the process for
manufacturing phthalic anhydride from
naphthalene (see Section 4.6.2), and maleic
anhydride was also obtained as a byproductof phthalic anhydride. Oxidation of benzene
was a wasteful process, because two carbon
atoms of benzene were made into carbon
dioxide.
Therefore,amethodofmanufacturing maleic anhydride fromn-butylene was developed in 1962. Vanadium
pentoxide-phosphoric acid was used as acatalyst. However, after Monsanto developed
a method of manufacturing maleic anhydridefrom n-butane in 1974, the benzene andn-butylene processes were both rapidly
replaced by the butane process. Vanadium
pentoxide-phosphoric acid was also used as acatalyst for this method.
The third successful example of paraffinchemistry was the co-production of t-butyl
peroxide and t-butyl alcohol by oxygen
oxidation of isobutene. t-Butyl peroxide isused for oxidation of propylene to give
propylene oxide and t-butyl alcohol. t-Butyl
alcohol was in great demand from the 1980s
to the 1990s. This was due to MTBE being
used as a gasoline additive. However, thedemand for t-butyl alcohol decreased rapidly
after adding MTBE to gasoline wasprohibited in the early 2000s, meaning there
was no longer any use for this technology.
As mentioned above, the only successful
examples of paraffin chemistry had been forparaffins with four or more carbon atoms.
However, in the 2000s, promising processes
for paraffins with C2 or C3 were developed
one after another. This was pioneered by the
direct synthesis of acrylonitrile byammoxidation of propane developed by
Asahi Kasei. Industrial production wasstarted by a subsidiary of Asahi Kasei in
Korea in 2007 and after that in Thailand. A
plan is also being pushed forward toindustrialize it in Saudi Arabia. The catalyst
for this process is a complex oxide ofmolybdenum, vanadium, niobium, etc.

Following on from the ammoxidation of
propane, processes have been rapidly
developed for direct oxidation of propane for
manufacture of acrylic acid and directoxidation of ethane for manufacture of acetic
acid. The oxychlorination process, in which
vinyl chloride is directly obtained fromethane, chlorine and oxygen, is also
undergoing development. Although theseprocesses were expected to be industrialized
in the 2000s, none of them have beenindustrialized as yet. The issue lies with thelarge amounts of chlorinated hydrocarbon
byproducts.
BP/UCC developed a process for
manufacturing aromatic hydrocarbons by
cyclodehydrogenation of propane and butane.
In 1999, this process, also known as the
Cyclar process, was industrialized in Saudi
Arabia on a benzene production scale of
350,000 tons and a p-xylene production scaleof 300,000 tons. Thus commenced productionof aromatic hydrocarbons from paraffins withsix or less carbon atoms.
As mentioned above, it was not until
approximately 50 years after the synthesis ofacetic acid by liquid-phase oxidation thatparaffin chemistry began to rival olefinchemistry in any way.
6.2.5 Post-metallocene catalysts
With the industrialization of thesingle-site metallocene catalyst in contrast to
the multi-site Ziegler-Natta catalyst in the
1990s, coordination anionic polymerization
began to attract much attention again in the
1990s. As a result, various single-site
non-metallocene catalysts and late transition
metal catalysts were successively developed
as post-metallocene catalysts in the latter halfof the 1990s (Fig. 6.25). The former catalysts
use ligands other than cyclopentadienyl,
which is used in metallocene catalysts. Unlike
the metallocene catalyst using early transition
metals such as zirconium and titanium, thelatter catalysts use late transition metals suchas iron, nickel and palladium.
Many post-metallocene catalysts that are
more active than the Ziegler-Natta andmetallocene catalysts have been developed. It
is especially promising that these catalysts are
not easily fractured by water or polar
Systematic Survey on Petrochemical Technology

167monomers. The applicable monomers andconditions used to be limited to a large extent
for ionic polymerization than for radical
polymerization. It is expected that newlarge-scale polymers will be created bycopolymerization of olefins with polar
monomers.

6.3 Historyoftechnology andtechnologies

petrochemical
epoch-making

Since petrochemistry has long beenclosely related to industrial organic chemicals
and polymers since even before its creation, it
is considerably difficult to identify purely
petrochemical processes using natural gas andpetroleum as raw materials (petrochemical
processes in the narrow sense). However,sinceSection
6.5
discussesthesystematization of petrochemical processes,
in this section we shall only review thehistoryofpetrochemical
technology
according to the narrow sense, using natural
gas and petroleum as raw materials, andintroduce those epoch-making technologies
for petrochemistry.
6.3.1

History of petrochemical
technology
To review the history of petrochemical
technology, petrochemicals can also beclassified three ways; namely, basic
petrochemicals, industrial organic chemicals
and polymers.
(1) Technologies for basic petrochemicals
Production of basic petrochemicals
started at in the early 1920s with the
production of ethylene by steam cracking of
ethane in the United States. The ethane wasseparated from natural gas. This separation
process was an application of the cryogenic
distillation process developed in the industrial
gas industry in the 1900s. The thermal
cracking process for hydrocarbons was basedon the thermal cracking technology for heavy
oil that had been developed in the oil refining
industry in the 1910s. However, unlike
thermal cracking technology for heavy oil,the steam cracking process progressed frompetroleum refining to petrochemistry due to168

the technological innovation in lowering thepartial pressure of hydrocarbon by theaddition of steam. The application of steam
cracking was extended to include propane in
the 1930s and naphtha in the 1940s. It tookquite some time to widen the range ofapplications; this was because the types ofbasic petrochemicals produced by steam
cracking rapidly increased with each increasein the number of carbon atoms in the raw
material hydrocarbon, which meant it thenbecame necessary to develop technologies forseparating/refining them. Both production
technologies and separation and refining
technologies are important for basic
petrochemicals, as mentioned in Section 6.1.1(8). Steam cracking has been the mostimportant manufacturing technology for
ethylene since the 1920s. Althoughmanufacture of ethylene by catalytic crackingof hydrocarbon has long been studied, it has
not been industrialized yet.
The steam cracking of naphtha inpetrochemistry has become a major supply
source of not only ethylene but also
propylene, butylene, butadiene, benzene andp-xylene. It is also worth noting that thisprocess led to the started of production ofbasic petrochemicals not only in the UnitedStates, but all around the world, as mentioned
in Section 5.3.2 (2). Steam cracking of
naphtha was widely used in the 1950s in
Europe and Japan, from the 1970s onwards in
Asia and Latin America and in the 2000s in
China. Meanwhile, steam cracking of ethane
was only widely used in the Middle East in
the 1980s.
Thermal cracking and catalytic crackingof heavy oil are petroleum refining
technologies, because the main purpose isproduction of gasoline. These cracking
technologies are associated with thegeneration of large amounts of wastehydrocarbon gas containing propylene andbutylene.
Since there has long been less demand for
propylene than for ethylene, the main supply
source for it has been waste gas from steam
cracking of naphtha, mainly for producing
ethylene; in the United States and othercountries, it has been waste gas from catalytic
cracking of heavy oil, mainly for producing

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

gasoline. In other words, propylene has been
supplied by byproducts. However, from the
1990s onwards, the supply of propylene
became insufficient; consequently, propane
dehydrogenation and metathesis reaction(ethylene and n-butylene) were industrialized.
The only main purpose of these technologies
was the production of propylene.
Butadiene is mainly supplied by solvent
extraction and extractive distillation from theC4 fraction produced by steam cracking of
naphtha. This process was developed in the
1940s; modifications to it were developed
one after another in the 1950s and the 1960s
and have been used until now. In the UnitedStates, butadiene has also been produced
since the 1930s by dehydrogenation ofbutylene from waste gas obtained by catalytic
cracking of heavy oil. This technology may
also be classified as a petrochemical
technology.
Meanwhile, catalytic reforming of
naphtha is a petroleum refining technology,
mainly for producing high-octane gasoline.
Catalytic reforming was widespread in the
United States in the 1950s, followed by
Europe and Japan. The technology for
extracting aromatic hydrocarbons fromreformate is a petrochemical technology thatwas developed in the 1950s. The productionof aromatic hydrocarbons was industrializedusing the distillation of coal tar in the
mid-19th century. In the 1950s and the 1960s,
approximately 100 years later, the main
aromatic hydrocarbon supplier shifted fromcoal tar to petrochemistry, due to thedevelopmentoftwopetrochemical
technologies. These were the distillation of
cracked gasoline by steam cracking of
naphtha and the extraction of aromatichydrocarbons from reformate. Further,
petrochemical processes for producing
individual aromatic hydrocarbon products
came to include dealkylation of toluene(benzene), developed in the 1950s, anddisproportionation of toluene (benzene andxylene) and isomerization of m-xylene(xylene),developedinthe1960s.
Petrochemical technologies for separating
individual aromatic hydrocarbon products
came to include separation of p-xylene by
crystallization (1940s), separation of p-xylene

by solid adsorption (1970s), separation ofm-xylene by complex formation (1960s), etc.,
in addition to various distillation technologies,
including
extractive
distillationandazeotropic distillation.
A technology for producing syngas was
originally developed in the 1910s as a syngas
reaction of coke. Since the main purpose ofthis technology was to obtain hydrogen inorder to synthesize ammonia, a water gas
reaction was also carried out. In this watergas reaction, carbon monoxide was reactedwith steam to give hydrogen and carbon
dioxide. Syngas was made in large quantities
to produce methanol in the 1920s andartificial petroleum by the FT process in the
1930s. In petrochemistry, production ofsyngas from hydrocarbons such as natural gas,
propanone/butane, naphtha and crude oilwent into full swing in the 1950s.
As mentioned above, the basic
petrochemical
producttechnologies
manufactured from petroleum or natural gas
became fully industrialized in the 1920s for
ethylene, the 1940s for butadiene and the1950sfor propylene andaromatichydrocarbon/syngas (Fig. 6.28).
(2) Technologies for industrial organic
chemicals
As shown in Fig. 6.29, there are a large
number of major industrial organic
chemicals; furthermore, many of them havebeen industrially produced since before thecreation of petrochemistry. Therefore, it isdifficult to gain a sense of the overall flow ofpetrochemical technologies in the narrow
definition. For this reason, the history ofindustrial organic chemicals is reviewed hereaccording to the system of technologies usedin Section 6.1.2 Technological system ofindustrial organic chemicals.
Addition reactions to the double bond of
olefins by the sulfuric acid process beganwith the production of IPA in the 1920s andthe production of butanol and ethanol in the
1930s. Also in the 1920s, the production of
ethylene oxide, EG and propylene oxidebegan by the chlorohydrin process. The
production of EDC by addition of chlorine
was also performed in the 1920s, although itsoon came to nothing. These processes were
Systematic Survey on Petrochemical Technology

169

all stoichiometric reactions using highly
reactive chemicals. In the 1930s, addition
reactions using catalysts were developed one
after another. For example, ethylene oxide
was made by epoxy-addition of oxygen toethylene; ethylbenzene and cumene weremade by addition of benzene to ethylene;
polymer gasoline was made by addition of
olefins to olefins; alkylate gasoline was madeby addition of isobutane to olefins andbutyraldehyde was made by the oxo processwith propylene. From the 1940s to the 1950s,
alcohol was produced by direct hydration
reaction to the double bond of olefins, while
ether was produced by direct addition
reaction of alcohol to the double bond of
olefins.
Development of the epoxy addition
process to the double bond of propylene wassubstantially delayed. In the 1960s, theHalcon process was developed, using
peroxide. However, this process was notconvenient, as the stoichiometric reaction
produced propylene oxide along withbyproducts (styrene, t-butyl alcohol, etc.). In
the 1990s, the hydrogen peroxide process wasdeveloped, with water as a byproduct, and theabove problem was solved. However, direct
addition reaction with oxygen has not yet
been industrialized.

