Water Requirements of 

the Styrene, Butadiene 

and Synthetic-Rubber 

Industries

By CHARLES N. DURFOR

WATER REQUIREMENTS OF SELECTED INDUSTRIES

GEOLOGICAL SURVEY WATER-SUPPLY PAPER 1330-F

A study of manufacturing processes, 

with emphasis on present water uses and 

future requirements

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1963
UNITED STATES DEPARTMENT OF THE INTERIOR 

STEW ART L. UDALL, Secretary

GEOLOGICAL SURVEY 

Thomas B. Nolan, Director

For sale by the Superintendent of Documents, U.S. Government Printing Office 

Washington 25, D.C.
CONTENTS

	Page 

Abstract________________________________________________________ 221

Introduction ______________________________________________________ 222

Purpose and scope_____________________________________________ 222

Types of synthetic rubber._____________________________________ 223

History of synthetic rubber in the United States_________________ 223

Basis for reporting water-use data _______________________________ 225

Use of water in the manufacture of styrene___________________________ 226

How water is used_______________ _______________________________ 226

Dow process______________________________________________ 226

Formation of ethylbenzene____________________________ 226

Dehydrogenation of ethylbenzene to styrene ______________ 227

Purification of styrene______________________ __________ 227

Carbide and carbon process_________________________________ 230

Cosden process.--------------.---------------------------- 230

Findings of the survey_-_____-____-__________________--------_ 231

Sources_________________________________________________ 231

Chemical quality__-___-__--___________________-__-__--_--- 232

Treatment of makeup water._______________________________ 235

Quantity of water withdrawn and consumed__________________ 238

Treatment of waste waters_____________________________ __ 239

Use of water in the manufacture of butadiene._________-_____-----_--_ 239

How water is used_____________________________________________ 239

Butadiene from petroleum._____________-__________--_-----_ 239

Feed preparation_______________________________--_____ 240

Dehydrogenation_ _____________________________________ 240

Butadiene purification________________________________ 244

Butadiene from alcohol___________________________________ 245

Findings of the survey_________________________________________ 245

Sources __________________________________________________ 245

Chemical quality_________-_-__________-____---___--------- 246

Treatment of makeup water._________________-_-__--__-_--_ 248

Quantity of water withdrawn and consumed_________________"_ 248

Treatment of waste waters________________________________ 251

Use of water in the manufacture of styrene-butadiene rubber____________ 251

How water is used________________________________-___--_____-_ 251

Feed preparation __________________________________________ 252

Latex formation_________________________________________-_ 252

Recovery of butadiene and styrene __________________________ 253

Conversion of latex into dry rubber____________-___________-_ 257

Findings of the survey___-______-___-_____--_______-___--____-_ 259

Sources__ _ ______________________________________________ 259

Chemical quality_-___-____-_____________-__--___-_---_--_- 260

Treatment of makeup water________________________________ 261

Quantity of water withdrawn and consumed_____.____-_____-- 262

Treatment of waste waters____________________-_-_---_-_-- 265

Aggregate quantity of water required to produce styrene-butadiene

rubbers..______________________________________________ 265

in
IV CONTENTS

	Page

Use of water in the manufacture of special-purpose synthetic rubbers.___ 268

How water is used_-__-__-____--_-------------_--------------__ 268

Nitrile rubber_______________________________________ 268

Butyl rubber__________________________________________ 269

Neoprene _________________________________________________ 269

Thiokol.- -- --- --_ - ----- - --- -_ 271

Findings of the survey_________________________________________ 271

Sources___ _ _____________________________________________ 271

Chemical quality__________________________________________ 272

Treatment of makeup water______-____-__-__-__-___________ 273

Quantity of water withdrawn and consumed __________________ 274

Treatment of waste waters________________________________ 276

Future water requirements of the synthetic-rubber industry..___________ 276

Summary__________________________________________________ _______ 277

Selected bibliography ______________________________________________ 279

Index____________________________________________________________ 283

ILLUSTRATIONS

Page 

FIGURE 33. Flowsheet illustrating the use of water in the manufacture of

styrene _____________________________________________ 229

34. Types of makeup water used in the manufacture of styrene__ 235

35. Cooling tower to lower the temperature of warmed recirculating cooling waters.__-_--_______- _-_-_______-____-_ 236

36. Flowsheet illustrating the use of water in the manufacture of

butadiene _ _________________________________________ 243

37. Flowsheet illustrating the use of water in the manufacture of

styrene-butadiene rubber._____________________________ 255

38. Water use in the recovery of styrene from latex_______._-.__ 256

39. Dewatering of SBR crumb by means of a rotary filter______ 258

40. Near-minimum amounts of makeup water used to produce

styrene-butadiene rubber. ____________________________ 266

41. Flowsheet illustrating the use of water in the manufacture

of neoprene and butyl rubbers...-_____________________ 270
CONTENTS V

TABLES

Page 

TABLE 1. Sources of makeup water used in the manufacture of styrene__ 231

2. Chemical properties of untreated makeup water used in the

manufacture of styrene______________________________ 233

3. Treatment of makeup water at styrene plants____________ 237

4. Quantity of makeup water used in the manufacture of

styrene.____________________________________________ 238

5. Sources of makeup water used in the manufacture of butadiene _______________________________________________ 246

6. Chemical properties of untreated makeup water used in the

manufacture of butadiene.----__---_---_---_--_-______ 247

7. Treatment of makeup water at butadiene plants ___________ 249

8. Published quantities of makeup water required in the manufacture of butadiene __________________________________ 250

9. Quantity of makeup water used in the manufacture of butadiene. ______________________________________________ 250

10. Sources of makeup water for styrene-butadiene rubber._____ 259

11. Chemical properties of untreated makeup water used in the

manufacture of styrene-butadiene rubbers.______________ 260

12. Treatment of makeup water at styrene-butadiene-rubber

plants.-__-------__---__---__--_-----__--------_---. 262

13. Quantity of makeup water used in the manufacture of styrenebutadiene rubber___________________________________ 263

14. Published quantities of makeup water required to produce

styrene-butadiene rubber____________________________ 265

15. Minimum and maximum quantities of makeup water required

to produce styrene-butadiene rubbers._________--___--__ 267

16. Sources of makeup water used in the manufacture of specialpurpose synthetic rubbers_________-_-_-____---________ 272

17. Chemical properties of untreated makeup water used in the

manufacture of special-purpose synthetic rubbers___-_---_ 273

18. Treatment of makeup water at specialty-rubber plants______ 274

19. Quantity of makeup water used in the manufacture of specialpurpose synthetic rubbers___--_-__-____-_______------- 275

20. Summary of water sources used in the manufacture of styrene,

butadiene, SBR, and special-purpose synthetic rubbers__ 278

21. Summary of makeup water requirements of industries manufacturing styrene, butadiene, SBR and special-purpose 

synthetic rubbers___________________________________ 278

WATER REQUIREMENTS OF SELECTED INDUSTRIES

WATER REQUIREMENTS OF THE STYRENE, BUTADIENE, 

AND SYNTHETIC-RUBBER INDUSTRIES

By CHARLES N". DURFOR

ABSTRACT

About 710 million gallons of makeup water is withdrawn daily by the styrene, 

butadiene, styrene-butadiene rubber (SBR), and specialty-rubber industries; 88 

percent of this water is used only for once-through cooling. About 429 million 

gallons of water daily (mgd) is withdrawn by the butadiene industry; 158 ragd 

is withdrawn by the styrene industry; 94 mgd is used to make special-purpose 

synthetic rubber; and 29 mgd is used in the direct manufacture of SBR.

The amount of makeup water withdrawn to produce SBR ranges from 11,400 

to 418,000 gallons per long ton of finished rubber. The amount of makeup water 

withdrawn depends upon the type of rubber, the processes used to make SBR 

and its intermediates (styrene and butadiene), and the availability of water at 

the styrene, butadiene, and SBR plants. The amount of makeup water used to 

make styrene ranged from 2.19 to 123 gallons per pound; to make butadiene, 

ranged from 5.38 to 22.0 gallons per pound; and in the direct manufacture of 

SBR, ranged from 0.883 to 10.2 gallons per pound of finished rubber. The 

amount of makeup water withdrawn for use in the manufacture of specialpurpose synthetic rubber ranged from 8.45 to 104 gallons per pound.

About 64 percent of the makeup water was obtained from salty water sources. 

These waters, which were used only in once-through cooling, contained as much 

as 35,000 ppm of dissolved solids. About 26 percent of the makeup water was 

obtained from fresh-water streams and lakes, and most of the other makeup 

waters were obtained from ground water. Less than 1 percent of the makeup 

water was obtained from reprocessed municipal sewage. Most makeup water 

from fresh-water streams, lakes, and wells contained less than 1,000 ppm of 

dissolved solids, and most makeup water used in the manufacture of SBR contained less than 500 ppm of dissolved solids. The maximum hardness of the 

untreated fresh makeup waters; used in the manufacture of SBR was less than 

500 ppm.

About 97 percent of the makeup water withdrawn was discharged to surface 

waters; the warmed salty waters were returned to their source. The remaining 3 percent, or about 23.6 mgd, of makeup water was used consumptively. 

The styrene industry consumptively used about 2.0 percent of its intake; the 

butadiene industry, about 4.5 percent; the specialty-rubber industry, about 

9.1 percent; and the SBR industry, about 11 percent. The water shipped in the 

synthetic-rubber products increased the consumptive use of water by these 

industries.

221
222 WATER REQUIREMENTS OF SELECTED INDUSTRIES

INTRODUCTION 

PURPOSE AND SCOPE

This report describes the uses of water and the ranges of makeup 

water required in the production of styrene, butadiene, and synthetic 

rubbers in the United States. It is one of a series describing the water 

requirements of selected industries that are of national importance 

and has been prepared at the request of and in consultation with the 

Water and Sewerage Industry and Utilities Division, Business and 

Defense Services Administration, Department of Commerce. It is 

designed to serve the dual purpose of providing basic information 

for national defense planning and, at the same time, of providing 

assistance to business and industry.

This investigation consisted of a field survey and a literature survey of the uses of water in the manufacture of styrene, butadiene, 

styrene-butadiene rubber, and other synthetic rubbers. The field survey was made during the summer of 1959. Information was obtained 

on the sources, quantity, chemical character, temperature, and required treatment of makeup waters l supplied to plants making these 

products. The adequacy of water supply for present capacity production and for future expansion was determined.

Special acknowledgment is given to the officials and management of 

companies manufacturing styrene, butadiene, and synthetic rubber 

who permitted the author to visit their plants and who supplied information on the use of water in their plants. Photographs were 

furnished by the Texas-U.S. Chemical Co. and Firestone Synthetic 

Rubber and Chemical Co.

The amounts of water and the quality of the water withdrawn for 

cooling, process, boiler-feed, sanitary, and other uses in the manufacture of these products were determined. The consumptive use 2 and 

the amount of water discharged to waste after being used for cooling, 

process, boiler feed, sanitary, and other services were balanced against 

the water intake. Information was also obtained on the treatment and 

disposition of waste water from each plant.

The uses of the makeup water were classified according to the definitions of O. D. Mussey (1961).

Process water is water that comes in contact with an end product or with materials incorporated in an end product. Cooling water is water that is used only 

for cooling. Water used to cool a product by being brought into contact with 

it is classified as process water, not as cooling water. Boiler-feed water is that 

introduced into boilers for conversion into steam. Sanitary and service water

1 Makeup water is water added to a system to make up for the water consumed or discharged to waste.

2 The quantity of water discharged to the atmosphere or incorporated in the products of 

the process in connection with ... an industrial process (MacKichan, 19S7,, p. 2).
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 223

is that used for drinking, showers, general cleaning, flushing wastes, and company 

cafeterias and housings.

Water for steam brought into contact with a product is classified as 

boiler-feed water and not as process water.

TYPES OF SYNTHETIC RUBBER

Only one synthetic rubber has been developed as a general-purpose 

replacement for natural rubber. This rubber is composed principally 

of about one part of styrene and about three parts of butadiene and is 

known as styrene-butadiene rubber, or SBR; it was formerly known 

as Buna-S -and GRS. About 80 to 90 percent of the synthetic rubber 

produced in the United States is SBR.

No synthetic rubber has the chemical composition or all the properties of natural rubber. However, some special-purpose synthetic 

rubbers have been developed which have particular properties that 

are superior to natural rubber for specific purposes. The four principal special-purpose synthetic rubbers are nitrile, neoprene, butyl, and 

thiokol.

Thiokol is used where high resistance to oils and chemicals, which 

attack natural rubber, are desired and where its unpleasant odor is 

not objectionable. It retains rubbery characteristics to 60°F. Neoprenes have high resistance to mineral oils, heat, oxidation, ozone, 

sunlight, and burning. Mtrile rubber competes with neoprene where 

resistance to oil and gasoline is desired. Almost all nitrile rubber 

produced during World War II was used in self-sealing fuel tanks, 

gaskets, cable covers, and similar equipment for military aircraft. 

Butyl rubber is markedly superior to natural rubber in air retention 

and is used for inner tubes (Whitby, 1954).

HISTORY OF SYNTHETIC RUBBER IN UNITED STATES

The water requirements of the synthetic rubber industry have 

changed since the first batch of SBR was made just prior to World 

War II. A brief examination of the history of the industry will help 

in understanding the variations in water requirements in the manufacture of synthetic rubbers.

The unavailability of natural rubber in 1942 and the demands of 

an expanding Army and Navy made rubber a critical defense material. 

Of the million long tons of rubber consumed in 1941, only 6,260 long 

tons were synthetic rubber. Plants had to be built to manufacture 

SBR, which was selected as the general-purpose rubber substitute for 

natural rubber. Styrene had been made commercially, and additional 

plants were built using, mainly, a process developed by the Dow Chem658641 O 62 2
224 WATER REQUIREMENTS OF SELECTED INDUSTRIES

ical Co. The Carbide and Carbon Company at Institute, W. Va., 

built a plant to produce styrene by another process.

New techniques were developed to produce butadiene, another essential product for the production of SBE. Plants using the process 

of making butadiene by dehydrogenation of grain alcohol were built 

quickly and supplied about 64 percent of the butadiene made in 1944. 

After the war, these plants could not compete unsubsidized with plants 

manufacturing butadiene from petroleum and were shut down. No 

plants were producing butadiene from alcohol at the time of this 

survey. However, "in case of another general war, the production 

of SBE might again need to depend heavily upon butadiene-fromalcohol plants" (U.S. National Production Authority, 1952).

In the latter part of World War II, plants were built to produce 

butadiene by the dehydrogenation of butylene and butane, which are 

obtained from petroleum. These plants are still in operation.

Most SBE, plants originally were built of a standard design and 

used a standard formula to combine styrene and butadiene into SBE. 

Since 1944, the individual operating companies have modified the 

SBE formula and operating techniques to incorporate some of the 

following improvements:

In 1944, carbon-black slurry was introduced into SBE latex prior 

to coagulation. This procedure was initiated because of the lack of 

facilities at the rubber finishing plants to incorporate carbon black 

into the SBE crumb and to overcome the lack of tackiness of SBE 

crumb. The introduction of carbon-black slurries into the latex increased (a) the amount of process water used to prepare the slurry 

and to wash the increased volume of rubber crumb and (b) the amount 

of steam needed to dry the increased volume of rubber crumb.

In the same year, 1944, operating techniques were devised to manufacture SBE by a continuous process that levels off the peak demands 

for steam, process, and cooling water.

In 1947, "cold rubber" was manufactured at 41 °F; initially all 

SBE had been manufactured at a reaction temperature of 121 °F (hot 

rubber). This cold rubber was superior to hot rubber in resistance 

and wear and became the principal rubber for passenger tires. SBE, 

manufactured at 41° F requires vastly more cooling water than rubber 

made at 121 °F.

In 1951, "oil-extended" SBE was made by mixing an extender oil 

with the latex prior to coagulation. This oil-extended rubber had 

improved tread wear and resistance. It required less reactor charge 

water but required more washing water and steam to dry the apparent 

increase in volume of rubber crumb.
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 225 

BASIS FOR REPORTING WATER-USE DATA

In this report the uses of water in the styrene, butadiene, SBR, 

and specialty-rubber industries are considered separately. The wateruse data for the manufacture of styrene and butadiene represent the 

total water use by these industries. The amounts of water required 

by these intermediate materials for use in the manufacture of SBR 

are discussed under "Aggregate quantity of water required to produce 

styrene-butadiene rubber (SBR)." The amounts of makeup water 

used in these industries were reported as being typical for capacity 

production. Production in excess of design capacity decreases the 

makeup water requirements, and production below design capacity 

increases the makeup water requirements. Makeup water requirements in gallons per unit of product may be higher in summer and 

lower in winter than the data reported.

Although styrene is made by several different processes, the water 

requirements have been summarized for the entire industry; data 

are not given for the various processes. Water use is reported in 

gallons of water per pound of styrene.

Butadiene is manufactured from petroleum by two principal 

processes and from two principal feed stocks. Small amounts of 

butadiene are produced as a byproduct from other industrial operations. Water requirements have been summarized for the entire 

industry and are not given for the various operating techniques. 

Water use is reported in gallons of water per pound of butadiene.

Styrene-butadiene rubber is manufactured as SBR latex, SBR 

crumb, oil-extended SBR, carbon-black crumb, and oil-extended 

carbon-black crumb. It is manufactured at 41°F and 121°F by batch 

and continuous processes. Some plants use several operating processes 

and produce a variety of products. Water-use data were not available for each type of rubber produced. Thus, the water required for 

the direct manufacture of SBR is reported in gallons of water per 

pound of finished rubber crumb. For latex plants, the water use is 

reported on the basis of gallons of water per pound of rubber solid.

The water required to produce 1 pound of SBR is approximately 

the sum of the water required to produce one-fourth pound of styrene 

plus three-fourths pound of butadiene, plus the water required in the 

direct manufacure of 1 pound of SBR. The amount of water required 

to produce 1 pound of extended rubber depends upon the amount of 

styrene, butadiene, extender oil, and carbon black in the finished 

product.

During this water-use survey 2 butyl, 2 neoprene, 2 thiokol, and 3 

nitrile rubber plants and 1 specialty-rubber plant were visited.
226 WATER REQUIREMENTS OF SELECTED INDUSTRIES

USE OF WATER IN THE MANUFACTURE OF STYRENE

Most producers of styrene use a method developed by the Dow 

Chemical Co., but some styrene is made by a process developed by the 

Carbide and Carbon Chemicals Corp., and some by a process developed by the Cosden Petroleum Co.

HOW WATER IS USED 

DOW PROCESS

Most of the styrene manufactured in the United States in 1959 was 

made by the Dow Chemical Co. process. In this process ethylene, an 

unsaturated gas commonly obtained from petroleum, reacts with 

benzene to form ethylbenzene. Purified ethylbenzene, diluted with 

superheated steam, is catalytically dehydrogenated to form styrene. 

Figure 33 is a flowsheet of the manufacture of styrene, showing these 

steps. The use of water in these operations is shown in shading; the 

use of steam is shown in dotted lines.

About 98 percent of the makeup water is used to cool gases and 

liquids and to condense vapors from distillation columns and reactors. 

Less than 1 percent of the makeup water is used for washing ethylbenzene and for quenching gases from the ethylbenzene dehydrogenation reactor. Less than 3 percent of the water is used for makeup to the steam boilers. Superheated steam is used for heating and 

for diluting the ethylbenzene feed to the dehydrogenation reactor.

The uses of water can best be understood by dividing the process into three parts: (a) formation of ethylbenzene, (b) dehydrogenation of ethylbenzene to styrene, and (c) purification of styrene.

FORMATION OF ETHYLBENZENE

High-purity benzene, recycle benzene, and catalyst "mud" are 

pumped continuously to a large brick-lined cylindrical reactor containing liquid about 30 feet deep. Ethylene gas is pumped into the 

bottom of the reactor and reacts with benzene to form ethylbenzene. 

Heat is evolved and the reaction is maintained at about 200°F by the 

evaporation of benzene and the refluxing of the condensate. The 

benzene is condensed and cooled in heat exchangers in which water 

is circulated.

The crude alkylate overflows from the reactor, is cooled by water in 

a heat exchanger, and is pumped to a settling tank where the entrained 

catalyst mud precipitates. The oil layer is decanted and washed with 

water and caustic solution. After it has settled, the water layer is 

decanted and discharged to waste. The neutralized crude ethylbenzene is distilled to a purity of more than 99 percent in a series of 

fractionating towers. The unreacted benzene is recovered by distil-
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 227

lation, condensed and cooled in water-cooled heat exchangers, and 

mixed with fresh benzene.

In the fractionating system, a part of the benzene vapors from 

the benzene column and a part of the vapors from the ethylbenzene 

column are condensed and cooled in water-cooled heat exchangers and 

returned to the column. This cooled condensate regulates the operating temperature of the top of the column. A part of the higher 

boiling materials discharged from the bottom of each distillation 

column (called "bottoms") is reheated in steam reboilers and returned 

to the column. This reheated bottom material is the source of heat 

for the distillation operation.

The purified ethylbenzene is cooled by water and sent to be 

dehydrogenated to styrene.

DEHYDROGENATION OF ETHYLBENZENE TO STYRENE

Purified ethylbenzene is mixed with and heated by superheated steam 

to 1,170°F and injected into a dehydrogenation reactor. As the 

vaporized ethylbenzene flows up through the catalyst bed and out of 

the reactor, a part of it is dehydrogenated to styrene. The hot reactor 

gases are cooled by heat exchange with the incoming ethylbenzene and 

steam, and are quenched in a desuperheater by a water spray. After 

the oil-water mixture has condensed and settled, part of the water 

layer is recycled to the water spray, and the rest of the water layer is 

discharged to waste (Mitchell, 1946); or the water layer is stripped of 

organic materials by steam distillation, and the recovered water is sent 

to the steam plant (Smith, 1947, and Martin and Rostenbach, 1953). 

The oil layer, containing about 40 percent styrene and 59 percent 

ethylbenzene, is sent to storage prior to distillation of the styrene.

PURIFICATION OF STYRENE

Crude styrene is purified by a series of distillations that separate 

styrene from benzene, toluene, and ethylbenzene. The benzene and 

toluene phase is vacuum distilled from the crude styrene and then 

further fractionated to yield benzene and toluene. The ethylbenzene-styrene phase is fractionated in a two-stage ethylbenzene distillation column. Ethylbenzene is distilled from the first stage, 

condensed in water-cooled heat exchangers, and recycled to the dehydrogenation reactor. The bottoms from the second stage, containing 98 percent styrene, is further distilled to 99.5 percent of purity.

The purified styrene is stabilized to inhibit polymerization, which 

is the linking together of a large number of molecules to form a 

polymer. The polymer formed has a molecular weight much higher 

than and properties different from the constituent links of styrene 

molecules (calledmonomers).
228 WATER REQUIREMENTS OP SELECTED INDUSTRIES 6TYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 229

O

1sI

 4-J I

a

o>a
230 WATER REQUIREMENTS OF SELECTED INDUSTRIES

Each distillation tower used in the fractionation and purification 

of crude styrene is equipped with water-cooled heat exchangers to 

condense the vapors from the tower and to regulate the temperature 

of the refluxed condensate. These distillations are operated at low 

temperatures maintained by cooling water and at subatmospheric 

pressures maintained by steam jet ejectors. A portion of the bottom 

material from each column is reheated by steam to supply the heat 

needed for the distillation operation.

CARBIDE AND CARBON PROCESS

As in the Dow process, ethylbenzene is formed from ethylene and 

benzene. The liquid ethylbenzene is oxidized catalytically by air to 

acetophenone. The temperature of this exothermic reaction is controlled at about 260°F by water circulating in cooling coils around 

the reactor. Steam in the reactor gases is condensed in water-cooled 

heat exchangers and is used to prepare caustic solutions.

The reactor liquor, which is principally acetophenone, phenylethyl 

alcohol, and unreacted ethylbenzene, is cooled to about 81°F in heat 

exchangers circulating water, mixed with a 10 percent caustic solution, and sent to a settling tank. The aqueous (bottom) layer in the 

tank is withdrawn, stripped of organic material by steam distillation, 

and sent to waste. The organic layer from the settling tank is washed 

by a spray of water in a scrubbing tower. The resultant water phase 

is sent to waste.

The organic layer containing ethylbenzene, acetophenone, and 

phenylethyl alcohol is stripped of ethylbenzene by distillation. The 

resultant acetophenone-phenylethyl alcohol fraction is further refined 

in another distillation tower. The distillate is catalytically hydrogenated to phenylethyl alcohol, which is then dehydrated catalytically 

to styrene. The crude styrene is distilled to a purity of more than 

99 percent styrene.

The vapors from each distillation column are condensed and cooled 

in water-cooled heat exchangers. The refluxing of these condensates 

controls the temperature of the top of the distillation column. The 

heat to each column is supplied by a portion of the bottoms, which is 

returned to the column after being heated in steam reboilers.

COSDEN PROCESS

In this process, ethylbenzene is obtained by the "ultrafractionation" of a mixed xylene stream containing about 30 percent ethylbenzene obtained from certain petroleum fractions (Chemical and 

Engineering News, 1960b). The recovered ethylbenzene is diluted 

with steam and dehydrogenated catalytically to styrene. Data on 

water requirements for the recovery of ethylbenzene from the xylene
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 231

steam and for the dehydrogenation of ethylbenzene to styrene were 

not available. However, the major use of water is in the dehydrogenation of ethylbenzene to styrene.

FINDINGS OF THE SURVEY 

SOURCES

At capacity production, about 158 million gallons of water is withdrawn daily from wells, lakes, streams, and ocean bays, and purchased 

from private water companies and from municipal water and sewage 

supplies for use in the manufacture of styrene. About 155 million 

gallons is obtained from surface-water sources and about 3 million 

gallons is withdrawn from ground-water sources. A small fraction 

of the total makeup water is obtained from municipal sewage. The 

sources of makeup water used in the styrene industry are summarized 

in table 1.

TABLE 1. Sources of makeup water used in the manufacture of styrene

Source

Well water: 

Self -supplied _____ _ ______ ___

Surface water:

Water company _ ___

Number of plants being served by indicated 

source

Oncethrough 

cooling 

water

2

2

1

Recirculated 

cooling 

water

1 

1

3

1

Process 

water

1 

1

1

Boilerfeed 

water

1 

1

4

2

Sanitary and 

service 

water

1

2

2 

1

About two-thirds of the styrene plants use more than one source 

of water supply. At only two plants is surface water used as the 

sole source of supply; the other plants supplement the surface-water 

supply with well water, sewage, or bay water. At only one plant is 

ground water used as the only source of supply; the other plants 

supplement the ground water with surface water or municipal sewage. At some plants, the secondary source of supply was maintained 

only as a standby source for emergencies. At plants using sewage and 

bay water, it was necessary to use another source of water for sanitary use. The plants located in the northeastern part of the United 

States and along the Gulf Coastal Plain use predominately surface 

water. The styrene plants at Big Spring, Tex., and at Odessa, Tex.,

658641 O 62 3
232 WATER REQUIREMENTS OF SELECTED INDUSTRIES

use treated municipal sewage for a substantial part of the water supply (Connell and Berg, 1958). Galveston Bay is a source of cooling 

water at Texas City, Tex. (Hebbard, Powell, and Rostenback, 1947). 