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Product

Before 1900

1900s

SyngasCoke oven gas

HydrogencyanideAcetylene

Castner process (metal Na, coke andammonia)

1910s

Carbide process

Thermal decomposition ofheavy oil

Propylene

Dehydration of
fermentation ethanol

Thermal decomposition ofheavy oil

Coke oven gas separation
Pipe-type steam cracking of naphtha
Pipe-type steam cracking of naphtha→ Waste gas
utilization

Heavy oil fixed-bed catalytic cracking
Acetaldehyde
condensation process

Butylene

1940s

Arc process of natural gas→ Waste gas
utilization
Ethane steam
cracking

Butadiene

Higher olefin
BenzeneMixed xylene
p-Xylene

1930s

Formamide process
Thermal cracking of heavy oil

Ethylene

1920s
Syngas reaction ofcoke→ Waste gas
utilization

Coal tar distillation

Pipe-type steam cracking of naphtha
Butylene dehydrogenation process
Butane dehydrogenation process
Heavy oil fixed-bed catalytic cracking
Pipe type steam cracking of naphtha
Pipe-type steam cracking of naphtha
Pipe-type steam cracking of naphtha
Crystallization separation process

Fig. 6.28 Technological history of basic petrochemicals (before 1900 – 1940s).

Systematic Survey on Petrochemical Technology

171

Product

1950s
Steam reforming of natural gas by partial
Syngascombustion, steam reforming
Hydrogen The Andrussow process using natural gas ascyanideraw material

1960s

1970s

1980s

After 1990s

AN byproduct of Sohio
process
High-temperature steam
Byproduct by steam cracking of ethane andAcetylene
cracking process of naphtha
naphthaand crude oil
High-temperature steam
Trial for various naphtha cracking processes cracking process of naphtha
Ethyleneand crude oil

Propylene

Metathesis process
Strengthening fluidized-bed catalytic
cracking
Propane dehydrogenation process
MTP process

Heavy oil fluidized-bed catalytic cracking

Butadiene
Butylene

Heavy oil fluidized-bed catalytic cracking
Propylene tetramerization

HigherolefinBenzeneMixedxylenep-Xylene

Isobutane
dehydrogenation

Catalytic reforming oil extraction ofnaphthaToluene dealkylation process
Catalytic reforming oil extraction ofnaphthaPyrolysis of n-paraffin
Ethylene oligomerization

Separation from FT artificial
petroleum
Separation from FT artificial
petroleum

Toluene disproportionation
process

Cyclode-hydrogenation of
propane/butane

Toluene disproportionation
m-Xylene isomerization
Octafining process

Solid adsorption separation
processFig. 6.28 Technological history of basic petrochemicals (1950s – after 1990s).

172

Ethylene dimerization

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m-Xylene isomerization HTI processProduct
Ethylbenzene

Before 1900

1900s

1910s

1920s

1930s
Aluminum chloride catalytic process
EB dehydrogenation process byalumina-chromia catalyst
EB side chain chlorination, dehydrochlorination
process
Acetophenone process

StyreneMethanol

Wood carbonization process

Ethanol

Coke-based syngas process
Fermentation process

IPA
n Product byacetone-butanol
fermentation process

Butanol

Sulfuric acid and hydration
process of propylene
n Product by condensation
and reduction process ofacetaldehyde
High-pressure hydrogen
reduction of oils and fats
Chlorohydrin process
EDC process and chlorohydrin
process
Chlorohydrin process

Higher alcohol
EO
EG
PO
Glycerin

Hydrolysis process of oils andfats

AcetoneDecomposition process ofwood carbonization Acetateof limeAcrylonitrile

Sulfuric acid and hydration process of ethylene

1940s

Direct hydration
process of
ethylenesec and tert Product from sulfuric acid andhydration process of n-butylene andisobutylenen and iso Product from Co catalyst oxo reaction
and reduction process of propylenen-Paraffin oxidation process
Silver catalyst direct oxidation process
EO water addition process
Epichlorohydrin
process

Acetone-butanol
fermentation process

Dehydrogenation process of
IPA

Acetylene/steam process
Ethylene cyanohydrin process
Ethylene cyanohydrin process

Acrylic acid

Fig. 6.29 Technological history of major industrial organic chemicals. (Ethylbenzene – Acrylic acid before 1900 – 1940s)

Systematic Survey on Petrochemical Technology

173

Product

Before 1900

1900s

1910s

MMA

1920s
Acetone cyanohydrin process

1930s

Propylene, chloroacetic acidprocess

Acetaldehyde
Acetic acid

Wood carbonization process

Vinyl acetate

Mercury sulfate catalyst
hydration process ofacetylene
Oxygen oxidation of
acetaldehyde
Liquid-phase acetic acidaddition process toacetylene

Vinyl chloride
Coal tar distillation
Sulfuric acid process ofbenzenePhenolEthanol oxidation process

Gas-phase acetic acidaddition process to acetylene
Alkali dehydrochlorination
process of EDC

HCl addition process to acetylene by Mercury
chloride catalyst

Chlorobenzene process

Raschig process
Phenol - cyclohexanol - nitric acid oxidation
process
Phenol - anon - oxime - Beckmann
rearrangement process

Adipic acid
Caprolactam
Terephthalicacid
Phthalic
anhydride
Maleicanhydride

Fuming sulfuric acid oxidationof naphthalene

Catalytic oxidation processof naphthalene
Phthalic anhydride
byproduct recovery process

Catalytic oxidation process of benzene

Fig. 6.29 Technological history of major industrial organic chemicals. (MMA – Maleic anhydride before 1900 – 1940s)

174

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1940s

Product

1950s

1960s

1970s

Ethylbenzene

Phosphoric acid catalytic process

BF3-HF catalytic process

ZSM-5 catalyst process

StyreneEB dehydrogenation process ofsteam dilution by iron oxide
catalyst

Methanol
Ethanol
IPA

ButanolHigher alcoholn and iso Product from Reppe
process (CO, water) of propylene

tert Product from Halcon
process (PO co-production
process)

Ziegler-Alfol process

EO
EG

Halcon process (oxidation by
peroxide)PO

tert Product from direct hydration process byacidic IM catalyst of isobutylene
n Product from Rh catalyst oxo reaction (CO,hydrogen) and reduction process of propylene
Oxo reaction and reduction process of higher
olefinDimethyl oxalate reduction process

Acrylonitrile

Acrylic acid

Direct oxidation by hydrogen
peroxide
Allyl alcohol
process

Glycerin
AcetoneAfter 1990s

Halcon process (PO co-production process)Natural gas-based syngas process
Direct hydration process of
propylene

1980s

Wacker atmospheric oxidation
process of propylene
Sohio process (ammoxidation of
HCN addition process to acetylene
propylene)
Modified Reppe process(carbonylation of acetylene)
Ketene - propiolactone process
AN hydrolysis process

Biodiesel byproductCumene process

Ammoxidation process of
propanePropylene oxidation process (via acrolein)

Fig. 6.29 Technological history of major industrial organic chemicals. (Ethylbenzene – Acrylic acid in 1950s – after 1990s)

Systematic Survey on Petrochemical Technology

175

Product

1950s

1960s

1970s

MMA

Acetaldehyde

Hydroxylation of ethylene (Hoechst-Wacker
process)

Acetic acid

Oxygen oxidation process of naphtha

Vinyl acetate

Acetic acid oxidation of ethylene (Hoechst-Wacker
process)

Vinyl chloride
Cumene process

PhenolCyclohexane - cyclohexanol - nitric acid oxidation
process

Adipic acid

Caprolactam

Terephthalicacid

Phthalic
anhydride
Maleicanhydride

Cyclohexane - Anon - oxime - Beckmann
rearrangement process
Peracetic acid process (cyclohexane - Anon caprolactone - lactam)
Two-stage nitric acid oxidation process of PX
Air oxidation and nitric acid oxidation process of
PX
The 1st Henkel process (o-phthalic acidisomerization)
DMT process
Amoco - mid-century process

Oxygen oxidation of ethylene processacetaldehyde

Carbonylation process
of methanol

1980s
Isobutylene oxidation process(via methacrolein)
t-Butanol oxidation process (viamethacrolein)
Ethylene raw material process

After 1990s
MGC process
Direct meta process of isobutylene

Direct oxidation process of ethylene

Chlorine addition to ethylene, de-HCl
Oxychlorination processprocess (EDC process)
Acetylene-ethylene combination process
Oxidation process of cyclohexane
Benzoic acid process
Photonitrosation process (cyclohexane oxime hydrochloride - Beckmann
rearrangement)
Cyclohexane - nitric acid nitration - oximehydrogen reduction and rearrangement
process

Cyclohexane - Anon - ammoximation gas phase Beckmann rearrangement
process

The 2nd Henkel process (benzoic aciddisproportionation)

Catalytic oxidation process of o-xylene
Catalytic oxidation process of butylene

Catalytic oxidation
process of n-butane

Fig. 6.29 Technological history of major industrial organic chemicals. (MMA – Maleic anhydride in 1950s – after 1990s)

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Technology

Before 1900
Celluloid
Nitrification cotton
process rayon

Utilization of natural polymer
Synthetic polymer(Addition condensation)(condensation
polymerization,
thermosetting)(condensation
polymerization, thermal
plasticity)(Oxidative polymerization)(radical polymerization)

1900s

1910s

1920s

1930s

Nitrocellulose lacquer

Viscose processrayon(viscose) cellophane
Acetate fiber, coating
Phenolic resin

Urea resin

Melamine resin

Nylon
Dry oil paint

Alkyd resin
Vinyl acetate resin
Vinyl chloride resin

Polystyrene
PMMA
LDPE
Chloroprene rubber
SBR
NBR(Ion polymerization)(Metathesis)

Fig. 6.30 History of major polymer technology (before 1900 – 1930s)

Systematic Survey on Petrochemical Technology

177

Technology

1940s

Utilization of naturalpolymer
Synthetic polymer(Additioncondensation)(condensation
polymerization,
thermosetting)