The amounts of water available at the individual establishments 

are adequate for capacity production. Many styrene plants are near 

or are a part of a large petroleum refinery or a chemical complex. 

These styrene plants commonly use the electricity, power, water, and 

sewer facilities of the larger operation. The water used by some of 

these styrene plants is only a small part of the total water used in 

the larger operation.

CHEMICAL, QUALITY

The chemical quality of the makeup water from streams and wells 

is determined to a large extent by the environs of the watershed and 

the aquifer. Well waters are usually higher in pH, hardness, alkalinity, and dissolved solids than most rivers and lakes. Waters from 

estuaries, bays, and the ocean contain very high concentrations of 

chloride, sulfate, and other dissolved solids. The chemical quality 

of municipal sewage depends to a large extent upon the constituents 

in the water prior to treatment at the municipal sewage treatment 

plant.

The chemical quality of the untreated ground water, surface water, 

and sewage used for makeup to cooling towers and steam boilers has 

been summarized in table 2. This table presents the minimum, maximum, median, lower, and upper quartile values of the more important 

constituents in the untreated makeup waters used at styrene plants. 

These data do not represent any specific analysis; for example, the 

water with the minimum hardness is not the water with the minimum 

sodium and potassium content.

The chemical composition and the amount of dissolved solids in 

the makeup water influence the rate of corrosion, the rate of scale 

formation, and the chemical treatment required. Most natural waters 

have calcium and magnesium as the principal cations and minor 

amounts of sodium and potassium. Where natural softening occurs, 

the principal cation will be sodium, with minor amounts of calcium, 

magnesium, and potassium also present. The principal anions present 

in most natural waters are generally carbonate and bicarbonate. Minor amounts of sulfate, chloride, fluoride, and nitrate are commonly 

present.

Waters containing large amounts of calcium and magnesium ions 

form insoluble curds with soap and are classified as hard waters: the 

more calcium and magnesium, the harder the water. Waters containing large quantities of calcium, magnesium, bicarbonate, car-
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 233

TABLE 2. Chemical properties of untreated makeup water used in the manufacture

of styrene

[Chemical analyses were furnished by plants manufacturing styrene and by the U.S. Geological Survey]

Constituent or 

property

Silica (SiOn)-. 

Sodium (Na) and poBicarbonate (HCOs) 

Carbonate (COs)---.--

Sulfate(S04)----~. 

Chloride (01). ......

Dissolved solids: 

Residue on evaporation at 180° C. 

Hardness as CaCOs . 

Noncarbonate hardpH.. ...... .........

Cooling

o>ft

"S 

1

*

7 

8 

7

6 

9 

11

9 

9

7 

9

9 

9

Parts per million

£

| 'c

S

5.7 

1.1 

2.2

9.2 

22 

0 

8.6 

4.8

107 

2

0 

6.9

Lower quartile

6.0 

19 

2.8

21 

84 

0 

17 

17

242 

60

0 

7.0

Median

13 

32 

8.0

58 

151 

0 

42 

33

356

117

28 

7.5

quartile Upper 

25 

66 

26

121 

201 

2 

101 

238

726 

288

123

8.2

Maximum

31 

118 

28

218 

251 

27 

270 

351

1,120 

404

320 

9.1

Boiler feed

I

S 

1

I 

fc

8 

8

7

7 

9 

9 

8 

9

8 

9

9 

9

Parts per million

Minimum

0.5 

1.1 

2.2

9.2 

22 

0 

8.6 

4.8

107 

2

0 

5.6

Lower quartile

5.8 

19 

2.8

21 

84 

0 

17 

17

188 

60

0 

7.0

Median

6.8 

32 

8.0

55 

124 

0 

36 

27

320 

114

28 

7.4

Upper quartile

24 

36 

9.0

121 

192 

1 

92 

204

645 

183

88 

8.2

I 

w

31

118 

26

218 

251 

27 

270 

351

1,120 

404

320 

9.1

bonate, and sulfate ions have a tendency to form coatings on metal 

pipes. At temperatures below boiling, waters containing large 

amounts of calcium and carbonate ions deposit coatings of scale. At 

temperatures above boiling, waters containing large amounts of calcium and bicarbonate ions deposit coatings of calcium carbonate scale, 

and waters containing large amounts of calcium and sulfate ions deposit an extremely hard scale that is difficult to remove. Scale acts as 

an insulator that lowers the rate of heat transfer and reduces the 

effective pipe diameter; this reduction decreases the pumping efficiency. 

Water used for makeup to steam boilers should be low in hardness and 

should contain no calcium sulfate. The "Progress report of the committee on quality tolerances of water for industrial uses" recommended that boiler-feed water for boilers operated at pressures below 

150 psi (pounds per square inch) have a hardness less than 80 ppm 

(as CaCO3 ), and for boilers operated at pressures in excess of 400 

psi have a hardness less than 2 ppm (Moore, 1940).

Waters that contain low concentrations of calcium and magnesium 

and whose predominant anions are sulfate and chloride can cause 

metallic corrosion. The greater the concentration of sulfate and 

chloride and the higher the temperatures, the greater the corrosion. 

The presence of large amounts of dissolved gases, particularly dissolved oxygen, also accelerates corrosion.
234 WATER REQUIREMENTS OF SELECTED INDUSTRIES

Large amounts of sodium and potassium salts in boiler-feed water, 

in the presence of suspended matter, are believed to cause foaming, 

which accelerates scale formation and corrosion in the boilers (Powell, 

1954). Salts of sodium and potassium carbonate in recirculating 

cooling water can cause the delignification of wood in cooling towers. 

When the deterioration of the wood is extreme, the remaining cellulose cannot hold nails or support other fastenings (Blohm and 

Frazier, 1950).

Most natural waters contain silica in excess amounts; it can cause 

problems in steam generation. At elevated temperatures and pressures, especially in the presence of calcium, silica forms a low thermal-conductivity, hard, glassy scale that causes structural failures. 

Silica also is deposited on turbine blades as a scale that is difficult 

to remove and that causes operating difficulties (Nordell, 1951).

Phosphate is usually not present in natural waters but, as a result 

of the use of household detergents, is commonly present in municipal 

sewage. Although phosphate is added to cooling-tower and boilerfeed waters to control scale and corrosion, excessive amounts of it 

can form an undesirable scale in cooling towers and steam boilers 

(Sullivan, 1958).

The presence of iron is undesirable and, fortunately, is seldom 

found in most surface waters; but concentrations of iron in excess of 

1 ppm are common in ground water and acid surface water (Rainwater and Thatcher, 1960). Excessive amounts of iron cause staining 

of porcelain fixtures and increase the hardness, turbidity, and color 

of natural waters.

Many types of water were supplied to plants making styrene; figure 

34 illustrates two types. The percentages of the reacting weights of 

the more important constituents are plotted as fractions of the circle. 

The radius of these composition diagrams was drawn in proportion 

to the dissolved-solids content. The diagram on the right represents 

a water containing sodium and potassium and chloride as the principal 

constituents. Smaller amounts of calcium, magnesium, bicarbonate, 

chloride, and nitrate also were present. This type of water was 

obtained from some coastal streams, ground waters, and municipal 

sewage in Texas. These sodium chloride waters had a dissolved-solids 

content that ranged from 100 to 1,120 ppm. The diagram on the left 

represents a water containing calcium and bicarbonate as the principal 

constituents. Minor amounts of magnesium, sodium and potassium, 

sulf ate, chloride, and nitrate also were present. This type of water 

contained much less dissolved solids and represented the less mineralized type of makeup water used in the styrene industry.
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 235

EXPLANATION 

Cononi Aniom

Calcium Bicarbonate

Magnesium Sulfot.

Sodium aand Chlorid* ond 

pofauiuin nitrate

Cirde rodiut of 1 inch = 400 ppm 

of dissolved solids

HCO,

Calcium bicarbonate

type of water Sodium chloride typ* «f water

FIGUKE 34. Types of makeup water used in the manufacture of styrene.

Other types of water used contained sodium and bicarbonate, 

sodium and sulf ate, calcium and sulf ate, and calcium and chloride, 

respectively, as their principal constituents. In summary, many chemical types of water were used. All waters contained less than 1,150 

ppm of dissolved solids, with the exception of salty water that was 

used only for once-through cooling.

TREATMENT OF MAKEUP WATER

The type and degree of treatment given to makeup water are governed by the chemical composition of the water and its use in the plant. 

The types of treatment given makeup water in the styrene industry are 

summarized in table 3.

The minimum requirements for cooling water are that the water 

should be free of sediment, debris, and algae that could clog pipes. 

As indicated in table 3, waters used for once-through cooling are given 

a minimum of treatment generally clarification and chlorination. 

Chlorine and chlorine compounds reduce growths of slime and algae 

that reduce the effective pipe diameter and the rate of heat transfer.

Water used as makeup to cooling towers, such as the one shown in 

figure 35, requires additional treatment. In these cooling towers 

the warmed water is cooled by heat exchange with air and by evaporation of the water spray. In the process of being cooled, the water
236 WATER REQUIREMENTS OF SELECTED INDUSTRIES

to induce air 

through cooling^ 

tower

FIGURE 35. Cooling tower to lower the temperature of warmed recirculating cooling water.

becomes saturated with oxygen from the air, and this accelerates 

metallic corrosion. The dissolved oxygen is removed usually by 

deaeration or by such chemical inhibitors as chromates and phosphates. 

About 0.2 percent of the water circulating through the tower is lost 

as spray to the wind, and about 1 percent of the water is evaporated 

and lost for each 10°F drop in water temperature (DeFlon, 1950, p. 

790). The evaporation of the wT ater increases the dissolved-solids 

content and causes the recirculated water to have higher dissolved 

solids than the makeup water. Water that does not form scale when 

used only once may become scale forming after it has been concentrated several times in cooling-tower use. To reduce the formation of 

scale, a fraction of the recirculated water is discharged to waste as 

blowdown. The treatment of makeup waters with sulfuric acid, 

which converts calcium carbonate into the more soluble calcium sulfate, and the softening of the makeup water also reduces scale formation.
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 237

TABLE 3. Treatment of makeup water at styrene plants 

[Does not include prior treatment of purchased water]

Treatment

None__ _ _ _ _ _ . _

Clarification (screening, coagulation, 

settling, and filtering)

Disinfection: chlorine or chlorine cornPrevention of corrosion and scale:

Softening :

Number of plants using indicated treatment

Oncethrough 

cooling 

water

3 

3

Recirculated 

cooling 

water

3 

5

3

1

2 

2

Process 

water

2

2

1

Boilerfeed 

water

1 

3

2

3 

5

4

Sanitary 

and 

service 

water

2

4

1

The Dow Chemical Co., at Freeport, Tex., uses sodium pentachlorophenate to control algae and slime and to eliminate delignification of cooling-tower wood. "When alkalinity is high and excessive 

amounts of chlorine are used, the chlorine can react with the lignin 

in the wood, and the wood quickly deteriorates due to separation of 

celluloid fibers" (Chem. Eng. Prog., 1960).

The temperatures in high-pressure steam boilers favor the formation of scale and corrosion; therefore, makeup water for them commonly is treated by ion exchange, lime, and phosphate. The dissolved gases in boiler-feed makeup are eliminated to prevent corrosion 

and pitting.

Treatment of water varies with its use. Water for sanitary purposes is commonly treated with a disinfectant to ensure that the water 

is safe for human consumption. The dissolved-solids content and the 

hardness are reduced by chemical treatment, where necessary, to make 

the water palatable and usable for showers. Waters used for scrubbing tanks and floors, and other services, usually receive a minimum 

of water treatment.

Owing to the presence of high concentrations of phosphate, detergents, and fluctuating chemical concentrations, the treatment of municipal sewage is usually more complex than the treatment of water 

obtained from surface- and ground-water sources. The use of municipal sewage presents problems that require individual attention. However, at Big Spring, Tex., the treatment of this sewage is cheaper 

than the treatment of the available ground water, which is highly 

mineralized (McCormick and Wetzel, 1954).
238 WATER REQUIREMENTS OF SELECTED INDUSTRIES

QUANTITY OF WATER WITHDRAWN ANI> CONSUMED

The quantity of water withdrawn for use in the styrene industry 

varies with the local availability of water. In parts of the country 

where large amounts of surface water are available, water is used 

once for cooling and then discarded. In other parts of the country, 

where water supplies are not plentiful, the cooling water is recirculated and the water use decreases. In the High Plains of Texas, 

municipal sewage is the principal source of plant water, and all uses 

of water are carefully inventoried. In these areas of low availability 

of water, air cooling is supplementing or replacing cooling by water. 

Table 4 summarizes the quantities of water withdrawn for cooling, 

process, boiler feed, and sanitary and service uses by the styrene 

industry.

The largest withdrawals are used for cooling water. Although 

only four plants use once-through cooling water, more than 95 percent of the water withdrawn is used once in a heat exchanger and then 

discharged to waste. No water was used consumptively for oncethrough cooling.

About 5.7 million gallons of water is withdrawn daily at capacity 

production and used as makeup to cooling towers. Cooling water 

is circulated through cooling towers, on the average, about 65 times; 

at one plant it is circulated about 160 times. Of the water circulating 

through the cooling tower, 0.276 to 1.59 gallons of water per pound 

of styrene is lost by evaporation or as wind spray, or is otherwise 

consumed.