1950s

1960s

(acetate) Photographic film

(acetate) Cigarette filters

1970s

1980s

After 1990s(acetate) Liquid crystal polarizing film

Unsaturated polyester
Polyurethane

Polyimide

Epoxy resin
Silicone(condensation
polymerization,
thermal plasticity)(Oxidative
polymerization)(radical polymerization)(Ion polymerization)

PET film

PPO
Polyurethane-type
thermoplastic rubber
Polysulfone

Polycarbonate

Meta-aromatic aramid

Polyester PET

PBT

PEEK

PES
Para-aromatic
aramidPolyetherimide
Liquid crystal polymer

PPO
VinylonAS resin
ABS resin
Fluororesin

Acrylic

Butyl rubber

Low-pressure process HDPE
Medium-pressure process HDPE
Polyacetal

Styrene-type thermoplastic
rubber

L-LDPE

Metallocene PE(Post-metallocene PE)

Polypropylene
EPDM rubber
Polyisoprene rubber
cis-1,4-Butadiene-based
rubber(Metathesis)

COP

Fig. 6.30 History of major polymer technology (1940s – after 1990s)

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Development of technologies using
reactions to places other than olefin double
bonds took considerably longer than thetechnologies using additions to olefin double
bonds. These technologies are all catalytic
reactions. Allyl chloride was made frompropylene in the 1940s, followed by the
Hoechst-Wacker process (acetaldehyde fromethylene) in the 1950s, vinyl acetate byacetoxylation of ethylene, acrylonitrile byammoxidation of propylene and maleic
anhydride by oxidation of butylene in the
1960s, acrolein and acrylic acid by directoxidation of propylene in the 1970s, MMA
by oxidation of isobutylene in the 1980s, andso on.
In the 1920s, production of vinyl chloride
started with the formation of EDC by anaddition reaction of chlorine to ethylene,
followed by dehydrogenation with an alkali.
However, due to the fact that this processwasted hydrogen chloride, it came to be
replaced by the acetylene process. In the
1950s, the EDC process revived as a result ofa cheap supply of ethylene and the hydrogenchloride being collected by thermal crackingof EDC. However, this process was really
only applicable when there was a consumer
with a demand for the collected hydrogenchloride. One such consumer was the
ethylene/acetylene coproduction process, inwhich hydrogen chloride was added toacetylene. For this purpose, even processes
for manufacturing basic petrochemicals(co-production of acetylene and ethylene) by
flame
crackingofnaphthaandhigh-temperature steam cracking of crude oil
were developed. In the 1970s, the ethylene
oxychlorination process was developed, andvinyl chloride was subsequently only
produced using the
EDC process combined with theoxychlorination process.
Althoughsomemanufacturing
technologies for aromatic industrial organic
chemicals had long been used in coal tar
chemistry, most of the petrochemical
technologies in the narrow sense weredeveloped between the 1950s and 1960s,
coming after the manufacturing processes forolefins. In the 1950s, phenol became apetrochemical product, with the developmentof the cumeme process superceding theexisting coal chemistry technology., The
cyclohexane process was also developed in
the 1950s for manufacture of adipic acid andcaprolactam, replacing the phenol process,which had been used since the coal chemistry
period. Manufacture of pthalic anhydride bycatalytic oxidation of o-xylene was developedin the late 1960s. This technology
superceded the oxidation of naphthalene fromcoal tar. It may be said that terephthalic acidas a raw material for polyester is an industrialorganic chemical that was developed between
the periods of coal chemistry and petroleum
chemistry, because it has been in demandsincepetroleumchemistry
becamewidespread to Europe and Japan in the 1950s.
Accordingly, in the 1950s, coal chemistry
technologies (first and second Henkel
processes) and petrochemistry technologies(air oxidation/nitric acid oxidation of
p-xylene, DMT process and Amoco process)were both developed one after another,
competing with each other.
Of the technologies for manufacturingindustrial organic chemicals with syngas,
only the manufacture of acetic acid bycarbonylation of methanol, developed in the
1970s, may be classified as a petrochemical
technology in the narrow sense. The bases for
production technologies for methanol,
formaldehyde, etc. had already formed in thecoal chemistry period.
As mentioned above, among thetechnologies for manufacturing industrialorganic chemicals by petroleum chemistry in
the narrow sense, addition reaction to the
double bond of olefins began withstoichiometric reactions in the 1920s, later
replaced by catalytic reactions in many cases
from the 1930s onwards. Reaction processes
to places other than olefin double bonds weredeveloped in the 1950s and have since thenbeen extending the range of olefin chemistry.
Manufacturing technologies for aromatic
industrialorganic
chemicalsbypetrochemistry bore fruit based on coal tar
chemistry in the 1950s. However, the maintechnologies for many products including
caprolactam and adipic acid, were establishedduring the period of coal chemistry.

Systematic Survey on Petrochemical Technology

179

(3) Polymer technology
The history of polymer technologies has
been mentioned in some detail in Section
6.1.3. It is summarized in Fig. 6.30. In the
1940s, 1920s petrochemistry combined withpolymerization for the first time in the UnitedStates; at that time, large amounts ofsynthetic rubber (SBR) were being produced
from butadiene in line with United Statesnational policy. This triggered dramaticdevelopments in petroleum chemistry fromthe 1950s onwards. However, perhaps
unexpectedly, the basic technology ofsequential polymerization was formed in thecoal chemistry era before the 1940s, as shownin Fig. 6.30. Nevertheless, sequential
polymerization has also created many newpolymers in petrochemistry since the 1960s,
such as the recently developed functional
polymers.
Meanwhile, in chain polymerization,
radical polymerization has produced many
significant polymers (polyvinyl chloride,
vinylacetateresin,
poly(methylmethacrylate),polystyrene,
chloroprenerubber, SBR, NBR, ABS resin, acrylic fiber,
LDPE, etc.). The main monomers for radical
polymerization
were
producedandindustrialized in coal chemistry (acetylene
chemistry and coal tar chemistry) andfermentation chemistry (ethanol). These basic
technologies were established independentlyof petrochemistry. In the 1940s, ionicpolymerization produced butyl rubber, BR,
etc. mainly from petrochemical raw materials.
As mentioned above, monomers formany polymerization technologies weredeveloped and industrialized independentlyof petrochemistry. In contrast, coordination
anionic polymerization was only created inpetrochemistry in the 1950s. This technology
subsequently made a substantial contribution
tothedramatic
developmentof
petrochemistry. As this technology is alreadydescribed in detail in Section 6.1.3 (1) 4), any
further explanation of it is omitted here.
(4) Essence of petrochemical technology
As discussed above, when reviewing thehistory of petrochemical technology in the
narrow sense, the petrochemical technologies
that have played the most important role in

180

the
technologicaldevelopmentof
petrochemistry since it was created to thepresent can be considered to be olefin
manufacturing
processesforbasic
petrochemicals,
olefinchemistryforindustrial organic chemicals and olefin
polymerization processes for polymers
Of the processes for manufacturing basic
petrochemicals (Fig. 6.2), the technologies
for manufacturing syngas and aromatichydrocarbons supplement the technologies
formanufacturingolefins.
Syngasmanufacturing technologies were essentiallyestablished in coal chemistry; the same is trueof aromatic hydrocarbon technology inpetroleum refining technologies. These priortechnologies flowed over into petrochemistry.
Of the manufacturing technologies forindustrial organic chemicals (Fig. 6.16),
aromatichydrocarbon
chemistry,
cycloparaffin chemistry, C1 chemistry andother organic synthetic chemistry supplement
olefin chemistry. Aromatic hydrocarbon
chemistry, C1 chemistry and other types oforganic synthetic chemistry were developedin coal chemistry or fermentation chemistry
and then flowed over into petrochemistry.
Cycloparaffin chemistry came into being inpetrochemistry but has not flourished, otherthan for cyclohexane.
Of the polymer manufacturing technologies(Figs. 6.22 and 6.24), coordination anionicpolymerization,
includedinionicpolymerization of chain polymerization, hasplayed a central role. On the olefin
polymerization
technologies,
radicalpolymerization (LDPE) in the 1930s, anionicand cationic polymerization (polybutadiene
and butyl rubber) in the 1940s and metaloxidepolymerization(HDPE)
weredeveloped. Since the 1950s, coordination
anionic polymerization has been a mainstream of the technological development ofpolymers. Sequential polymerization andradical polymerization technology, whose
foundation was already laid before thecreation of petrochemistry, flowed over into
petrochemistry, thus supplementing thetechnologies for manufacturing polymers inpetrochemistry. However, the importance ofsequential polymerization revived from the
1980s onwards, because petrochemistry

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began aiming towards functional chemistry.
6.3.2

Epoch-making petrochemical
technology
Table 6.4 summarizes the epoch-making
technologies
that
made
substantial
contributions
totheprogressofpetrochemistry in its history of more than 100
years.
Table 6.4 Epoch-making technologies in thehistory of petrochemistry

It is well known that petrochemistrybegan with the production of isopropyl
alcohol by the sulfuric acid process fromwaste gas obtained by thermal cracking ofheavy oil in 1920. However, this process isonly part of the organic synthetic processes
that have been accumulated since the 19th
century, because thermal cracking of heavy
oil is a petroleum refining process for
producing gasoline, and because the sulfuric
acid process is a stoichiometric reaction using
propylene and sulfuric acid. Therefore, itcannot be classified as an epoch-making
petrochemical process. It is not well known
that the steam cracking of ethane separated
from natural gas was also industrialized in
1920. This process, however, can be said tobe the first epoch-making technology inpetrochemistry, because it subsequently
played a very important role in the
petrochemical industry, due to the fact that its
main purpose was the production of ethylene
as a raw material for chemicals, and the factthat a decrease of partial pressure by additionof steam was a versatile technology that wasapplicable to the production of otherpetrochemicals. Nevertheless, the process forsteam cracking of naphtha and separation of
products developed in the 1940s was still
important, because it laid the foundation forthe creation of petrochemistry in Europe andJapan in the 1950s.
Production technology for ethylene oxidein the presence of a silver catalyst wasinvented in France in the early 1930s andindustrialized in the late 1930s. This
technology was the first to be industrializedusing a solid-supported catalyst in the historyof petrochemistry. It is also very significant
that the reaction associated with high risk of
explosion, in which ethylene was mixed withoxygen or air to directly synthesize ethyleneoxide, was successfully industrialized early inthe history of petrochemistry.
Production technology for acetaldehyde
by the Hoechst-Wacker process andproduction technology for acrylonitrile byammoxidation in the 1950s and production
technology for EDC by oxychlorination
process in the 1960s markedly widened therange of olefin chemistry. These were
epoch-making technologies, because they
provided petrochemistry with a basis forcompletely dominating coal chemistry. In the
1980s, the metathesis reaction was developed,
following on from the above three types ofolefin chemistry. It, too, extended the rangeof olefin chemistry.
In the 1950s, the Ziegler-Natta catalyst
was developed in
the period of
petrochemistry. This catalyst became astarting point for coordination anionicpolymerization, which is still making
advances to this day. It was also
epoch-making in that it produced large-scale
petrochemical products (polyethylene, PP andvarious synthetic rubbers).
The zeolite ZSM-5 process developed in
the 1960s is a solid catalyst/adsorptive
separation technology that utilizes stericstructure-controlled empty holes. This
technology was widely used in various areasof petrochemistry and, moreover, it became astarting point for the utilization of stericstructure-controlled empty holes other thanthose of ZSM-5.