TABLE 4. Quantity of makeup water used, in gallons per pound, in the manufacture of styrene

Water use

Number of plants

Minimum

Lower quartile

Median

Upper quartile

Maximum

Oncethrough 

cooling 

water

4

2. 75

121

Recirculated 

cooling 

water

7

. 496

. 981

1. 42

1. 88

3. 31

Process 

water

3

. 002

. 190

Boilerfeed 

water

8

. 319

. 450

. 926

1. 52

1. 86

Sanitary 

and 

service 

water

9

. 003

. 064

. 209

. 385

. 711

All 

uses

9

2. 19

2. 26

4. 86

60. 8

123

At most plants the amount of process water used is negligible; 

the maximum reported value is 0.190 gallon of water per pound of 

styrene. No process water is consumed.

About 4.43 million gallons of water is withdrawn daily and used 

as makeup to steam boilers. About 40 percent of this makeup water 

is consumed. Because of the high quality of water required in steam 

boilers, the water is used, on the average, less than five times.
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 239

Some of the steam condensate is not returned to the boiler house 

but is used as makeup to the cooling tower or as process water. Some 

steam becomes contaminated with oils and cannot be reused for boiler 

feed until the oils are removed. For example, in the dehydrogenation 

of ethylbenzene, about 2.6 pounds of steam is mixed with each pound 

of ethylbenzene and must be discarded unless the oil is removed. The 

amount of makeup water for boiler feed ranges from 0.319 to 1.86 

gallons of water per pound of styrene.

Water for sanitary and other services is used once and discharged 

to wT aste; the amounts of these waters range from 0.003 to 0.711 

gallon of water per pound of styrene.

TREATMENT OF WASTE WATERS

Waste waters from styrene plants that are a part of large chemical 

complexes are combined with waste waters from other parts of the complex. The combined waste waters are then treated according to their 

composition.

At some styrene plants the oils and tars in waste waters are separated by gravity, and the resultant water phase is neutralized. The 

settleable solids in the waste water are then precipitated in a series of 

settling basins. The water is then filtered through hay or straw 

(Martin and Rostenback, 1953). At other styrene plants, the waste 

waters containing oils and tars are steam distilled. The 150 million 

gallons of water withdrawn daily, used once in cooling equipment, 

and then discharged is given almost no waste treatment before being 

discharged to surface waters. Although the dissolved-solids content 

has increased, the 4.8 million gallons of waste water discharged 

daily from cooling towers and boilers commonly is given no waste 

treatment. All sanitary-waste waters are discharged to municipal 

sanitary sewers or are treated in company-owned Imhoff tanks or 

septic tanks.

USE OF WATER IN THE MANUFACTURE OF BUTADIENE

HOW WATER IS USED 

BUTADIENE FROM PETROLEUM

Most butadiene is produced by cracking n-butylene, diluted with 

steam, and by cracking n-butane in the absence of steam. Butadiene 

is also produced by cracking n-butane to n-butylene, in the absence 

of steam, and cracking the n-butylene, in the presence of steam, to 

butadiene.

658641 O 62 4
240 WATER REQUIREMENTS OF SELECTED INDUSTRIES

A flowsheet of the manufacture of butadiene by dehydrogenating 

purified n-butylene is shown in figure 36. The uses of water in this 

process are shown in shading; the uses of steam are show in dotted 

lines. About 96 percent of the water withdrawn is used for cooling; 

about 91 percent is used once for cooling and then discarded; about 

4.7 percent is used for makeup to cooling towers. Large amounts of 

cooling water are used to cool and condense the overhead fractions 

from distillation columns, to quench the products from the dehydrogenation reactors, and to maintain the extraction solvents at about 

10°F.

About 2.7 percent of the water withdrawn is used for makeup to 

steam boilers. Steam is used to (a) supply the heat required for 

the cracking of n-butylene to butadiene, (b) eliminate the necessity 

of dehydrogenating in a vacuum, (c) decrease the amount of cracking 

in the furnace, (d) regenerate the catalyst, and (e) supply heat in the 

distillation towers.

The uses of water in the manufacture of butadiene can best be understood by separating the process into (a) feed preparation, (b) dehydrogenation, and (c) purification.

FEED PREPARATION

The purpose of feed preparation is to separate n-butylene from the 

other constituents in the butane-butylene (B-B) stream and to concentrate the n-butylene. The degree of feed preparation varies with 

the concentration of n-butylene in the B-B feedstream. Isobutylene 

is removed from the B-B stream by dissolving the isobutylene in sulfuric acid. The acid layer is then processed to recover the acid and the 

isobutylene. Cooling water is used in this separation to remove the 

heat evolved in the dissolving of isobutylene in the acid. Water 

is also used to cool and wash the recovered isobutylene. Butane is 

commonly removed from the B-B stream by extractive distillation. 

These distillation towers use steam reboilers to supply heat to the 

column and use water-cooled reflux condensers. The lower the concentration of n-butylene in the B-B stream, the more water is required 

in the concentration of the n-butylene.

The butane feed stock for the catalytic dehydrogenation of butane 

to butadiene requires no feed preparation.

DEHYDROGENATION

In the steam-dilution method, prepared butylene is mixed with 10- 

20 volumes of steam which has been preheated to about 1,300°F. The 

hot butylene-steam mixture enters the top of a large brick-lined vertical drum and passes down through a shallow bed of catalyst with little
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 241

drop in temperature. Immediately below the catalyst bed, the gases 

are quenched with sprays of water to suppress polymerization of 

butadiene. The hot reactor gas is further cooled in waste heat boilers, 

where the heat of the gas is used to generate steam that is further 

heated in superheaters and used for diluting the butylene feed to the 

reactor.

The hot reactor gases are further cooled in an oil quench tower by 

passing them up through a spray of cooling oil. The heated oil is 

cooled by water in heat exchangers and recirculated. The product 

stream from the oil quench tower is cooled by water in heat exchangers 

and is further cooled in a water quench tower. Heated oil and water 

from these quench towers are cooled by water in heat exchangers and 

reused in the quench towers. At some plants this system of oil-andwater quench towers is replaced by a series of oil quench towers and 

at other plants by a series of water quench towers. At all plants using 

quench towers, the cooling liquid in the towers is cooled by water in 

heat exchangers. At some plants, water-cooled heat exchangers instead of quench towers are used to cool the gas from the reactor.

The cooled reactor gas and steam condensates are compressed to a 

liquid, cooled by water, and allowed to separate in a vapor-condensate 

separator. The water layer is withdrawn and after treatment is 

reused as cooling-tower makeup or discarded.

The hydrocarbon layer from the condensate separator is fractionated 

in a series of distillation towers, where crude butadiene is separated 

from hydrocarbons having lower and higher boiling points. These 

towers operate with water-cooled reflux condensers to control the tower 

temperature and the quality of the distillate, and with steam-heated 

reboilers to maintain the distillation temperature. The crude butadiene, containing butane, n-butylene, isobutylene, and butadiene is 

sent to be purified to SBR-grade butadiene.

In the Houdry process, butane is dehydrogenated catalytically to 

butadiene in the absence of steam. Butane, mixed with recycle butylene, is vaporized, heated, and passed through a layer of catalyst in 

an insulated horizontal drum reactor. Immediately below the catalyst bed, the hot reactor gas is quenched by sprays of water. The 

reactor gas is further cooled in waste-heat boilers where the heat of 

the reactor gas is used to generate steam.

The hot reactor gas is then cooled to about 100°F in oil quench and 

water quench towers. The cooling liquids in these quench towers 

are cooled by water in heat exchangers. The cooled reactor gas is 

then compressed, cooled, and fractionated to recover the crude butadiene, as in the steam-dilution method.
242 WATER REQUIREMENTS OF SELECTED INDUSTRIES

~rZT\ C"C'""":"'"';^J k.s^ei%Z^3 f~W

8TYREJSTE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 243

a

=3
244 WATER REQUIREMENTS OF SELECTED INDUSTRIES

After about 8-10 minutes of cracking, the reactor is purged by 

steam to remove oil from the catalyst. Heated air is then passed over 

the catalyst to burn off the carbon, which reactivates the catalyst. The 

hot flue gases from this regeneration operation are pumped through 

water-cooled quench tanks, water-cooled heat exchangers, waste-heat 

boilers, and barometric condensers, which intimately mix the hot gases 

with cooling water. At some plants the cooling water from the barometric condensers is used as cooling-tower makeup; at others, it is 

discarded to waste.

In the combined steam-dilution and Houdry process, some plants 

use butane and butylene as raw materials and operate the Houdry process to crack butane to butylene and the steam-dilution method to 

crack butylene to butadiene.

BUTADIENE PURIFICATION

Butadiene is commonly extracted from the crude butadiene by cold 

solutions of aqueous cuprous ammonium acetate (CAA). (See fig. 

36.) The crude butadiene steam is mixed with CAA, and the butadiene is absorbed by the solution of CAA. The butadiene-free hydrocarbon phase and the CAA phase containing butadiene are separated 

by gravity. The hydrocarbon phase is washed with wT ater and 

recycled. The CAA layer is sent to a distillation tower where the 

butadiene is distilled from the CAA. The heat for this distillation 

is supplied by reheating a portion of the CAA bottoms in steamheated reboilers. The remainder of the CAA is cooled by water and 

recycled.

The butadiene distillate contains ammonia, which is removed by 

passing the butadiene-ammonia mixture up through a spray of water 

in a scrubbing tower. The ammonia-free butadiene is then redistilled 

to a purity of 98 percent butadiene. The SBR-grade butadiene is 

stabilized to prevent the formation of higher molecular-weight polymers that range in consistency from a tacky liquid to a resinous 

solid.

The ammonia water is distilled to remove the volatile ammonia and 

is then reused to dissolve ammonia from the butadiene-ammonia mixtures.

The distillation towers are operated by condensing the distillate in 

water-cooled heat exchangers and by reheating the bottoms in steam 

reboilers. The extraction of butadiene with cuprous ammonium acetate (CAA) is commonly operated at about 10°F and requires large 

amounts of cooling water for the refrigeration equipment.

Butadiene is also commonly purified by extractive distillation with 

furfural. The crude butadiene is stripped, by distillation, of n-butyl-
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 245

ene and then pumped to an extractive-distillation tower where the 

butadiene is absorbed by furfural. The butadiene-furfural phase is 

distilled to separate the furfural, which is recycled to the solvent 

tow^er, from the butadiene, which is redistilled to a purity of better 

than 98 percent butadiene. The refined butadiene is stabilized to prevent polymerization. Each of these distillation towers operates with 

water-cooled reflux condensers and steam-heated reboilers.

BUTADIENE FROM ALCOHOL

Butadiene was not manufactured from alcohol commercially at the 

time of this survey. However, because butadiene was made from 

alcohol during World War II and because alcohol may be an important source in the event of another national emergency (U.S. National 

Production Authority, 1952), a brief discussion of this method and 

of the water requirements is included.

The vapors of ethyl alcohol are catalytically dehydrogenated to 

acetaldehyde. The crude acetaldehyde is scrubbed with water to recover the acetaldehyde and ethyl alcohol. This acetaldehyde-alcohol 

phase is then distilled from the water and catalytically dehydrogenated to butadiene. In this process the main use of water is for 

cooling and for makeup to steam boilers.

FINDINGS OF THE SURVEY 

SOURCES

At capacity production, about 429 million gallons of makeup water 

is withdrawn each day in the manufacture of butadiene. A large 

part of this water is salty and is obtained from the Gulf of Mexico, 

bays, estuaries, and the Pacific Ocean. About 25.6 million gallons a 

day (mgd) is withdrawn from ground-water supplies and about 14 

mgd is obtained from nonsaline surface-water sources. A small part 

of the water is obtained by processing municipal sewage. The sources 

of makeup water used in the manufacture of butadiene are summarized in table 5.

Most butadiene plants use more than one source of water supply. 

Of the 12 butadiene plants visited, 10 use ground water for all or part 

of the water supply. One of the other plants supplements its surfacewater supply with estuarine waters. Those plants using salty water 

for once-through cooling use it for no other purpose. At Odessa, 

Tex., municipal sewage is used as makeup for cooling towers and 

steam boilers, well water is used for sanitary purposes, and drinking 

water is purchased (Chemical and Engineering News, 1957a).

Many plants use the same source of water for more than one use. 

Of the 12 plants visited, 9 use the same source of water for makeup to
246 WATER REQUIREMENTS OF SELECTED INDUSTRIES

steam boilers and cooling towers; 6 plants use the same source of water 

for process and cooling-tower makeup; 7 plants use the same source 

of water for sanitary and service purposes and for cooling-tower 

makeup.

TABLE 5. Source of makeup ivater used in the manufacture of butadiene

Source

Well water: 

Self-supplied _

Water company.

Surface water: 

Self-supplied

Municipal water supply

Water authority

Sewage

Bay, estuary, ocean

Number of plants being served by indicated 

source

Oncethrough 

cooling

water

2

1

2

3

Recirculated 

cooling 

water

6 

1

2 

1 

1 

1

Process 

water

4 

1

2

2

Boilerfeed 

water

5 

1

2 

2 

2 

1

Sanitary 

and 

service 

water

9

1 

1 

1

Most butadiene plants are a part of a complex that produces more 

than one petrochemical. Many of these establishments have a central 

water intake, treatment, and disposal system. At a few complexes 

the makeup water used for butadiene is a small part of the total water 

intake. At the present time all producers are obtaining sufficient 

water for capacity production; however, at some plants the present 

sources of water would not be adequate if production were increased 

or if the allowable intake of water were reduced.

If ground water is available, it is used for sanitary purposes because 

less treatment is required. Where ample supplies of ground water 

and surface water are available, the selection of the source to be used 

for the various purposes is dictated by the chemical quality and the 

temperature.

CHEMICAL QUALITY

The chemical analyses of water withdrawn for use in the manufacture of butadiene are summarized in table 6. This table contains the 

minimum, lower quartile, median, upper quartile, and maximum 

values of each constituent. These data include chemical analyses of 

the municipal sewage used but do not include a chemical analysis of 

water from any estuary, bay, or ocean.

The significance of the more important chemical constituents in 

water has been discussed on page 232. Four companies manufacturing butadiene also make styrene and use the same sources of water for 

both petrochemicals. In addition, some butadiene plants are near
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 247

styrene plants and use the same type of water as used in the manufacture of styrene. The chemical quality of the makeup water used 

to make butadiene is similar to that of the makeup water used to make 

styrene.

TABLE 6. Chemical properties of untreated makeup water used in the manufacture

of butadiene

[Chemical analyses were furnished by plants manufacturing butadiene and by the U.S. Geol. Survey]

Constituent or property

Silica (SiD2 )__________ ______

Iron (Fe)._______ _ ____..

Calcium (Ca) ___ _

Magnesium (Mg)_

Sodium (Na) and potassium 

(K)___ .___.______.____._

Bicarbonate (HCO3)__ ___

Sulfate (SO4)- -- _ 

Chloride (Cl)_______________

Fluoride (F)_. ______________

Nitrate (NO8)-_ -__ 

Dissolved solids: 

Residue on evaporation 

at 180°C____ _________

Hardness as CaCO3

Noncarbonate hardness as 

CaCO3 - --._--_______-

pH_________. ______________

Number 

of 

samples

14 

6 

13 

13

9 

20 

18 

17 

20 

5 

5

18 

18

20 

20

Parts per million

Minimum

5.0 

.04 

4.7 

1.2

9.2 

15 

0 

0.0 

8. 5 

. 1 

. 5

107 

12

0 

6. 9

Lower 

quartile

10 

.07 

7.9 

2.0

36 

112 

0 

2.7 

26 

. 1 

. 8

276 

29

0 

7.2

Median

18 

. 10 

33 

7.5

60 

170 

0 

17 

51 

. 3 

1. 5

382

74

8 

8.0

Upper 

quartile

31 

. 14 

40 

14

166 

232 

4 

168 

108 

. 4 

1.7

553 

154

40 

8.2

Maximum

53 

.40 

91 

28

207 

445 

12 

325 

362 

. 4 

1. 7

1,010 

342

170 

8.6

With the exception of the saline waters, most makeup waters contained less than 1,000 ppm of dissolved solids. Although most of the 

butadiene plants are in Texas and Louisiana, the composition of the 

makeup water varies widely. Plants in the Houston and Baton 

Kouge area withdraw ground waters of low hardness, whose principal 

constituents are sodium and bicarbonate. The natural softening is 

the result of cation exchange in the acquifer (Meyer and Turcan, 

1955). These waters have a dissolved-solids content of about 250- 

550 ppm.

Plants withdrawing fresh water from the Neches, Sabine, and 

Brazos Kivers in Texas and from aquifiers near Odessa and Orange, 

Tex., use sodium-chloride waters. The municipal sewage water at 

Odessa also contains sodium and chloride as the principal constituents 

but contains appreciable amounts of sodium phosphate from detergents (Sullivan, 1958). The plants obtaining salty water from 

Neches Kiver, Gulf of Mexico, and Pacific Ocean use water which may 

contain as much as 35,000 ppm of dissolved solids, 19,000 ppm of

658641 O - 62 - 5
248 WATER REQUIREMENTS OF SELECTED INDUSTRIES

chloride, and 11,000 ppm of sodium and potassium. Because of the 

high concentration of salts, these salty waters are used only for oncethrough cooling.

TREATMENT OF MAKEUP WATER

Salty waters used for once-through cooling are treated with chlorine 

to suppress the growth of algae and slime, but no treatment is given 

to the other waters used only once for cooling.

Table Y summarizes the treatment methods used on makeup water at 

butadiene plants. Water used as makeup to cooling towers is given 

considerably more treatment than water used for once-through cooling. The majority of the butadiene plants that recirculate cooling 

water treat the makeup water to the cooling towers with chlorine to 

reduce the growth of algae and slime, adjust the pH, and treat the 

cooling-tower makeup water with phosphate and chromate to prevent 

corrosion. A few of the plants reduce the hardness and the dissolved 

solids of the cooling tower makeup water by treating the water with 

lime-soda and by ion exchange.

The principal treatment given to makeup water for steam boilers 

is softening by ion exchange, lime-soda, and phosphate to suppress 

the formation of scale. As indicated in table Y, most waters are 

treated by ion exchange. Many of the surface-water supplies and 

none of the ground-water supplies are given a clarification treatment 

before the water is sent to the boilers.

The majority of the waters withdrawn for sanitary and other 

services are obtained from ground-water sources, and many of these 

ground-water supplies are given no treatment. The treated ground 

waters generally are given only a chlorination treatment. The surface-water supplies for sanitary and other services commonly are 

clarified and chlorinated.

QUANTITY OF WATER WITHDRAWN AND CONSUMED

The few published quantities of makeup water required in the butadiene industry have been summarized in table 8. All plants that made 

butadiene from alcohol used once-through cooling water, and the 

amount of cooling water used at Kobuta, Pa., should be representative of the amounts of makeup water used at the three plants that 

made butadiene from alcohol during World War II.

The amount of makeup water withdrawn varies with (a) composition of the feedstock, (b) process used, (c) method of purification of crude butadiene, and (d) availability of water supply. The 

amounts of makeup water withdrawn for once-through cooling, recirculated cooling, process, boiler-feed, and sanitary and service uses
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 249

TABLE 7. Treatment of makeup water at butadiene plants 

[Does not include prior treatment of purchased water]

Treatment

Clarification:

Filtration. ..____ __

Disinfection: chlorine and chlorine cornPrevention of scale and corrosion:

Softening:

Numbe

Oncethrough 

cooling 

water

4

2

r of plants

Recirculated 

cooling 

water

2

7

8

7

1

2

using inc

Process 

water

2

1

1

3

2

1

1

licated tre

Boilerfeed 

water

1

1

2

1

6

10

3

atment

Sanitary 

and 

service 

water

6

1

5

in the butadiene industry are summarized in table 9. Water used to 

generate steam that is not used somewhere in the butadiene plant is 

not included in this summary, but some butadiene plants sell steam.

Butadiene plants located near an ample supply of salty water use 

this source for once-through cooling, withdrawing more once-through 

cooling water per pound than plants withdrawing from fresh-water 

sources. Neches Butane Products Co., one of the large producers of 

butadiene, states in a company brochure that it withdraws enough 

water to supply a city the size of Cleveland, Ohio. More than 98 

percent of this water, which is obtained from the leches estuary, is 

used for once-through cooling. In all, less than 1 percent of the water 

used in the butadiene industry for once-through cooling comes from 

fresh-water supplies.

Butadiene plants circulate water through cooling towers about 

45 times on the average. At one plant the cooling water is circulated about 83 times. The amount of water lost by evaporation, 

wind spray, or other consumptive uses ranges from 0.750 to 10.1 

gallons per pound of finished butadiene. Most makeup to the cooling 

towers is obtained from fresh-water supplies; but a few plants use 

makeup water which has been used elsewhere in the plant. The 

amount of makeup withdrawn from fresh-water supplies ranges from 

1.19 to 11.3 gallons per pound of finished butadiene. Plants that use a 

combination of once-through cooling water and recirculated cooling 

water require smaller amounts of cooling-tower makeup water per 

pound of finished butadiene. Plants extracting the crude butadiene
250 WATER REQUIREMENTS OF SELECTED INDUSTRIES

TABLE 8 Published quantities of makeup water required in the manufacture of 

butadiene in the United States

Location

Toledo, Ohio_ ____ _

Kobuta, Pa . _

Entire industry (U.S.)

Entire industry (U.S.).

Los Angeles, Calif

Use

Recirculated cooling

Once-through

cooling.

_____do_--_-________

___-_do_-__-_____-__

Water 

required 

(gallons per 

pound)

5.2

2.8

144

4. 2

160

11. 0-363

3. 65-105

Source reference

Thayer and others,

1942. 

Chem. Eng., 1954.

Stein, 1945.

Do.

Gorman, 1943.

United Nations,

1958. 

O'Connell and

Gregory, 1944.

TABLE 9. Quantity of makeup water used in the manufacture of butadiene

Water use

Oncethrough

cooling

water

6

Recirculated

cooling

water

11

Process

water

8

Bojlerfeed

water

12

Sanitary

and

service

water '

12

All

uses

12

Gallons per pound

Minimum __

Lower quartile _ _ _ Median

Upper quartile _ _____

Maximum __ _

0.392

2.94

9.88

48. 6

217

1. 19

1. 65

3. 60

4. 84

11.3

0.020

. 110

. 172

.218

1.31

0.045

1.08

1.47

2. 57

5. 85

0.023

. 115

.402

. 752

1. 72

5.38

7.21

9. 60

14. 6

221

Million gallons per day

Total for industry _ 391 20. 1 2. 10 11. 6 4. 10 429

i Includes water supplied to company town.

with CAA use less cooling-tower makeup water than plants extracting 

crude butadiene with furfural.

Some plants use no process water; some use water that has been used 

elsewhere for process water; some use a mixture of water used elsewhere and new makeup water; and others use only new makeup 

water. The amount of process water withdrawn from surface- and 

ground-water supplies ranges from 0.020 to 1.31 gallons per pound of 

finished butadiene. Plants using butane-butylene feed stock withdraw less process water per pound of finished butadiene than plants 

using butane as the feed stock.

Most plants operate steam-generating boilers; and a part of the 

steam condensate, commonly, is collected and returned to the boiler-
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 251

house. The water in the steam system is circulated, on the average, 

about four times: at one plant the boiler water is circulated about 

15 times. The amount of steam lost by evaporation or otherwise consumed ranges from 0.087 to 1.36 gallons per pound of finished 

butadiene. To replace the boiler feed consumed and the blowdown 

from the boilers requires between 0.045 to 5.85 gallons of water per 

pound of finished butadiene.

Plants manufacturing butadiene by mixing about 10 to 20 volumes 

of steam to each pound of hydrocarbon sent to the dehydrogenation 

reactor require larger amounts of boiler-feed makeup than plants 

making butadiene by the Houdry process. Plants using a combination 

of Houdry and steam-dilution methods require less boiler-feed makeup 

than plants manufacturing butadiene by the steam-dilution method, 

but more than plants using the Houdry process.

Water for sanitary and other services commonly is used once and 

discharged to waste. At one plant these services include supplying 

water to a company-operated town. The amount of water for sanitary and service ranged from 0.023 to 1.72 gallons per pound of 

finished butadiene.

TREATMENT OF WASTE WATERS

The butadiene industry at capacity production discharges about 

410 million gallons of waste water each day to surface waters. Most 

of this effluent is salty and is returned to its source without any waste 

treatment. Some waste waters from cooling towers and steam boilers 

are discharged also without any waste treatment.

Most butadiene plants operate oil-separation systems to remove 

oily hydrocarbons from waste waters. Usually the waste waters are 

neutralized by adjusting the pH, and the settleable solids are removed 

in a series of settling basins. At some plants the -waste waters are 

neutralized, freed of oil and settleable solids, diluted with cooling 

water, and discharged to waste.

All sanitary waste waters are discharged to sanitary sewers or 

treated in company-operated Imhoff tanks or septic tanks. Blue 

water leakages from CAA equipment contain copper and usually are 

treated to recover the copper.

USE OF WATER IN THE MANUFACTURE OF 

STYRENE-BUTADIENE RUBBER

HOW WATER IS USED

Styrene-butadiene rubber (SBR) is made by forcing styrene and 

butadiene to react in a soapy water solution and form minute particles 

of synthetic rubber. This suspension of rubber in soapy water, called
252 WATER REQUIREMENTS OF SELECTED INDUSTRIES

latex, is coagulated to form a rubber crumb that is washed and dried. 

Aqueous solutions of oil and carbon black may be added to the latex 

before coagulation, to extend the volume of rubber.

About 61 percent of the water withdrawn for use in the manufacture 

of SBR comes into direct contact with the rubber. Most of this 

process water is used to (a) make the aqueous solutions of soap and 

other chemicals, (b) make carbon-black slurries and oil solutions, and 

(c) wash the rubber crumb. About 17 percent of the water withdrawn is used for cooling polymerization reactors and heat exchangers 

used in the recovery of unreacted butadiene and styrene. Makeup 

water to the boilers generating steam for use in the styrene stripping 

column and in drying the rubber crumb requires about 11 percent of 

the water withdrawn. The remainder of the water is used for general 

services in the plant.

The amount and quality of water used in the manufacture of this 

synthetic rubber can be best described by dividing the process into 

four phases: (a) feed preparation, (b) latex formation, (c) recovery 

of butadiene and styrene, and (d) conversion of latex into dry rubber. 

Figure 37 is a simplified flowsheet of the manufacture of SBR with 

the uses of steam shown by dotted lines and the uses of water by 

shading.

FEED PREPARATION

The principal raw materials pumped to the reactor are styrene, 

butadiene, and aqueous solutions of soap and other chemicals. Styrene requires no feed preparation, and it and butadiene are stored 

in steel tanks that, at some plants, are sprayed with cooling water 

during hot weather to reduce polymerization. The small amount of 

polymerization inhibitor in styrene is not removed. Butadiene 

received from a distance contains a polymerization inhibitor that is 

removed by (a) mixing butadiene with a caustic solution, (b) allowing the solutions to separate by gravity, (c) decanting off the butadiene, (d) mixing the butadiene with water, (e) allowing the solutions 

to separate by gravity, and (f) decanting off the butadiene.

The solutions of soap and other chemicals are generally prepared 

in waters containing less than 10 ppm of hardness.