6.4 Japanese petrochemical technology
Thissectiondiscusses
Japanesepetrochemical technology in the context ofthe history of petrochemical technology
Systematic Survey on Petrochemical Technology

181

worldwide. Currently, Japanese companies
are leading the world in the development ofsome petrochemical technologies, including
technology
utilizing
C4
olefins,
post-metallocene catalysts and paraffinchemicals. Japan’s new initiatives infunctional chemistry are also dramaticallychanging
theexisting
conceptsofpetrochemistry.
6.4.1 ThehistoryofJapanesepetrochemical technology
Prior to petrochemistry, Japan alreadyhad a long history in developing
mass-producing chemical industries, such ascoal chemistry. Although these chemicalindustries were dealt a devastating blow by
the Second World War, the technology was
not
lost.
When
adopting
Westernpetrochemical technology in the 1950s, Japandrew on its existing technological expertise,quickly absorbing petrochemical technology
and moving on to being an active player in
the Sturm und Drang period of
petrochemistry. This laid the foundation forJapanese companies to become frontrunners
in functional chemistry from the 1980s
onwards, and to spark new trends inpetrochemical technology.
(1) The 1950s: Japanese petrochemistry
launches on domestically-produced
technology
As discussed in Section 5.3.3 (2),petrochemistry in Japan started in 1952 withthe production of syngas and methanol byJapan Gas Chemical using natural gas from
Niigata as a raw material. Methanol had been
produced in Japan since the start of the 20th
century by the wood retorting industry;syngas had been produced since the 1930s
using coal as a raw material. Accordingly,
Japan already had the technology to produce
methanol from syngas since before theSecond World War. The technology to
produce syngas from natural gas had beendeveloped through joint research between
Japan Gas Chemical and Japan Gasoline(Table 6.5). Leading up to the early 1950s,
there were a number of instances of Japanesecompanies using their own technology
developed before and during the war to
produce acetylene chemical products and coal182

tar chemical products, as shown in Table 6.5.
The technology developed by Japan Gas
Chemical was one such example.
Table 6.5 In-house technology of industrialorganic chemicals and polymers developed
after the Second World War and up to thefirst half of the 1950s
Year
1946

Company
Toshiba
Corporation
Shonan,Yokahama Rubber

1947

The Nippon
Synthetic
Chemical Industry

1948
to
1951

Tekkosha, Denki
Kagaku Kogyo andothers1950

Kurashiki Rayon

1951

Toyo Rayon

1951

Toagosei
Chemical Industry

1952

Nippon Shokubai

1952

Japan Gas
Chemical, Japan
Gasoline

1953

Nippon Shokubai

1953

Kureha Chemical
Industry

Product
Start of production ofacetylene-process vinyl
chloride resin
Production resumed onacetylene-process vinyl
acetate (Start of productionin 1936)
Start of production ofacetylene-process vinyl
chloride resin
Start of production of
polyvinyl alcohol and vinylon
Completion of a plant toproduce nylon with a 5t
daily production capacity
Completion of caprolactam
synthesis technology
Completion of maleic
anhydride facility ofbenzene gas-phaseoxidation process
Completion of steam
catalytic reforming
technology of natural gas
Start of anthraquinone
production by anthracene
gas-phase oxidation
Start of production ofvinylidene chloride resin

Source: Prepared from reference [5] and each company's
homepage

Of course, not all such technology
developments were necessarily successful.
“On the Petroleum-Based Synthetic Chemical
Industry,” published by the Ministry ofInternational Trade and Industry, Organic
Division on June 1, 1951, noted the research
by Japan Gas Chemical, as well as
experiments by Gas Denko Bunkai to
produce acetylene gas and hydrogen by arc
cracking natural gas. It stated that there wereplans to industrialize acetylene-process vinyl
chloride and vinyl acetate based on thissuccess. However, domestic technologicaldevelopment of the arc method ultimately
never came to fruition.
With oil refineries reaching a certain

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level of development, as mentioned in
Section 5.3.3 (3), Nippon Petro Chemicals
produced isopropyl alcohol and acetone frompetroleum waste-gas propylene in 1957,
while Maruzen Petrochemical produced
sec-butyl alcohol and MEK from n-butylene,
also found in petroleum waste gas. This is
generally regarded as the start ofpetrochemistry in Japan. While Nippon Petro
Chemicals was using introduced technology,
Maruzen Petrochemical had developed its
own. We must not forget that Japanesepetrochemistry did not start out on introduced
technology alone, but with a wealth ofindependently-developed technology as well.
(2) The 1960s: The introduced technology
rush
anddomestically-produced
petrochemical technology
In the 1950s, Japan was on the receiving
end of an influx of information about major
petrochemical developments in the West, notonly within the field of petrochemistry, butalso in petrochemistry-related technology
fields that were new to the pre-war chemicalindustries(chemical
engineering,
instrumentation and control technology,
instrumental analysis and plastic molding, as
discussed in Chapter 2). The Japanesechemical industry was shocked by the major

technology gap with the West that had sprungup during the information blackout period in
the Second World War. Japan started
increasing its imports of PVC, polystyrene,
polyethylene and other polymers. This
presented a significant problem, given theforeign currency situation at the time.
Accordingly, Japan immediately set about
licensing the petrochemical and related
technologies that were lacking in Japan, andaimed towards creating a petrochemicalindustry in Japan, starting with thesteam-cracking of naphtha. The Japanese
government pushed and supported this. As
shown in Table 6.6, the vast majority of thepetrochemical products initially produced by
Japan in the last 1950s were achieved throughintroduced technology. Later, as the Japanesepetrochemical industry began to become
more established through more technology
licensing from the West in the 1960s, the idea
began to take hold in Japanese society that
almost all petrochemical technology in Japanwas introduced technology. Delegations of anumber of Japanese chemical companies
flocked to Italian company Montecatini,which developed PP, in the hope ofestablishing technology licenses; this isjokingly referred to as the “Monte visit.”

Table 6.6 The earliest stage of petrochemical products and technologies in Japan

However, as mentioned in Chapter 5, as
Systematic Survey on Petrochemical Technology

183the United States petrochemical technology
transferred to Europe in the 1950s, it blended
with European chemical technology. Manysignificant petrochemical technologies had
their origins in Europe, while the UnitedStates began to import these European
technologies in return. From the 1950s
onwards, petrochemical technology began tospread beyond borders, unlike the situation
before the Second World War. This was partof the international spread of petrochemical
technology; it was not necessary to humiliate
itself for licensing. As a result, Japan’s
introduced technology rush from the late
1950s to the early 1960s saw Japan opt fortechnology licensing instead of the time, costs
and various risks involved in in-housedevelopment. One typical example is thelicensing of nylon technology by Toyo Rayon(now Toray). Toray had started researchingnylon before the war and started productionin 1951 using its own in-house technology, as
shown in Table 6.5. Prior to that, it had
developed the market with products such as
fishing lines and fish nets at the protoypestage,
which
boosteditsbusiness
performance immediately after the war.
Nevertheless, it outlaid significant capital andtook the plunge into introduced technology.
This was due to wanting to secure the market
at an early stage using technologies thatwould develop the market for clothing
applications, such as weaving and dyeing, as
well as polymerization, spinning and othernylon production technologies; avoiding
patent disputes with DuPont was also afactor.
There was one field of petrochemical
technology in which Japan had absolutely noprior underlying experience: steam-cracking
technology, developed from petroleum
refining technology. There were similar
situations in Europe; Japan was not the only
place to heavily rely on introduced
technology. However, Zeon and Kureha
ChemicalIndustrydevelopedandindustrialized high temperature steam
cracking for naphtha and crude oil in thisvery field, just as Europe was attempting
crude oil cracking and naphtha catalytic
cracking. The aim of this steam-cracking
technology was to co-produce acetylene and184

ethylene and to produce vinyl chloride by the
EDC process and the acetylene process at thesame time.
In those early days of petrochemistry,when Japan was caught up in introduced
technology, the industrialization of oxo
alcohols by Mitsubishi Kasei in 1960 using
its own technology is worth noting. This issaid to have been the result of researchundertaken with reference to the post-war PB
Reports researched and published by theUnited States on wartime German scienceand technology.
As shown in Table 6.7, althoughtechnologies were developed in the Westfrom the late 1950s to the early 1960s, Japanwas often the first or among the first to
industrialize them. In several cases, Japanesecompanies played a very significant role infinishing off industrial technologies forWesterntechnologicaldevelopment
companies. Examples of this include HDPE
by Mitsui Petrochemical Industries, PP by
Mitsui Chemicals, and acrylonitrile by Asahi
Kasei. Each of these is a very significant fieldof technology in the global history of
petrochemistry.
Table 6.7 Examples of world first or very
early industrialization in Japan ofpetrochemical technology
Product

Technology

Low-pressurepolyethylene

Ziegler
process

Terephthalicacid

The 1stHenkelprocess

Terephthalicacid

Mid-century
process

Mediumpressurepolyethylene

Standard
process

Polypropylene
Acrylonitrile
Naphtha steam
cracking
Terephthalicacid
AcetoneMontedisonprocess
Sohio
process
Esso typefurnace
The 2nd
Henkelprocess
Wackerprocess

Industrializationcompany
MitsuiPetrochemic
al Industries
Kawasaki
Kasei
Chemicals
MitsuiPetrochemic
al Industries
Furukawa
Kagaku
Kogyo
Mitsui
ChemicalsIndustrializationyear

Asahi Kasei

1962

Tonen Sekiyu
KagakuMitsubishi
ChemicalIndustries
Daikyowa
SekiyuNational Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

1958
1958
1958
1959
1962

1962
1963
1964

Alfin rubber

SolutionprocessSBR

Source: Prepared from reference [5]KagakuNippon Alfin
Rubber1970

Furthermore, as shown in Table 6.8, anumberofsignificant
petrochemical
technologies were developed in Japan as
early as the mid-1960s. Some of thistechnology was produced in Japan andexported to the West, such as the GPBprocess by Zeon. The GPB process has since
been exported to 49 plants in 19 countries.
Table 6.8 Important petrochemical
technology developed in Japan in the 1950s
to the 1960s
Industrialization
year

Product

Technology

1957

Methyl ethyl
ketone1959

Ethylene
oxide

FCCwaste gas
utilization
Ethyleneoxidation
process

1960

1960
1963
1964

1964
1965
1965
1966
1967
1967
1967
1968

1970

Development
company
MaruzenPetroleum
NipponShokubai

MaruzenPetroleum,
p-Xylene
Resources
Research
Institute
Mitsubishi
Propylene oxo
Oxoalcohol
Chemicalprocess
Industries
Caprolactam
PNC process
Toyo Rayon
Naphtha highKurehatemperature
ChemicalIndustry,
Vinyl chloride decompositionof Kureha
Chiyodaprocess
Corporation
Ammoxidation
NipponPhthalonitrile
process
ShokubaiJapan
Synthetic
Polybutadiene
JSR process
Rubber,Bridgestone
Zeon
Butadiene
GPB process
Corporation
Oxychlorination
Toyo Soda
Vinyl chloride
process
Manufacturing
Urea adductn-Paraffin
Nippon Mining
process
Dealkylation of
Mitsubishi
BenzeneMHCprocess Petrochemical
Zeon
Vinyl chloride
GPA process
Corporation
m-Xyleneextraction
Japan Gas
Mixed xylene
isomerization
Chemicalprocess
Propylene
NipponAcrylic acidoxidation
Shokubai
ester
process
Circulation
treatment
process

1970

Vinyl chloride

Crude oil hightemperaturedecompositionof Kureha
process

KurehaChemicalIndustry

Source: Prepared from reference [5] and each company's
homepageIn the late 1960s, a very large number ofplants started up through domestically
produced technology, as shown in Table 6.9.
Surprisingly, within only 5–10 years of
petrochemistry taking hold in Japan withintroduced technology at its core, a large
number of latecomer companies wereentering the market with their own
independent
technology
inevery
petrochemical product field. This alsosuggests that newcomers to the Japanesepetrochemical market in the late 1950s were
eager to industrialize their products throughintroduced technology and were first trying totake a firm hold of the market.
Table 6.9 Examples of industrialization bydomestic technology in the second half of
1960s
Name of company
Daicel Chemical
Industries
Denki Kagaku Kogyo
Showa Denko K.K.
Showa Denko K.K.
Mitsui Toatsu
ChemicalMitsui Petrochemical
Industries
Daicel Chemical
Industries
Tokuyama Soda
Sumitomo Chemical
Toyo Soda
Manufacturing
Mitsubishi Chemical
Industries
Daicel Chemical
Industries
Showa Denko K.K.
Mitsui Toatsu
ChemicalIdemitsu
Petrochemical
Idemitsu
Petrochemical
NipponProduct

Start ofproduction

Alkylamine

1965

Polystyrene
Isophthalonitrile
Xylylenediamine

1965*
1966
1966

Polystyrene

1966

Polypropylene

1967

Acrolein

1967

Vinyl chloride byoxychlorination
process
Meta-, para-cresol

1967
1967

Ethyleneamine

1967

Medium-pressurepolyethylene

1968

ABS resin

1968

Chlorinatedpolyethylene
Vinyl chloride byoxychlorination
process

1968
1968

Polycarbonate

1968

Polystyrene

1968

Petroleum resin

1968

Systematic Survey on Petrochemical Technology

185

Petrochemicals
Daicel Chemical
Industries
Showa Denko K.K.
Dainippon Ink
Mitsubishi
Petrochemical
Mitsubishi Chemical
Industries
Mitsui Petrochemical
Industries
Mitsui Petrochemical
Industries
Tokuyama Soda
Tokuyama Soda
Sumitomo Chemical
Asahi Kasei

Synthetic glycerin

1969

Polypropylene
Polystyrene

1969
1969*

Ethylene

1969*

Maleic anhydride

1970

EPR

1970

Meta, paracresol

1970

Polypropylene
Chloromethanes
High-pressurepolyethylene
Medium-pressurepolyethylene

1970
1970
1970*
1970

Idemitsu
Styrene1970
Petrochemical
Denki Kagaku Kogyo
ABS resin
1970*
Note: The asterisk (*) denotes the technology development
year.
Source: Prepared from reference [6]Nevertheless, even at this time there werestill some fields that were highly dependent
on introduced technology. These were fieldsof technology that had been established in the
1920s–1940s, when the petrochemicalindustry only existed in the United States(steam cracking, LDPE, styrene, synthetic
rubber SBR). This was the point of difference
afforded by a history of technology
accumulation. By contrast, the petrochemical
technologies that had come about in the
1950s era of fused Western technology weresuccessively being developed as domestically
produced technology. These included HDPE,
PP, styrenic polymers and oxychlorination
process for vinyl chloride.
While Japan came in towards the end of
the Sturm und Drang period of
petrochemistry, it was just in time to imbibe
the atmosphere of that era. Not only did it
simply adopt technologies developed in theWest, it also became an active player in the
Sturm und Drang period. Japanesepetrochemistry had the good fortune to startout in a completely different era from many
developing nations from the 1970s onwards.
[Footnote 6]

the petrochemical industry in the 1970s, air
pollution, water pollution and other negative
aspects began to manifest. Overseas
introduced technology could not be relied
upon to combat air and water pollution; thiswas resolved within a relatively short spaceof time through domestically-produced
technology. Japanese chemical companies
were quick to respond, having already put
high-pressure fat reduction technology, which
produces straight-chain higher alcohols, touse since before the war; this technology wasused to combat the issue of foam pollution
from synthetic detergents in the mid-1960s.
The petrochemical technology to extractn-paraffin, a starting material for obtaining
higher alcohols from kerosene, was also
developed by Nippon Mining in 1967 (Table
6.8).
Having caught up with the West in the
1970s, Japan was no longer lagging behindWestern companies in its technologicaldevelopments, even with the emergence ofseveral negative aspects of petrochemistryfrom the 1970s onwards, as discussed in
Section 5.5. Japan developed PCB processing,chlorofluorocarbon alternatives, processing
for nitrous oxide produced in the course of
making the raw materials for nylon andcountermeasures for plastic waste issues.
(4) The 1980s: Increased research anddevelopment expenses for Japanesechemical companies
In the 1980s, Japanese chemicalcompanies were increasingly very active inresearch and development, as shown in Fig.
6.31. Petrochemical companies are shown in
Fig. 6.31 as “Diversified Chemicals /Chemical Fibers.” While petrochemistry had
a lower R&D/sales ratio than other industries
such as pharmaceuticals, the expense of
research and development increased in the
1980s, and the R&D/sales ratio plateauedthroughout the 1990s and 2000s.

(3) The 1970s: Technologies developed in
response to negative aspects emerging
With major developments taking place in186

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 6.31 Change of the ratio of research anddevelopment expenses to sales of Japanesechemical companies.
Researchanddevelopmentby
petrochemical companies in the 1980s tended
towards
propylene/butylene
chemistry,developing polymer structural materials,
energy-conserving
technologies
andlow-polluting technologies. At the same time,functional chemistry was being explored indeveloped nations, as the mass-produced
petrochemicalmarketwasobviously
well-developed. This resulted in the early
appearance of engineering plastics utilizing
polymer technology, semiconductor resists
and photosensitive resins for print
platemaking and other applications.
(5) From the 1990s onwards: Functional
chemistry comes into full bloom
While functional polymer development
continued to be at the core, the expansion intofunctional chemistry by Japanese chemicalcompanies in the 1990s followed a different
business model from the conventional
petrochemistry in the West, namely, thedevelopment of functional chemical products
through the integration of polymer processing.
The expansion into polymer structural
materials in the 1980s had still centered ontechnological developments focused on theproperties of the material itself, such asheat-resistant or high-tensile engineering
plastics, or superabsorbent polymers.
However, the Japanese petrochemistrybusiness model from the 1990s onwards went
beyond the boundaries of petrochemistry(basic petrochemicals, industrial organic
chemicals and polymers), the scope of thepresent study, even incorporating theparts/products stage of products made frompolymers. Accordingly, the scope of researchand development went beyond the boundaries
of polymerization, even incorporating
polymer
processing
technology
andparts/products assessment technology, which
generated much added value. Table 6.10
shows the functional polymer materials andfunctional chemical products focused on by
Japanese petrochemical companies from the
1990s onwards. Japanese chemical companies
lead the world in one of these fields,
functional film, shown in Table 6.11. We
cannot forget that petrochemical technology,
particularly polymer technology, provided thebasis for the technology to develop thesefunctional chemistry products.
Meanwhile, Japanese petrochemicalcompanies have also been markedly active inthe fields of petrochemistry that fall within
the scope of this study, even while many
Western companies have been withdrawing
from petrochemistry. A number of Japanesecompanies have contributed to the new
synthesis technology for acrylic acid andmethacrylic acid. This is the field of olefinchemistry, hydrocarbons with three or morecarbon atoms and paraffin chemistry.
Japanese companies have also played a keyrole worldwide in the development of
post-metallocene catalysts.

Table 6.10 Functional polymer materials and molding products developed since the 1990s

Systematic Survey on Petrochemical Technology

187

Table 6.11 Functional film and its utilization area

6.4.2

World-class Japanesepetrochemical technologies
Tables 6.7 and 6.8 show thepetrochemical technologies developed by
Japanese chemical companies in the 1950s–
1960s. As a great many Japanese companies
developed their own technology from the1970s onwards, not all of them can be shownin these tables. Table 6.12 shows some ofthese independently-developed, world-class
Japanese petrochemical technologies. We

188

have already mentioned some of these: theoxo process by Mitsubishi Chemical (Section
5.4.2 (2) 1)); butadiene extraction by Zeon
(Section 6.4.1 (2)); highly active catalysts for
PP by Mitsui Chemicals (Section 6.1.3 (1)4)); nitrite process by Ube Industries (Section
6.2.3); the others we shall mention briefly.
Table 6.12 World-class Japanesepetrochemical technology
Industrialization year

Company

Technology

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

1959
1960
1962

NipponShokubai
Mitsubishi
ChemicalToray
Industries

Ethylene oxide production
technology
Oxo reaction technology
Caprolactam production
technology of photonitrosation
process

Zeon
Butadiene extraction technology
Corporation
Mitsubishi
m-Xylene separation,
Gas
derivatives production
1968
Chemicaltechnology
Company
Acrylic acid production
Nippon1970
technology of propylene direct
Shokubaioxidation process
MitsuiHigh activity catalyst technology
1977
Chemicals
for polypropylene
SanyoSuperabsorbent polyacrylic acid1978
Chemicalresin production technology
Mitsubishi
Methyl methacrylate production
Rayon and1982
technology of isobutylene
Nipponprocess
Shokubai
Mitsubishi
Acrylamide production
1984
Rayon
technology bio process
Ube
Oxidative carbonylation
1992
Industries technology (nitrite technology)
Polycarbonate production
2002
Asahi Kasei technology of carbon dioxide as
raw materials
Caprolactam production
technology that produces no
Sumitomo
2003
ammonium sulfate as a
Chemical
byproduct
Acrylonitrile production
2007
Asahi Kasei
technology of propane process
Note: The company names are the current ones, not thenames that were in use at the time of industrialization.
1965

NipponShokubaisuccessfully
industrialized the production of phthalicanhydride by oxidation of naphthalene,
maleic anhydride by the oxidation of benzene
and anthraquinone by oxidation of anthracene
in the coal chemistry era, which is around theSecond World War. In 1959, the company
developed its own technology to produce
ethylene oxide by direct oxidation of ethylene,
and industrialized this in an industrial
complex in Kawasaki. Along with Mitsubishi
Kasei’s oxo process, this was one of the
pinnacle achievements in early Japanesepetrochemistry.
The
companyalso
successfully industrialized the production ofacrylic acid by direct oxidation of propylene
in 1970, and MMA by direct oxidation of
isobutylene in 1982. It has continued topursue the development of oxidation
technology.