LATEX FORMATION

Styrene, butadiene, soapy water, and other aqueous solutions are 

cooled and pumped into temperature-regulated, glass-lined pressure 

reactors. The thoroughly agitated emulsions of styrene and butadiene polymerize and form minute particles of SBR. Butadiene 

enters the reaction first, but as the polymerization proceeds the rubber 

formed contains increasing amounts of styrene. Increasing the sty-
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 253

rene content increases the tensile strength of the rubber; decreasing 

the styrene content favors the retention of resilience and flexibility 

at low temperatures. SBR is composed of about 6 butadiene units to 

each styrene unit. The styrene units may enter the system singly or 

in clumps and are randomly located in the chain. After the reaction 

has proceeded to the desired degree of completion, the catalyst is 

destroyed and the reaction stops.

The conversion of butadiene and styrene into SBR generates considerable heat that is dissipated throughout the agitated soap solution. In the manufacture of hot rubber, the temperature of the reaction is controlled to about 120°F by circulating cooling water in a 

jacket around the reactor. In the manufacture of cold rubber, the 

reaction temperature is regulated near 41°F. At some plants this 

temperature is regulated by circulating brine or methanol-water solution in a jacket around the reactor; the brine and methanol-water 

solutions are then cooled by water in heat exchangers. At some plants 

the temperature is regulated to 41 °F by the direct evaporation of 

ammonia in cooling coils inside the reactor; the ammonia is recondensed in water-cooled heat exchangers.

At some plants the raw materials are charged into the reactor, the 

reaction proceeds to the desired stopping point, and the batch is then 

dropped into a blowdown tank. This batch type of operation requires 

a large amount of process water and steam only at the start of the 

reaction and cooling water only during polymerization. The operation of a large number of reactors eliminates the surges of water 

demand.

At some plants butadiene, styrene, and aqueous solutions are pumped 

continuously into the top and out the bottom of a series of reactors. 

The flow rates of the raw materials are adjusted to obtain the desired 

viscosity or monomer conversion in the last reactor of the series. The 

continuous process allows about a 20 percent increase in effective 

reactor capacity (Whitby, 1954); therefore more steam, process, and 

cooling water is required as the result of the increased production.

RECOVERY OF BUTADIENE AND STYRENB

The latex in the blowdown tanks contains considerable amounts of 

unreacted butadiene and styrene that are recovered by flash evaporation 

and steam distillation. The recovery of these monomers requires large 

amounts of steam and cooling water. Steam is injected into the 

latex in the blowdown tanks. The heated latex and unrecovered 

monomers are transferred to butadiene "flash" tanks, where butadiene 

is evaporated or "flashed" from the latex. The butadiene vapors are 

compressed to a liquid and blended with fresh butadiene for reuse.
254 "WATER REQUIREMENTS OF SELECTED INDUSTRIES STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 255

I

M

s

B

 S

I
256 WATER REQUIREMENTS OF SELECTED INDUSTRIES

The latex and unrecovered styrene are pumped from butadiene flash 

tanks to the top of a styrene stripping column. The recovery of 

styrene from the latex is illustrated in figure 38. A stream of lowpressure desuperheated steam is injected into the bottom of the tower, 

passes up through the falling latex, and strips the vaporized styrene 

from the latex. The vapors of styrene and steam flow to a watercooled heat exchanger, where the steam and styrene are condensed. 

The condensed styrene and water flow to a styrene decanter tank, 

where the liquids are separated by gravity. Styrene overflowing 

from the decanter tank is blended with fresh styrene of higher purity

FIGUKE 38. Water use in the recovery of styrene from latex.
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 257

for reuse. Part of the water from the decanter is used in the "seal 

water system" of the butadiene recovery system, and part is released 

to waste. Water in the "seal water system" is used to seal and compress butadiene vapors in vacuum pumps and compressors.

The latex, stripped of monomers, is blended with latexes from 

several batches or production lines. About 7 percent of the latex 

produced in 1959 was sold before coagulation into the rubber crumb. 

The rubber content in the latex to be sold is commonly increased by 

evaporating water from the latex with steam heat.

CONVERSION OF LATEX INTO DRY RUBBER.

To prevent deterioration of the rubber, aqueous emulsions of antioxidant are added in the blend tank to latex that is to be coagulated 

and dried. The methods of coagulating and drying SBR vary from 

plant to plant. The following description, which emphasizes the 

use of water, is a composite of the techniques used in the industry.

Oil-extended SBR is made by adding an emulsion of oil, caustic, 

and water to the latex in the blend tank. SBR is master batched by 

mixing a slurry of 20 percent carbon black with the latex in the blend 

tank. Oil-extended master batch is made by adding extender oil 

and a slurry of carbon black to the latex. If the rubber is to be extended with oil and carbon black, the finished rubber may contain 

more than 100 pounds of extender oil and carbon black for each 100 

pounds of standard SBR.

Latex with carbon black, oil-extended latex, and latex extended with 

oil and carbon black are coagulated and dried in the same manner 

as standard SBR latex, except that additional water is required for 

washing and additional steam for drying the larger volume of apparent rubber.

Latex is pumped from the blend tank and mixed with a water solution of sodium chloride in the coagulation tank. The brine causes 

a partial flocculation of the latex particles, which changes the consistency of the latex to that of a heavy cream. The coagulation of 

the crumb is completed by the addition of dilute sulfuric acid to the 

latex in the coagulation tank . After the flocculation is completed, 

the crumb overflows to the soap-conversion tank, where any residual 

soap is converted to fatty acid. The slurry of coagulated rubber 

overflows from the soap-conversion tank to a vibrating screen or to 

a skimmer tank, where the rubber crumb is separated from the water 

serum. The serum which contains about 4 percent sodium chloride 

and residual sulfuric acid, is reused in the preparation of the brine 

solution and the dilute acid solution. Excess serum is sent to the 

sewer.
258 WATER REQUIREMENTS OF SELECTED INDUSTRIES

The rubber crumb is reslurried with fresh water to wash out residual 

salts and acids. As illustrated in figure 39, the overflow from the 

reslurry tank flows by gravity onto a large rotating vacuum drum, 

where the wash water is removed. The friable crumb shown in 

figure 39 is washed with hot water at some plants and with cold water 

at other plants to reduce even further any residual salt and acid. The 

large rollers compress the rubber crumb and water is drawn by vacuum 

through the screen. This wash water is recovered and used to reslurry the rubber crumb before it contacts the rotating filter.

FIGURE 39. Dewaterlng of styrene-butadiene-rubber (SEE) crumb.
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 259

The rubber, which comes from the filter and contains about 25-30 

percent water, is shredded and blown into a large dryer which is 

usually heated by steam. The water is evaporated from the rubber 

crumb and, at some plants, is condensed and reused as boiler-feed 

water. The crumb, which comes from the drier and contains less than 

0.5 percent water, is compressed in a hydraulic baler. The 75-pound 

bales of rubber are then sprayed with talc or wrapped in polyethylene 

film.

FINDINGS OF THE SURVEY

SOURCES

At capacity production about 15.9 million gallons of ground water 

and about 12.8 million gallons of surface water are withdrawn each 

day in the production of styrene-butadiene rubber. The 28.7 million 

gallons of water required each day is obtained (a) by pumping from 

ground or surface water sources or (b) by purchasing from municipal 

supplies, water authorities, public utility companies, or neighboring 

industries. No water from the ocean or other saline sources was used 

in the manufacture of the styrene-butadiene rubber. The sources 

of supply used for cooling water, process water, boilerfeed water, and 

sanitary and service water by the SEE, plants are summarized in table , 

10. Municipal sewage water was used only for boiler-feed makeup 

water.

TABLE 10. Sources of makeup water for styrene-butadiene rubber

Source

Well water:

Water company _ _ _

Surface water: 

Self-supplied _ _ _ _

Neighboring industry, __ _ _ _

Number of plants being served by indicated 

sources

Oncethrough 

cooling 

water

1

2

Recirculated 

cooling 

water

7 

2

2

2 

3

Process 

water

7 

2

1

2

4

Boilerfeed 

water

4 

2

2

1

Sanitary 

and 

service 

water

6 

1 

1

1 

1 

2

4

The majority of the SEE, plants obtain ample water from present 

sources of supply; however, some plants are obtaining just enough 

water for present capacity production. If the amount of water available at present should be reduced or if production should be greatly 

increased, these plants would have difficulty in obtaining sufficient
260 WATER REQUIREMENTS OF SELECTED INDUSTRIES

water from the present sources of supply; therefore these plants are 

planning to develop additional supplies.

Two-thirds of the plants visited used more than one source of supply. The other third used only ground-water supplies. Of the 15 

SBR plants, 14 used the same source of water for process use and for 

makeup to the cooling towers. Five of the plants purchased steam, 

and all the other plants used the same source of water for boiler-feed 

makeup and for makeup to the cooling towers.

CHEMICAL QUALITY

The chemical properties of untreated makeup water used in the 

manufacture of SBR are summarized in table 11. The table contains 

the minimum, lower quartile, median, upper quartile, and maximum 

values of each constituent in the makeup water for recirculated cooling water, process water, and boiler-feed water. Because 14 out of 15 

plants use the same sources of water for cooling and process use, the 

analytical data for these 2 uses were combined. The data for boilerfeed makeup water included the chemical analyses, where available, of 

the raw water used to generate the purchased steam. The chemical 

analyses of sewage water have been included in the preparation of this 

table. The significance of the more important chemical constituents 

were discussed on page 232.

TABLE 11. Chemical properties of untreated, makeup water used in the 

manufacture of styrene-butadiene rubbers

[Chemical analyses were furnished by plants manufacturing SBR and by the U.S. Geol. Survey]

Constituent or 

property

Silica (Si02).-_ -

Iron (Fe).. -~ 

Calcium (Ca). ......

Magnesium (Mgl ... 

Sodium (Na) and 

potassium (K) __ 

Bicarbonate 

(HC08)- - -

Carbonate (CO3)___ 

Sulfate (SOi)---- 

Chloride (Cl).......

Nitrate (NO3) ......

Dissolved solids: 

Residue on evaporation at 180° C _ _ Hardness as CaCOs. 

Noncarbonate hardness as CaCO3 _ _

KvTT

Cooling and process

Number 

of 

samples

13 

13 

15 

15

15

16 

16 

15 

16 

5

10 

16

16 

13

Parts per million

Minimum

1.8 

.00 

4.0 

1.0

4.1

8 

0 

0.0 

3.5 

.0

38 

16

0 

6.7

Lower 

quartile

7.8 

.06 

7.8 

2.2

19

42 

0 

4.4 

9.7 

.2

107 

34

2 

7.0

Median

14 

.10 

25 

5.2

38

133 

0 

17 

25 

1.0

223

77

17 

7.5

Upper 

quartile

26 

.80 

34 

8.0

70

241 

0 

50 

36 

16

335 

135

40

7.8

Maximum

40 

1.9 

139 

36

129

366 

5 

213 

52 

32

526 

495

231 

8.6

Boiler feed

Number 

of 

samples

10 

5 

10 

10

6

13 

13 

11 

13

89 

13

12 

11

Parts per million

Minimum

4.5 

.08 

4.0 

1.0

13

8 

0 

.0 

6.7

38 

16

0 

6.7

Lower 

quartile

9.0 

.08

7.8 

1.5

21

31 

0 

4.4 

9.8

107 

31

2 

6.9

Median

14 

.10 

15 

2.8

22

144 

0 

17 

27

236 

65

12 

7.2

Upper 

quartile

24 

.82 

32 

7.3

55

224 

6 

95 

44

309 

326

54 

7.6

Maximum

40 

1.5 

139 

36

61

366 

8 

213 

298

900 

495

231 

8.6
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 261

The makeup water, exclusive of municipal sewage, generally was 

of good quality and had maximum dissolved solids of about 526 ppm; 

the sewage water had dissolved solids of 900 ppm. Most makeup 

waters were of a calcium bicarbonate type, but the hardness was less 

than 500 ppm and the bicarbonate less than 370 ppm. A few water 

supplies in Texas and Louisiana, where natural ion exchange may have 

occurred, had sodium and bicarbonate as the principal constituents. 

In these waters the maximum sodium reported was 129 ppm, and the 

maximum bicarbonate was 317 ppm. The principal constituents of 

the makeup water from municipal sewage and the Lower Neches Valley Authority were sodium and chloride. In these waters the maximum chloride was 298 ppm.

The median hardness of recirculated cooling and process water 

is about 77 ppm. At some plants the hardness in the makeup water 

for process use was reported to cause problems. D. W. Cate (1958 ?) 

in advising on the handling and storage of Firestone latices states, 

"Polyvalent ions such as iron, calcium, magnesium or aluminum cause 

coagulation of latex." The rubber plant at Institute, W. Va., reported that waters having a hardness in excess of 50 ppm caused rubber latex to coagulate in tanks, pipelines, and other pieces of plant 

equipment (Borg, 1945).

TREATMENT OF MAKEUP WATER

The treatment given to makeup waters withdrawn for cooling, process, boiler-feed, and sanitary and service uses is summarized in table 

12. Of the 15 plants manufacturing SBK, only 2 plants use oncethrough cooling water. One plant adjusts the pH clarifies by the 

addition of alum and filtration, and chlorinates the makeup water. 

The other plant purchases the makeup water that had been similarly 

treated by a municipality; this plant does not treat the makeup water 

further.

The makeup water for cooling towers is given more extensive treatment. All SEE plants recirculate cooling water through cooling 

towers; of 15 plants, 11 add chromates or phosphates to the coolingtower makeup water to suppress corrosion; 4 treat the makeup water 

with lime or ion exchange resins to lower the hardness and to prevent 

the formation of calcium carbonate scale; 11 chlorinate the coolingtower makeup water; and 2 of the remaining 4 plants purchase water 

that has been chlorinated.