Mitsubishi Gas Chemical was anotherJapanese petrochemical company like Nippon
Shokubai that used its own technology to
expand into unique areas of business. Its
predecessor, Japan Gas Chemical, was thefirst to embark on petrochemistry in Japan
with the industrial production of syngas andmethanol from natural gas in 1952.
Mitsubishi Gas Chemical was the first in theworld to successfully isolate high-purity
m-xylene from mixed xylenes in 1968, using
its mastery of super-acid HF-BF3. It has
expanded into product categories that are
unique worldwide: high-purity isophthalicacid (a raw material for PET denaturation andmeta-aramid fiber) and m-xylenediamine (araw material for aliphatic diisocyanates andMX nylon) from m-xylene.
There are two types of noteworthy
caprolactam production technology: thephotonitrosation method developed by Torayin 1962, and a method developed by
Sumitomo Chemical in 2003 that produces noammonium sulfate byproduct (developed
from gas phase Beckmann rearrangement
technology). Both technologies are truly
notable in the history of caprolactam
technology worldwide. Further details onthese technologies are discussed in Section
6.1.2 (4).
The photonitrosation method developedby Toray is the only instance in the world of
producing industrial organic chemicals using
photoreaction. Similarly, Mitsubishi Rayon(Nitto Chemical Industry at the time, mergedin 1998) developed a bio method for
producing acrylamide through hydration ofacrylonitrile using microorganisms as acatalyst. A little later, Mitsui Chemicals also
developed a bio method for acrylamide
production, industrializing it in Korea andlicensing the technology to Finland in 2013(see Section 3.4.3 (7)). While bio methods areused to produce small quantities of chemical
products, such as amino acids, vitamins,
pharmaceutical intermediates and optically
active substances, there are no other instances
worldwide of such methods being used inmass production other than in petrochemistry.
Asahi Kasei developed a non-phosgene
polycarbonate production method using
carbon dioxide as a raw material, andSystematic Survey on Petrochemical Technology

189industrialized it through a joint venture in
Taiwan in 2002. This technology was later
exported to Korea, Russia, Saudi Arabia andother countries. Since it uses carbon dioxide
as a raw material for the polymer and also
does not use phosgene, it has received many
awards in Japan as a low-emission
technology, and also received an award fromthe American Chemical Society in 2014.
We
havealready
discussed
propane-based
acrylonitrile
production
technique, also developed by Asahi Kasei andindustrialized by a Korean subsidiarycompany, in Section 6.2.4. This is aninnovative technology with the potential tobreak away from the conventional frameworkof olefin-focused petrochemistry. The
propylene ammoxidation production method
for acrylonitrile is a world-dominating
technology held by British company BP. It
was thought that BP would also develop a
propane ammoxidation production method
for acrylonitrile; Asahi Kasei took the world
by surprise by doing it first. Section 6.3.2
introduced nine epoch-making petrochemical
technologies. Asahi Kasei’s propane-based
acrylonitrile production technology should be
the tenth on this list, with the potential toopen up a new field of petrochemistry,
namely, paraffin chemistry. It was notincluded in Section 6.3.2, as its historicalsignificance is not yet known.

6.5 Systematization of petrochemical
technology and discussion
Figure 6.32 shows a systematization of
petrochemical technology summarizing thecontents of this report, including technology
from the mass-producing chemical industries
that had developed prior to the creation of
petrochemistry.
As previously mentioned at length,
petrochemical technology consists of threeareas: basic petrochemicals, industrial organic
chemicals and polymers. Industrial organic
chemical technology has origins as early as
the 18th century wood retorting industry;other industrial organic chemical technology
dates back to coal tar chemistry in the late
19th century, carbide/acetylene chemistry in
the 1910s and coke-based syngas chemistry

190

in the 1920s. The wood retorting industry has
disappeared, unable to compete withcarbide/acetylene chemistry and syngas
chemistry in the 1930s. While oleochemistry
was created in the 1900s, it was in the 1920s
that higher alcohol production technology(high-pressurehydrogenreductiontechnology for fats and oils) emerged, which
would later have strong ties withpetrochemistry; it was in the 1930s that
production technology emerged for higher
alcohol sulfuric acid ester salts, the firstneutral detergent. Fermentation chemistry
was created as a mass-producing chemicalindustry in the 1920s.
Polymer manufacturing technology also
originated prior to petrochemistry; cellulose
chemistry (celluloid, rayon, cellophane,acetate) was created between the end of the
19th century and the 1920s, using naturalpolymers in chemistry, and greatly flourished.
Meanwhile, production technology for phenol
resin, the first synthetic polymer, started in
the 1910s through coal chemistry. A
succession of polymers emerged in the 1920s
and 1930s through radical polymerization; themonomers usedas the raw materials for thesewere produced by acetylene chemistry. In the
1940s, industrial production of LDPE byradical polymerization commenced. Ethylene,
the raw material for LDPE, was mainly
produced by dehydration of fermentation
ethanol, as high purity was required.
By contrast, in the United States,industrial organic chemicals (IPA, EG,
ethylene oxide) were being produced frombasic petrochemicals (propylene from waste
gas from heavy oil cracking, ethylene fromsteam cracking ethane) in the 1920s. This
technology was purely petrochemical inorigin. By the 1930s, petrochemistry had
expanded to include various alcohols,
tetraethyl lead and other products; however,
petrochemistry only existed as a supply forindustrial organic chemicals, alongside coalchemistry, fermentation chemistry andoleochemistry, according to the technologicalstrengths of each industry. Petrochemistry as
yet had no connection with polymers.
Restrictions on raw materials also meant that
petrochemical technology had yet to spreadbeyond the borders of the United States.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

In the 1940s, the production of synthetic
rubber SBR from butadiene was promoted
strongly in the policies of the United States,
triggeringaconnection
betweenpetrochemistry and polymers. Butadiene wasbeing produced in the United States bybutylene dehydrogenation; new developmentsin petrochemistry were beginning to bud.
However, the United States butadiene
production by butylene dehydration could notmatch that of fermentation ethanol; even forbutadiene petrochemistry could not take thetitle on its own.
In the late 1940s, after the end of theSecond World War, the U.S. petrochemicalindustry suddenly expanded significantly,
driven by a raid growth in consumer demandfor polymers. Production of PVC andpolyvinyl acetate rapidly increased inacetylene chemistry, as did in nylon andphenol resin in coal tar chemistry, urea resin
in syngas chemistry and LDPE andpolystyrene in petrochemistry. The surging
demand for polymers spread to Europe andthen Japan in the 1950s. Naphthasteam-cracking technology was transferredfrom the United States, prompting the start ofproduction of basic petrochemicals in Europe
in the early 1950s, and in Japan in the late
1950s. An underlying factor to this may be
the beginning of Middle Eastern crude oilbeing exported around the world.
Petrochemical technology, which had
been developed in the United States since the1920s, also spread to Europe in the 1950s anddeveloped further, fusing with the chemical
technologies there. This resulted in major
developments in olefin chemistry and olefin
polymerization technology in the 1950s and1960s within the field of production
technology for industrial organic chemicals
and polymers. The quality and scale of steam
cracking technology also increased rapidly
during this time. In addition to olefins, thesupply of aromatic hydrocarbons shifted fromcoal tar to cracked gasoline by naphthasteam-cracking and reformate by naphtha
catalytic reforming. Industrial organic
chemicals, which had once been produced byfermentation chemistry and acetylene
chemistry, were almost exclusively switchingto olefin chemistry. Even for polymers, as therange olefin polymer products expanded,almost all of the polymers produced byradical and sequential polymerization shiftedto petrochemistry, where they had previously
been made from monomers supplied byacetylene chemistry and coal tar chemistry.
Consequently, monomers became cheaper,
which in turn markedly increased the demandfor polymers from radical and sequential
polymerization.
Conversely,
cellulosechemistry quickly fell into decline at this time,
under pressure from synthetic polymers.
The trends in the 1950s and 1960s show anear disappearance of acetylene chemistry
due to the rise of olefin chemistry, whilearomatic chemistry was incorporated into
petrochemistry as the source of aromatichydrocarbons changed almost completelyfrom coal tar to petroleum. Coke-based
syngas chemistry was also incorporated into
petrochemistry due to the near completechange to natural gas and petroleum-based
syngas. Oleochemistry fell under the rise ofindustrial organic chemicals (surfactants)
produced by petrochemical technology.
Cellulose chemistry fell under the rise ofpolymers produced by petrochemical
technology, and the industry decreased
significantly. In the field of fermentation
chemistry, acetone and butanol fermentation
disappeared as they were replaced bypetrochemical technology, while ethanol
fermentation also significantly reduced inscale, only surviving in fields in which the
only demand is for fermentation products(vinegar feedstock, food preservatives, etc.).
Thus, by the 1970s, the industrial organic
chemicals and polymers that had predated
petrochemistry had all completely switchedover to petrochemistry. Meanwhile, the era ofhigh economic growth ended in the 1970s in
Japan and in the West, and the rapid growthin demand for polymers also came to an end.
The continuing emergence of innovative
petrochemical technologies in the 1950s and1960s also ended. Nevertheless, from the1970s onwards, the explosive increase inpolymer demand and the internationalizationof petrochemistry spread from the moredeveloped nations to the resource-rich nationsof the Middle East, and then to Asia, andCentral and South America, thus preventing
Systematic Survey on Petrochemical Technology

191

the worldwide petrochemical industry fromstagnating. New technological challenges
arose in responding to energy conservationand environmental pollution issues, as well as
meeting new demand from developed nations(sudden increased demand for propylene,
functional
chemistry).
Technologicaldevelopment continued beyond the 1970s in
response to these issues. Steady progress was
also made in front-running petrochemical
technologies, such as acetic acid throughmethanol carbonylation, metathesis reactions,metallocene catalysts and post-metallocene
catalysts. The advent of paraffin chemistry
also attracted some attention in contrast toconventional olefin-based petrochemical
technology.
Due to the emergence of pollution
problems from propylene tetramer synthetic
detergents with poor biodegradability in the
1970s, synthetic detergents started being
produced using higher alcohols from fats andoils. Oleochemistry revived and continued
alongside petrochemistry. In the 2000s, there
was a rapid increase in production of
biodiesel oil made from fats and oils andmethanol. Oleochemistry and petrochemistrycontinue to coexist in biodiesel oil production.
Meanwhile, the 2000s also saw a rapid
increase in fermentation ethanol fromagricultural produce in the United States. Thiswas put to use as a substitute for gasoline
additive MTBE, which was regulated due togroundwatercontamination
issues.
Production grew significantly in scope tomatch the production of ethylene in the
United States. Fermentation chemistry
revived to reclaim one small foothold overpetrochemistry in response to global
environmental
issues.
Thus,variousenvironmental issues have had varying
impacts on petrochemistry. However,
petrochemistry can be expected to overcome
these various environmental issues, chemicalsafety issues and energy conservation issues
in future.