As indicated in table 12, the principal treatment given to process 

water is lowering the hardness by ion exchange. Most plants 

reduce the hardness of part or all of the process water to less than 

10 ppm.; a few plants lower to near zero the hardness of the water used
262 WATER REQUIREMENTS OF SELECTED INDUSTRIES

TABLE 12. Treatment of makeup water at styrene-butadiene rubber plants 

[Does not Include prior treatment of purchased water!

Treatment

None. _____________ ___ _____ _ __ ___

Clarification : 

Filtration. _ __ ____________ ____ _

Coagulation and filtration _ ____ ____

Disinfection: chlorine or chlorine cornPrevention of corrosion and scale: 

Chromate and phosphate. ___ __ ___

pH adjustment _______ ___ ______

Softening: 

Lime-soda_- ____ ___________ __

Ion-exchange _________ ___

Phosphate_____ ___ _ ____ _ __

Numbe

Oncethrough 

cooling 

water 1

1

1

1

1

r of plant.

Recirculated 

cooling 

water

2

2

2

11

11

5

3

1

> using in(

Process 

water

1

3

1

2

7

2

5

14

licated tr

Boilerfeed 

water

2

2

1

3

9

9

4

satment

Sanitary 

and 

service 

water

6

2

1

2

7

2

3

1

1 Only 2 plants use once-through cooling water.

to make reactor water solutions. Plants producing only SBR latex 

deionize all process water; plants producing dry SBR deionize 

between 10 and 50 percent of the process water. The water used to 

wash the rubber crumb, which is a large part of the process water, 

generally comes from the same source as the reactor charge water but 

is not demineralized.

Almost all plants reduced the hardness and the dissolved-solids 

content of the makeup water for boiler feed by ion exchange or by 

lime-soda treatment. Of all plants, 7 chlorinated the water for 

sanitary purposes, and 6 additional plants purchased water for sanitary purposes from municipalities that chlorinate the water before 

selling it to the plants. A few plants soften water for sanitary 

use in the locker rooms.

QUANTITY OF WATEK WITHDKAWN AND CONSUMED

The author was unable to find published information on the 

quantity of makeup water used in the direct manufacture of SBR. 

Published values of the aggregate amounts of water used to produce 

SBR and to produce its required amounts of styrene and butadiene 

are discussed later.

At capacity production, about 28.7 million gallons of water is 

withdrawn daily for use in the direct manufacture of SBR; about 15.9 

million gallons is obtained from ground-water supplies, and about 12.8 

million gallons is withdrawn from surface-water supplies. The
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 263

amount of water withdrawn varies with the process of manufacture of 

SBR and the availability of water supply at the plant. The amounts 

of makeup water withdrawn for recirculated cooling water, process 

water, boiler feed, and sanitary and service water are summarized 

in table IS.

Only two plants use once-through cooling water as well as recirculating cooling water. All SBR plants recirculate part of or all the 

cooling water through cooling towers. The recirculated cooling water 

does not come into contact with the product and is used as many as 

240 times. Recirculated cooling-water losses due to evaporation, 

wind spray, or other consumptive uses range from 0.054 to 2.6 gallons 

of water per pound of finished rubber. To replace consumptive losses 

and water discarded to waste from the cooling towers requires from 

0.065 to 4.71 gallons of water per pound of finished rubber. Rubber 

extended with oil and carbon black uses less makeup water per pound 

of finished rubber for cooling than latex or nonextended SBR. The 

seeming decrease in water use by the extended rubbers is due to the 

added weight of extender oil and carbon black in the finished apparent 

rubber. The three companies using the largest amounts of makeup 

water for recirculated cooling are located in areas of plentiful water 

supply.

TABLE 13.- -Quantity of makeup water used in the manufacture of styrene-butadiene 

rubber

Water use

Recirculated

cooling

water 1

15

Process

water

15

Boilerfeed

water

15

Sanitary

and

service

water

15

All

uses

15

Gallons per pound

Minimum

Lower quartile .

Median

Upper quartile _

Maximum _

0.065

. 351

.402

.954

4.71

0. 122

1.31

2. 33

2.88

3.91

0.087

.210

.406

.672

1.21

0.022

. 109

.431

. 830

1. 25

0.883

2.52

3.45

5.42

10.2

Million gallons per day

Total for industry. 3. 12 3.06 28. 7

i In addition, 2 plants used once-through cooling water.

The amount of water withdrawn for process use ranges from 0.122 

to 3.91 gallons per pound of finished rubber. Most plants have two 

types of process water: deionized process water and nondeionized process water. The deionized water is used for reactor charge and other
264 WATER REQUIREMENTS OF SELECTED INDUSTRIES

uses where the minerals in the water could cause coagulation of the 

latex. The minimum amount of deionized water required for standard SBR formulas is 0.22 gallon per pound of finished rubber. The 

amount of process water treated by ion exchange in most plants 

ranged from 0.25 to 0.78 gallon per pound of finished rubber. Some 

plants mix recovered steam condensate with deionized water for 

process use.

Plants making only latex do not wash any rubber crumb and 

thus use less process water than plants producing dry SBR. Latex 

plants use process water principally in the soap solution pumped to 

the reactor and therefore discharge little or no process water to 

waste. Most plants that do not produce latex do not use any process 

water consumptively. The amount of process water consumptively 

used by latex plants ranges from 0.065 to 0.421 gallon of water per 

pound of finished rubber.

The makeup water to boiler feed ranges from 0.087 to 1.21 gallons per pound of finished rubber. A large part of this makeup 

water is used to replace the steam injected into the blowdown tank 

and the steam contaminated in the styrene stripping. In both uses 

the steam is condensed and becomes part of the 0.035 to 1.21 gallons 

of the steam, condensate discharged to waste for each pound of finished 

rubber produced. The steam injected into the blowdown tanks commonly is lost in the coagulation and drying processes. The recommended steam rate into the styrene stripping tower illustrated in figure 

38 is 5.5 pounds of steam per pound of styrene in the column. At a 

monomer conversion rate of 72 percent, this requires 0.118 gallons of 

boiler-feed water per pound of rubber in the column (Johnson and 

Otto, 1949).. Lower conversion rates require more steam and thus 

more boiler-feed makeup.

Plants producing only latex use more makeup water, per pound of 

dry SBR, for boiler feed than plants producing dry SBR. Plants producing rubbers extended with oil and carbon black use less makeup 

water for boiler feed, per pound of finished rubber, than plants producing latex and nonextended SBR. The lower values of makeup 

water per pound of extended SBR may be caused by the increased 

weight of extender oil and carbon black in the extended rubbers.

In addition to the water used directly in the manufacture of styrenebutadiene rubber, water is used for company cafeterias, washing 

floors, other services, and sanitary purposes. The amount of water 

used for these services is summarized in table 13. Waters used for 

sanitary and service purposes are not recirculated in any plant.
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 265

TREATMENT OF WASTE WATERS

SBE plants, at capacity production, discharge about 25.5 million 

gallons of water each day principally to surface waters. Most of 

the effluent waters are given little or no treatment. The treatment 

given to effluent containing latex, rubber crumb, or other settleable 

solids generally consists of pumping the effluent to a settling basin, 

where the heavy solids are allowed to settle out and the floatable materials are retained by a separator at the basin discharge. At some 

plants chemicals may be added to aid flocculation.

The sanitary wastes are processed in Imhoff tanks or discharged 

to sanitary sewers to be processed further elsewhere.

AGGREGATE QUANTITY OF WATER REQUIRED TO PRODUCE STYRENEBUTADIENE RUBBERS

The published values of the quality of water required to produce 

SBE and its required amounts of styrene and butadiene are summarized in table 14.

The aggregate amounts of makeup water withdrawn to produce 

SBR-type synthetic rubbers depend upon the amounts of water withdrawn to make the raw materials, styrene and butadiene, and the 

amounts of water used in the direct manufacture of the synthetic rubbers. The near-minimum amounts of makeup water used to make 1 

pound of SBE composed of about 75 percent butadiene and 25 percent 

styrene is illustrated in figure 40. This schematic drawing shows the 

amounts of (a) makeup water, (b) effluent, and (c) water consumptively used in the manufacture of the required amounts of styrene 

and butadiene and in the direct manufacture of SBE. It is assumed 

that no once-through cooling water is used; in the manufacture of 

styrene or butadiene, once-through cooling water could require more 

than 40 times the amount of makeup water shown. It is also assumed 

that no SBE latex is made; the manufacture of SBE latex would 

decrease the amount of effluent and would increase the consumptive 

use of water.

TABLE 14. Published quantities of makeup water required to produce styrenebutadiene rubber in the United States

Location

Institute, W. Va. ______

Entire industry (U.S.) _ _

Water required

Gallons per 

pound

281 

13. 8-330

Gallons per ton

631, 000 

31, 000-740, 000

Source reference

Olive and Shreve 

(1947). 

United Nations (1958).
266 WATER REQUIREMENTS OF SELECTED INDUSTRIES

EXPLANATION 

Water out Water in

r

Effluent Consumptive Makeup 

use

Width of each square represents 2 

gallons of water per pound of 

product

Styrene

FIGURE 40. Near-minimum amounts of makeup water used to produce styrene-butadiene

rubber (SBR).
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 267

The amounts of styrene and butadiene used to produce 1 pound of 

SBR-type synthetic rubber depends upon the type of the synthetic 

rubber. A pound of SBR extended with carbon black and extender 

oil requires less styrene and butadiene than 1 pound of SBR. As a result, the amount of makeup water used to produce the styrene and 

butadiene used in 1 pound of SBR extended with carbon black and 

extender oil is less than the amount of makeup water needed to produce the styrene and butadiene needed for 1 pound of nonextended 

SBR.

The amounts of makeup water used in producing styrene and butadiene and the amount used in the direct manufacture of the SBRtype synthetic rubbers depends upon the process used and the availability of water supply. The amount of makeup water withdrawn 

to produce 1 pound of styrene ranges from 2.2 to 123 gallons; that 

withdrawn to produce 1 pound of butadiene ranges from 5.4 to 221 

gallons; and that withdrawn in the direct manufacture of SBR-type 

synthetic rubbers ranges from 0.883 to 10.2 gallons.

The minimum and maximum amounts of makeup water required 

to produce 1 pound and 1 long ton (2,240 pounds) of SBR latex, SBR, 

oil-extended SBR, and SBR extended with carbon black and extender 

oil are summarized in .table 15. The minimum (and maximum) 

quantities of makeup water were calculated by adding the minimum 

(and maximum) quantities of makeup water used to make the required amounts of styrene and butadiene in 1 pound of each type of 

synthetic rubber to the minimum (and maximum) quantities of 

water used in the direct manufacture of 1 pound of each type of synthetic rubber.

TABLE 15. Minimum and maximum quantities of makeup water required to produce 

styrene-butadiene rubbers (SBR)

Product

SBR latex... _.._____.__.____._._ __

SBR_ ________________________________

Oil-extended SBR__-__ _ ______ _ ___.

SBR extended with oil and carbon black, _

Makeup water required

Gallons of water per 

pound of finished 

rubber

Minimum

5. 1 

8.4 

6.2 

6.2

Maximum

187 

187 

164 

145

Gallons of water per 

long ton of finished 

rubber

Minimum

11, 400 

18, 800 ' 

13, 900 

13, 900

Maximum

418, 000 

' 420, 000 

368, 000 

324, 000
268 WATER REQUIREMENTS OF SELECTED INDUSTRIES

USE OF WATER IN THE MANUFACTURE OF 

SPECIAL-PURPOSE SYNTHETIC RUBBERS

During the last complete defense mobilization, in 1941-45, thiokol, 

neoprene, butyl, and nitrile rubbers were considered essential to the 

war effort. The shortage of certain kinds of these special rubbers 

was a detriment to the war plans. The use of water in these specialtyrubber plants was determined and is presented in order to give a more 

complete picture of the utilization of water in the synthetic-rubber 

industry. A brief description of water use in the manufacture of 

these special rubbers follows.

HOW WATER IS USED 

NITRILE RUBBER

Nitrile rubber, which is sold under the trade names of Perbunan, 

Hycar, Chemigum, and Butaprene, is commonly made by polymerizing butadiene and acrylonitrile, catalytically, in a soapy water solution. The preparation of nitrile rubber is similar to the preparation 

of SEE. (One plant is manufacturing nitrile rubber in equipment 

designed to produce SEE.)

About 22-24 gallons of distilled or deionized water, containing 

chemicals which control polymerization, are charged with each 75 

pounds of butadiene and 25 pounds of acrylonitrile into a glass-lined 

or stainless-steel reactor. The exothermic polymerization reaction is 

generally controlled at temperatures less than 80 °F by circulating 

cooling water in coils around the reactor. After the polymerization 

is terminated, the unreacted butadiene and acrylonitrile are recovered 

by procedures described in the section on the recovery of butadiene 

and styrene from SEE latex.

The controlled addition of brine to the nitrile rubber latex coagulates and flocculates the rubber particles to a rubber crumb. The 

rubber crumb is then separated from the slurry on a rotating vacuum 

filter and reslurried with water to remove soap and water-soluble 

salts. The washed crumb is refiltered, dried, and packaged for 

shipment.

In the manufacture of nitrile rubber, a large part of the makeup 

water is used to control the temperature of the reactor and to condense 

and cool recovered butadiene and acrylonitrile. At plants making 

nitrile rubber crumb, large amounts of water are used for washing 

the crumb; at plants manufacturing only nitrile latex, smaller amounts 

of process water are required principally to charge the reactor. The 

steam in the stripping column comes in contact with the latex and is 

not returned directly to the boilerhouse.
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 269

BUTYL RUBBER

Butyl rubber is made by mixing, at low temperatures, 98 percent 

isobutylene with 2 percent isoprene that contains methyl chloride, an 

inert diluent that controls polymerization. The manufacture of 

butyl rubber is illustrated schematically in figure 41. The isoprene 

and isobutylene are recovered from petroleum refinery products by 

absorption and distillation. Isobutylene and isoprene are cooled and 

sent to reactors regulated to 140°F, where they react, in the presence 

of a catalyst, to form fine particles of butyl rubber. The rubber 

polymer, along with unreacted hydrocarbons, is sent from the reactor 

into a large volume of vigorously agitated hot water in a flash tank. 