192

From the 1980s onwards, there has been apush for functional chemistry in Japan andother developed nations. For more than three
decades, Japan has furthered its functional
chemistrytechnology
beyondtheconventional bounds of petrochemistry, evenextending it as far as polymer molding
technology. Petrochemistry continues to growand change beyond its conventionalframework.
Bibliography[1] T. Takahashi, “The history of thechemical industry,” Sangyo Tosho, 1973.
[2] K. Weissermel, H. J. Arpe, “Industrialorganic chemistry,” Tokyo Kagaku-dojin
Publishing Company, Inc., 5th edition,
2004.
[3] H. A. Wittcoff, B. G. Reuben, J. S.
Plotkin, “Industrial organic chemicals,”
Wiley, 3rd edition, New York, 2013.
[4] I. Ogata, “Petrochemistry,” Kodansha,
1980.
[5] “Ten-year history of the petrochemicalindustry,”Japan Petrochemical Industry
Association, ed., Japan Petrochemical
Industry Association, 1971.
[6] “Twenty-year
historyofthepetrochemicalindustry,”Japan
Petrochemical Industry Association, ed.,Japan
Petrochemical
Industry
Association, 1981.
[7] “Thirty-year history of the petrochemicalindustry,” Japan Petrochemical Industry
Association, ed., Japan Petrochemical
Industry Association, 1989.
[8] “Fifty years of petrochemistry—The
half-century
timeline,”Japan
Petrochemical Industry Association, ed.,Japan Petrochemical Industry Association,
2008.
[9] P. Spitz, “Petrochemicals: The rise of anindustry,” Wiley, 1988.
[10] E.P. Moore, Jr, “Polypropylene
Handbook,” Kogyo Chosakai, 1998.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Before 1900

1900s

BT, naphthalene by
distillation of coal tar

1910s

1920s

Acetylene by carbide
process

Syngas from coke

1930s

PL, BL by fixed-bed
catalytic cracking ofheavy oilEL, PL, BD, BTX bysteam cracking of
naphtha

PL, BL by thermal
cracking of heavy oil
EL by steam crackingof ethane

Early US petrochemistry
EL by dehydration of
ethanol
Ethylene oxide bycatalytic oxidation
process, EG by EO
hydrolysis process

EG by chlorohydrin
process

Fermentation chemistry

1950s

1960s

Industrialorganic
chemicalHydrogenated oil offats and oils byhydrogenation process

Glycerin

Higher fatty acid of
high-pressurehydrolysis process offats and oils

Oleochemistry

IPA, butanol, ethanol
by sulfuric acidprocess

Butadiene
Progressive stageUSpetrochemistry

Ethanol by catalytic
hydration process

MTP
Integrating
periodwith European
technology
Petrochemistry

Period of Sturm
und
Drang
Petrochemistry

IPA by catalytic
hydration process

Higher fatty alcoholbased surfactant

Revival of oleochemistry

Artificial petroleum by
FT process

Carbonylation processacetic acid of
methanol

Vinyl acetate byacetylene process

Acetaldehyde, vinyl
acetate by HoechstWacker process

Vinyl acetate byacetylene process

Vinyl chloride by EDC
process

Phenol bychlorobenzene
process

Phthalic anhydride bynaphthalene/fuming
sulfuric acid process

AN by acetylene
process

Phenol by Raschig
process

Phenol by cumene
process

Vinyl chloride byoxychlorination
process

AN by propane proces s

Phthalic anhydride byo-Xylene/catalyticoxidation process

Functional chemistry
integrated
withpolymer molding

Cellulose-based polymer technology

Phenolic resin

Biodiesel oil

Paraffin chemistry

AN by sohio process

Nitrocellulose lacquer
Rayon by viscose
process
Cellophane

Polymer

AN by ethylene
cyanohydrin process

Phthalic anhydrideby
naphthalene/catalyticoxidation process

Celluloid
Rayon by nitrification
cotton process

Petrochemical
technology
New trends

Petrochemistry inmature era

Higher alcohol byhigh-pressure
Higher alcohol sulfuric
acid ester salt
hydrogen reduction ofoils and fats

Coal chemistry
Phenol by coal tar
distillation process,phenol by sulfuric acidprocess

PL by metathesis
process

Enlarging of steam cracking facility

Revival of fermentation chemistry

Synthetic methanol
Acetaldehyde, acetic
acid by acetylene
process

After 1990s

Ethanol byfermentation process

Wood carbonization chemistry

Woodcarbonization
methanol, acetic acid,
acetone

1980s

Propanedehydrogenation
process

Ethanol byfermentation process
Acetone-butanol byfermentation process

Soap

1970s

Syngas from natural
gas

Coal chemistry

Basic product

1940s

AcetateUrea resin
Alkyd resin

PET
Nylon

Polyvinyl chloride
Polyvinyl acetate
Synthetic polymer technology from coal chemistry and fermentation chemistry

LDPE
Polystyrene
PMMA

SBR, NBR

HDPE

Unsaturated polyester
Polyurethane

Polypropylene
Polycarbonate
Acrylic fiber

List of product abbreviations Ac: acetylene, EL: ethylene, PL: propylene, BL: butylene, B: benzene, T: toluene, X: xylene, AN: acrylonitrile

Fig. 6.32 Technology system of petrochemistry.

Systematic Survey on Petrochemical Technology

193

PolyimidePara-aramid
PES

PEEK
Liquid crystal polymer

Butadiene-based
L-LDPE
Metallocene PE
rubber
Thermoplastic rubber
EPR
Synthetic polymer technology from petrochemistry(Post-metallocene PE)
COP

7 Conclusion
It has been 60 years since theestablishment of the petrochemical industry
in Japan. However, an “official history” of
the Japanese petrochemical industry is morethan a mere “Ten-year history” or“Twenty-year history” such as those given in
bibliographic references 5 and 6 of Chapter 6.
The “Thity-year history” in bibliographic
reference 7 is too brief; the “Fifty years” inbibliographic reference 8 is little more than achronology.
The main reason an “official history” islacking is probably because the industry has
trended from growth towards stagnation sincethe 1980s and has lost its appeal as anindustry. An even more significant reason
probably lies in the fact that petrochemistry
has changed with the times, and even those in
the industry cannot define exactly “what is
petrochemistry?” In 2013, the Japan
Petrochemical Industry Association invitedsubmissions for a new name instead of“petrochemistry.” This is the extent to which
we are unable to define “what is
petrochemistry?”
Accordingly, we were at a loss, firstly indefining petrochemistry, and then how tonarrow down the study area, taking into
account the constraints of the investigation
period. However, convinced that narrowing
down the topic into a single area of
petrochemistry (e.g. ethylene production
technology) would not give adequate insight
into the overarching picture of petrochemistry
as a whole, we commenced researching this
topic without narrowing down a specificstudy area. Rather than focusing solely on
Japan, we also decided to aim theinvestigation as globally as possible and thenposition Japan within that. As a result, wehave boldly gone beyond the normal boundsof petrochemistry in identifying trends inJapanese petrochemistry from the 1990s
onwards, even incorporating polymer
molding. This has been the path taken by
Japanese petrochemical companies; they havenot followed in the footsteps ofpetrochemistry overseas, but have branched194

out into functional chemistry while still
remaining focused on petrochemistry.
Noted chemical companies in the Westarecontinuing
towithdraw
frompetrochemistry.
Britishcompany
ICI
developed methyl methacrylate MMA and
LDPE in the 1930s, polyester fiber in the
1940s, and engineering plastics PEEK and
PES in the 1960s and 70s. Showing no signsof slowing in its technological prowess, it
was the first to develop biodegradable
plastics in the 1980s, and also developed
chlorofluorocarbon alternatives in the 1990s.
Despite these successes, ICI started
withdrawing from the petrochemical industry
in the 1990s and quickly lost its corporate
identity. It sold off its operations insuccession, and in 2008, the lauded company
name disappeared through a merger. German
company Hoechst AG, known for developing
the Hoechst-Wacker process, HDPE andvarious kinds of engineering plastics,
followed a similar path. The company ceased
to exist once it lost the mainstay of its
technological core, readily setting aside its
corebusiness
andadvocating
non-petrochemistry. Many other major
Western players in the industry have similarly
abandoned the petrochemical industry, manyof them attempting to expand into
pharmaceuticals and agribusiness, withgrowing demand in developed nations, using
biotechnology, rapidly developed since the1970s, as their new technological axis.
However, in many cases they have later felt
on looking back that they have lost theirformer vitality and development potential.
Meanwhile, the companies that have explored
new areas of technology while remaining
focused on petrochemistry have seen steadyprogress.
Japanese petrochemical companies havefrequently been criticized for not having thesame dynamic management as theircounterparts in the West. However, theiroperations, while not showy, are solid andsteady, and they have expanded intofunctional chemistry without losing their core

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

focus on petrochemistry.
This report has intentionally focused
within the realms of petrochemistry, on basic
petrochemicals, industrial organic chemicals
and polymers, and avoided delving too deeply
into functional chemistry. However, it isinteresting to note the number of new trends
in petrochemistry since the 1990s, even
within that scope. We have now reached theplateauing of petrochemical technology thatwe spoke about in the 1970s, and are on theverge of breaking through into a new stage. It
is worth noting that Japanese petrochemicalcompanies have played a major role in thesetrends.
Since Japanese petrochemistry has longlacked an “official history,” its history has notbeen recorded. Consequently, this survey
report makes no attempt to summarize thecollective opinions of the Japanesepetrochemical industry; it is simply an“unofficial history” (privately composed
history) written at will by the author as anindividual. Given the present situation where
there is not even a consensus on “what is
petrochemistry?” there will of course be
many counterarguments to the “unofficial
history” presented by the author. However,this serves as an opportunity to start people
thinking about the history of petrochemistry
again. History does not simply end withrecording the past; it provides guidelines forthe future. The hope is that this survey reportwill to some extent serve in such a role.
Finally, the author would like to express
heartfelt thanks to those who made thisresearch opportunity possible, to the many
people who cooperated in this study and to
those who shared their valuable insights.

Systematic Survey on Petrochemical Technology

195

Location Confirmation of Historical Technology Resource Items from the Petrochemical Industry(including mass-produced chemical product items predating petrochemistry)Name

1

Rayon researchmaterials from theFormer Yonezawa
Higher Technical
School (prototype,glass nozzle, wooden
implements)
Rayon thread, rayon
ribbon straw

On
Prof. Itsuzo Hata
display Memorial Room, Main
Building, Former
Yonezawa Higher
Technical School

Faculty ofEngineering,
Yamagata
University,
Yonezawa,
Yamagata

On
Prof. Itsuzo Hata
display Memorial Room, Main
Building, Former
Yonezawa Higher
Technical School

1924-1930

Imperial
Artificial Silk
Co., Ltd.

3

High-pressure
methanol synthesis
catalyst KMA

In
Clariant Catalysts
storage Toyama Plant

Faculty ofEngineering,
Yamagata
University,
Yonezawa,
Yamagata
Toyama,Toyama1989

Toyo CCI Co.,
Ltd.

4

Celluloid compression
testerIn
Daicel Corporation
storage Himeji Production Sector
Aboshi Plant

Himeji, Hyogo

1954

Dainippon
Celluloid Co.,
Ltd.

2

196

FormatLocation, etc.

Place

Date of
Manufacturer
manufacture
1913
Prof. Itsuzo
Hata

No.

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Reason for selection
Itsuzo Hata produced the first successful
rayon prototype in Japan. A rayon factory
was set up in Yonezawa using thistechnology, eventually leading topresent-day Teijin. These items werediscovered when the old researchbuilding was being demolished.
Rayon thread and rayon ribbon straw
manufactured during the period of stable
operation of the Imperial Artificial Silk
Yonezawa Plant (1916-1934). One of the
few instances of early mass-produced
products being kept.
Methanol synthesis research started at theTemporary Nitrogenous Fertilizer
Laboratory in 1925. A catalyst production
method was patented in 1927; Toyo
Gosei successfully industrialized
methanol synthesis in 1933 in
Shimonoseki, Yamaguchi. Later, thiscatalyst was also sold to other Japanesecompanies and was used in the same
form and composition up until 1989.
Celluloid compression is a process
whereby cellulose nitrate and camphor
are mixed and then finished into blocks.
While machines 1 and 2 wereGerman-built and purchased in 1919, thisis machine 3, the first
domestically-produced machine.

5

Fermentation ethanol
mash distillation
columnIn
Japan Alcoholstorage Corporation Izumi
Factory

Izui,
Kagoshima

1938

State-run Izumi
Alcohol Plant

6

Fermentation ethanol
distillation column
platesIn
Japan Alcoholstorage Corporation Iwata
Factory

Iwata,
Shizuoka

1939

State-run Iwata
Alcohol Plant

7

Fischer-Tropsch
artificial petroleum
synthesis catalyst andprototypeIn
Institute for Chemicalstorage Research, Kyoto
University

Uji, Kyoto

1927-1938

Institute for
ChemicalResearch, Kyoto
University

8

Fischer-Tropsch
artificial petroleum
product
industrialization
resource
Raw material feedpump from Japan’s
first ethylene plant

In
Takigawa Local Museum
storageTakigawa,
Hokkaido

1942-1945

Hokkaido
Artificial
Petroleum Co.,
Ltd.

In
Mitsui Chemicals
storage Iwakuni Otake Factory

Iwakuni,
Yamaguchi

1958

Ethylene plantgas-driven compressor
power pistonIn
Mitsui Chemicals
storage Iwakuni Otake Factory

Iwakuni,
Yamaguchi

1962

MitsuiPetrochemical
Industries Co.,Ltd.
MitsuiPetrochemical
Industries Co.,
Ltd.

9

10

Systematic Survey on Petrochemical Technology

197

A mash distillation column from thesecond state-run alcohol plant to start
operating in Japan. Despite being
damaged in an air raid in August 1945, it
was rebuilt and remained in use until
1997.
The Iwata Plant was the sixth of Japan’s
13 state-run alcohol plants to start
operating. These plates are part of a
distillation column plate and a rectifying
column or dehydrating column plate.
Prof. Genitsu Kita’s laboratory at Kyoto
University started research on artificial
petroleum synthesis from syngas in 1927,
the year after the F-T process was
discovered in Germany. Iron-based
catalysts as a substitute for the existing
cobalt-based catalysts were discovered in
1937. These items are a catalyst and a
prototype.
Artificial petroleum product produced at
one of the large-scale F-T process
artificial petroleum factories establishedthrough state policy.
A raw material feed pump from the first
naphtha steam-cracking ethylene plant tostart operating in Japan. It operated from1958 to 1971.
A gas-driven compressor power piston,arguably the central component, from thesecond ethylene plant at the Iwakuni
Plant. Adopted as a state-of-the-art pieceof technology at the time, it could handle
a wide range of loads and fuel gas
compositions.

11Japan’s first
low-pressure HDPE
polymerization reactor

In
Mitsui Chemicals
storage Iwakuni Otake Factory

Iwakuni,
Yamaguchi

1958

MitsuiPetrochemical
Industries Co.,
Ltd.

12

High-pressure LDPE
pilot test data

In
Institute for Chemicalstorage Research, Kyoto
University

Uji, Kyoto

1951-1954

Institute for
ChemicalResearch, Kyoto
University

13

Japan’s firsthigh-pressure LDPE
product

On
Sumitomo Chemical
display Company Ehime Factory
History Museum

Niihama,
Ehime

1958

Sumitomo
Chemical Co.,
Ltd.

198

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Even on global standards, this is a very
early polymerization machine for
producing low-pressure polyethylene,
invented by Prof. Ziegler of Germany in1955. This operated from 1958 to 1989.
Diagrams, photographs, experiment notes
and internal reports from pilot tests for
producing high-pressure polyethylene
carried out after the war, based on
small-scale wartime experiments.
Japan’s first full-scale industrial
production of high-pressure polyethylene,
using licenced technology from UK
company ICI.

A list of abbreviations for the product names used in this document
Abbreviation
2,4-D

Name

Details

2,4-Dichlorophenoxyacetic acid

Herbicide (agricultural chemical)

Acrylonitrile-butadiene-styrene resin

Semi-general-purpose plastic

ACH

Acetone cyanohydrin

Organic intermediateAE

Alkylethoxylate, alcohol ethoxylate

Nonionic surfactant

AES

Alkyl ether sulfate

Anionic surfactant

AOS

α-Olefin sulfonate

Anionic surfactant

AS

Alkyl sulfonates

Anionic surfactant

Acrylonitrile-styrene resin

Semi-general-purpose plastic

BHC

Benzene hexachloride

Insecticide (pesticide)

BPA

Bisphenol A

MonomerBR

Butadiene rubber

General-purpose synthetic rubber

CMC

Carboxymethyl cellulose

Dispersion stabilizer for food, binder,
emulsifier

COP

Cyclic olefin polymer

Excellent plastic for optic use

CPP
Film

Cast polypropylene film

Transparent packaging film

CR

Chloroprene rubber

Synthetic rubber outstanding inweather resistance

DBP

Dibutyl phthalate

Plasticizer

DDT

Didchlorodiphenyl-trichloroethane

Insecticide (pesticide, drug for publicheath)DMF

N,N-dimethylformamide

Polar solvent

DMSO

Dimethyl sulfoxide

Polar solvent

DMT

Dimethyl terephthalate

Monomer

DOP

Dioctyl phthalate

Plasticizer

EDC

Ethylene dichloride

Organic intermediate

EDTA

Ethylenediaminetetraacetic acid

Chelating agent

EG

Ethylene glycol

Monomer, antifreeze

EPDM

Ethylene propylene diene monomer
rubberSynthetic rubber

EPR

Ethylene-propylene rubber

Synthetic rubber

EVA

Ethylene-vinyl acetate copolymer

Plastic, adhesive

HDPE

High-density polyethylene

General-purpose plastic

HIPS

High impact polystyrene

General-purpose plastic

ABS resin

AS resin

Systematic Survey on Petrochemical Technology

199

Abbreviation
HNBR

200

Name

Details

Hydrogenated nitrile rubber

Special synthetic rubber

IIR

Isobutylene isoprene rubber (butyl
rubber)Special synthetic rubber

IPA

Isopropyl alcohol

Solvent

IR

Isoprene rubber

General-purpose synthetic rubber

LAS

Linear alkylbenzenesulfonate

Anionic surfactant

LDPE

Low-density polyethylene

General-purpose plastic

L-LDPE

Linear low-density polyethylene

General-purpose plastic

MAO

Methylalumoxane

Component of polymerization
catalysts

MDI

Methylene diphenyl diisocyanate

Monomer

MEK

Methyl ethyl ketone

Solvent

MMA

Methyl methacrylate

Monomer

MTBE

Methyl tertiary butyl ether

Gasoline additive

MVA

Monovinylacetylene

Organic intermediate

NBR

Nitrile rubber, acrylonitrile butadiene
rubberSpecial synthetic rubber

OPP
film

Oriented polypropylene film

Transparent packaging film

PBT

Polybutylene terephthalate

General-purpose engineering plastic

PCB

Polychlorinated biphenyl

Heat transfer medium, solvent,insulating oil

PCP

Pentachlorophenol

Herbicide, disinfectant

PEEK

Polyether ether ketone

Super engineering plastic

PES

Polyether sulfone

Super engineering plastic

PET

Polyethylene terephthalate

Plastic, synthetic fiber

PP

Polypropylene

General-purpose plastic

PPE

Modified polyphenylene ether

General-purpose engineering plastic

PPO

Polyphenylene oxide

General-purpose engineering plastic

PPS

Polyphenylene sulfide

Super engineering plastic

PTA

High-purity terephthalic acid

Monomer

PTFE

Polytetrafluoroethylene (Teflon)

Plastic

PTMG

Polytetramethylene ether glycol

Monomer

SAN

Styrene acrylonitrile (same as AS
resin)

General-purpose plastic

SBR

Styrene-butadiene rubber

General-purpose synthetic rubber

National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Abbreviation

Name

Details

SBS

Styrene-butadiene-styrene block
copolymer

Thermoplastic elastomer

SIS

Styrene-isoprene-styrene block
copolymer

Thermoplastic elastomer

TDI

Toluene diisocyanate

Monomer

THF

Tetrahydrofuran

Solvent, monomer

ULDPE

Ultralow-density polyethylene

Plastic

VLDPE
Very low-density polyethylene
Plastic
Note: The above names are not based on the IUPAC Nomenclature, but are usually used in thechemical industry.

Systematic Survey on Petrochemical Technology

201