The hydrocarbons are vaporized from this tank and collected, compressed, dried, refined, and recycled to the reactor.

The slurry of butyl from the flash tank is pumped to a vibrating 

screen or a rotating vacuum filter, where the rubber crumb is separated 

from the water, which is recycled to the flash drum (see fig. 41). The 

rubber product is passed through a dryer to remove most of the 

remaining water; it is then extruded, milled, cut into squares, and 

packaged for shipment.

In the manufacture of butyl rubber, cooling water is used in condensers on distillation towers and to cool the refrigerant used to regulate the reactor temperature. Process water is used for scrubbing 

hydrocarbons. Steam is used to vaporize the hydrocarbons in the 

flash tank, to dry the rubber, and as a source of heat for distillation 

columns.

NEOPRENE

Neoprene is produced by polymerizing an aqueous emulsion of 

chloroprene. The basic steps in the manufacture of neoprene are 

shown schematically in figure 41. Acetylene is converted catalytically 

in a reactor to monovinyl-acetylene, which is separated from other 

reactor products by low-temperature condensation and by fractional 

distillation. The purified monovinyl-acetylene is reacted with hydrogen chloride, in the presence of a catalyst, to form liquid chloroprene. 

The crude chloroprene is purified by condensation and distillation to 

remove unreacted mono vinyl-acetylene and hydrogen chloride.

Purified chloroprene is emulsified in 100 °F water containing chemicals that regulate polymerization; about 20 gallons of water are needed 

for each 100 pounds of chloroprene charged to the reactor (Whitby, 

1954). The chloroprene emulsion is polymerized to a latex of butyl 

rubber in a polymerization tank. The latex from several polymerization tanks is blended and pumped onto a freeze roll maintained at 

about 10°F. Here the latex, which is composed of about 35 percent 

solids and 65 percent water, is frozen. A thin continuous film of
Jl ft Vapors compressed, 

dried and distilled

Hydrocarbon vapors 

Rubber

EXPLANATION 

Water 

Product

Steam

rubber 

crumb

Extruding, milling, 

and finishing

Manufacture of butyl rubber (modified from Chemical Engineering, 1944)

Monovinylacetylene

Crude chloroprene

Refined chloroprene

^~~~~^ Chloroprene emulsion 

1 Emulsion I / _ Neoprene

tank N -- 

I J PolymerFractionator izati°n 

tank

Manufacture of Neoprene (modified from Chemical Engineering, 1943) 

FIGURE 41.< Flowsheet illustrating the use of water in the manufacture of neoprene and butyl rubber.

3

H
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 271

polymer forms, which is stripped from the freeze roll. The frozen 

film of polymer is sprayed with warm water, which replaces "the 

aqueous phase in the film with pure water" (Youker, 1947). The 

washed film of rubber is then passed through squeeze rolls and dried 

in a steam-heated air drier. The dried film is formed into a rope, 

about an inch in diameter, which is cut and packaged for shipment. 

In the manufacture of neoprene rubber, cooling water is used to 

cool reactors, and refrigerants and to cool reflux condensers on the 

distillation towers . Process water is used to scrub intermediates, to 

make aqueous emulsions, and to wash the neoprene film. Steam is 

used in reboilers of the distillation towers and in the air drier.

THIOKOL

Thiokol is a synthetic rubber made by the condensation of an alkyl 

dihalide (commonly ethylene dichloride) and sodium polysulfide; the 

latter is made by mixing sulfur in an aqueous solution of sodium 

hydroxide. The exothermic condensation reaction between ethylene 

dichloride and sodium polysulfide is regulated to about 160°F by 

circulating cooling water in a jacket around the reactor. The product 

of polymerization is allowed to settle and is then washed with water. 

Part of the washed latex is shipped; part is coagulated into a crumb, 

filtered, dried, and milled for shipment; and part is mixed with a 

sulfur compound to form a liquid rubber which is washed with water 

and distilled.

Cooling water is used to cool reactors and to cool the reflux condensers of distillation towers. Process water is used for making the 

sodium polysulfide solution and for washing the latex, the crumb, and 

the liquid rubber. Steam is used in the distillation tower reboilers 

and in drying the rubber crumb.

FINDINGS OP THE SURVEY 

SOURCES

At capacity production, about 93.8 million gallons of makeup water 

is withdrawn daily by the plants visited in this survey that manufacture special-purpose synthetic rubbers. Of this amount, 13.9 million 

gallons a day is obtained from company-owned wells, and 79.9 million 

gallons a day of surface water is pumped by companies from, streams 

and is purchased from municipal supplies and State water authorities. 

No saline, ocean, or sewage-water supplies are used in the manufacture 

of these special rubbers. The sources of makeup-water supply for 

cooling, process, boiler-feed, and sanitary and service waters used in 

the specialty-rubber plants are summarized in table 16.
272 WATER REQUIREMENTS OF SELECTED INDUSTRIES

The majority of the plants visited obtain ample water for present 

and future production requirements. Several plants obtain adequate 

water from present sources but will require more water for anticipated 

increases in production. Several plants are exploring additional 

sources of water supply because of diminishing ground-water yields. 

One plant indicated that the present ground-water source is not adequate for present production. Of the 11 plants, 7 now obtain water 

from more than 1 source of supply. Several of the plants purchase 

steam.

TABLE 16. Sources of makeup water used in the manufacture of specialpurpose synthetic rubbers

Source

Well water: Self -supplied _ _

Surface water: 

Self -supplied, _ _

Water authority

Municipal water supply

Number c

Oncethrough 

cooling 

water

6

2

1

1

f plants be

Re circulated 

cooling 

 water

5

3

ing served

Process 

water

6

1

2

byindicat

Boilerfeed 

water

4

1

1

2

ed sources

Sanitary 

and 

service 

water

8

2

1

2

CHEMICAL QUALITY

The chemical constituents of untreated makeup waters used in plants 

manufacturing special-purpose synthetic rubbers are summarized in 

table 17. The table contains the minimum, lower quartile, median, 

upper quartile, and maximum values of each constituent of water used 

for makeup. Because many plants use the same sources of water for 

many purposes, the chemical analyses of all makeup waters were used. 

Chemical analyses of makeup water of purchased steam were not 

available. The significance of the more important chemical constituents in water were discussed on page 232.

As indicated in table 17, waters used as makeup to plants manufacturing special-purpose synthetic rubbers range from soft (less than 

60 ppm) to hard (618 ppm). The majority of the plants used waters 

having a hardness less than 60 ppm, and 75 percent of the plants used 

waters having a hardness of 132 ppm or less. The establishments 

manufacturing a special rubber whose latex is coagulated by calcium 

or magnesium try to use process-water makeup with low hardness.

Most of the makeup waters contain less than 500 ppm of dissolved 

solids. At one location, the high concentration of iron in the ground 

water causes problems and restricts the use of the water. Although 

the waters used for makeup for cooling, process, boiler-feed, .and sani-
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 273

tary and service purposes were similar in chemical quality, the waters 

used for makeup for process and boiler feed contain slightly less dissolved solids and have lower hardnesses than waters used for cooling 

and sanitary and service purposes.

TABLE 17. Chemical properties of untreated water used in the manufacture of 

special-purpose synthetic rubbers

Chemical analyses were furnished by plants manufacturing special-purpose rubbers and by the U.S.

Geol. Survey]

Constituent or property

Silica (SiO2)___-____-________

Iron (Fe)___--___-_-_---____

Calcium (Ca)_ ______

Magnesium (Mg) _____ _ _

Sodium (Na) and potassium

Bicarbonate (HCO3) ___ _____

Carbonate (CO3) __ _________

Sulfate (SO4) _-_ 

Chloride (Cl)________________

Dissolved solids: Residue on 

evaporation at 180°C___ _ _

Hardness as CaCOs- _ _ _

Noncarbonate hardness as 

CaCOs - ---------------

pH_.__. ____________________

Number 

of 

samples

10 

6 

11 

11

7 

18 

18 

14 

18

13 

18

18 

18

Parts per million

Minimum

5.7 

.01 

. 6 

. 1

3.9 

22 

0 

4.0 

4. 8

80 

2

0 

6.9

Lower 

quartile

13 

.05 

3. 2 

. 5

21 

107 

0 

5. 3 

7.0

183 

31

0

7. 1

Median

15 

. 14 

14 

2. 8

45 

153 

0 

12

28

218 

58

6

7. 6

Upper 

quartile

23 

.40 

30 

5. 3

72 

274 

0 

43 

55

312 

132

33 

8. 2

Maximum

46 

.57 

170 

45

121 

560 

18 

280 

378

1,039 

618

350 

9. 0

TREATMENT OF MAKEUP WATER

The treatments given to makeup waters withdrawn for cooling, 

process, boilerfeed, and sanitary and service purposes are summarized 

in table 18. This table does not include any treatment given to the 

makeup water prior to its entry into the plant. Of the 11 plants 

visited, 8 used once-through cooling water. Of the 4 plants that 

did not treat the once-through cooling water, 3 used ground waters 

with a hardness of less than 20 ppm; the other purchased water with 

a hardness of less than 60 ppm that had been clarified and chlorinated.

Of the 11 plants, 7 used recirculated cooling water; the treatment 

given to the makeup for recirculated cooling depending upon the 

quality of the water and the recirculation rate. Three plants, using 

naturally soft ground water, did not treat this makeup water. Of 

the 9 plants using process water, 6 plants did not treat the makeup 

water for process use. Three plants, manufacturing a latex that can 

be coagulated by calcium and magnesium, use a water supply having a 

hardness of less than 20 ppm, demineralize the process water, or use 

recovered steam condensate.
274 WATER REQUIREMENTS OF SELECTED INDUSTRIES

The makeup for boiler feed, at most plants, was treated to reduce the hardness, but a few plants used naturally soft ground water 

for boiler-feed makeup that does not require softening. Two plants 

purchased steam; the treatment of this makeup water is unknown. 

Many of the sanitary and service waters withdrawn from ground 

waters required no treatment; the most common treatments of the 

other water supplies were chlorination and softening.

TABLE IS. Treatment of makeup water at specialty-rubber plants 

[Does not include prior treatment of purchased water]

Treatment

None_ ____ ___ __ ___ ___ _ _ ___

Clarification (sedimentation, coagulation, 

settling, and filtering) ____ _ _____

Disinfection: Chlorine __ ____ __ ____

Prevention of corrosion and scale:

pH adjustment _ _ ___ ______

Softening : 

Lime-soda __ ___ _ ______

Ion exchange _____

Number of plants using indicated treatment

Oncethrough 

cooling 

water

4

2

4

2

1

Recirculated 

cooling 

water

3

1 

2

3

2

Process 

water

6

3

Boilerfeed 

water

1 

2

1 

1

1 

2 

5

Sanitary 

and 

service 

water

6

2 

3

1

1 

1

QUANTITY OF WATER WITHDRAWN AND CONSUMED

The author did not find published information on the quantity of 

makeup water required by the specialty-rubber industry. The 

amounts of makeup water used for once-through cooling, recirculated 

cooling, process, boiler-feed, and sanitary and service in the plants 

visited in this survey are sumarized in table 19. Most special-purpose 

synthetic rubbers are produced by exothermic polymerization reactions that are controlled by cooling waters. More than 90 percent 

of all water withdrawn by this industry is used for cooling. Specialpurpose synthetic rubbers that are produced at low temperatures require considerably more cooling water than rubbers that are produced 

at temperatures greater than 70°F.

Once-through cooling water is used in the manufacture of nitrile, 

thiokol, and neoprene rubbers, thus accounting for about 77 percent of all makeup water withdrawn by this industry. Neoprene uses 

more once-through cooling water than do the thiokol rubbers, which 

use more than do the nitrile rubbers. The minimum amount of oncethrough cooling water required for nitrile rubber was 3.43 gallons 

per pound of finished rubber, for thiokol was 5.85 gallons per pound, 

and for neoprene was 60.3 gallons per pound.
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 275

TABLE 19. Quantity of makeup water used in the manufacture of special-purpose

synthetic rubbers

Water use

Oncethrough

cooling

water

8

Recirculated

cooling

water

7

Process

water

10

Boilerfeed

water

11

Sanitary

and

service

water

11

All uses

11

Gallons per pound

Minimum__ _____

Lower quartile _ _ Median. _ __

Upper quartile _ _

Maximum___ _

3.08

4. 64

20. 8

65.0

97. 6

0. 156

1.57

3.43

5.43

14. 1

0. 522

1. 27

4. 78

9. 45

14. 6

0. 356

. 578

.775

1.03

5. 56

0.053

. 313

. 813

1. 81

13. 2

8. 45

17. 4

19. 8

62. 1

104

Million gallons per day

Total for industry _ _ _ 77.4 7. 5 3.9 2.2 2. 7 93. 8

Recirculated cooling water is used in the manufacture of butyl, neoprene, thiokol, and nitrile rubbers. Cooling water is circulated about 

47 times on the average and as much as 170 times at one plant. The 

amount of water consumed in recirculating cooling water through 

cooling towers ranges from 1.37 to 6.1 gallons per pound of finished 

rubber. Butyl and neoprene use more recirculated cooling-water 

makeup than nitrile rubber; the minimum amount of makeup water 

for butyl rubber is 1.57 gallons per pound. The range of makeup 

water to the cooling towers for the specialty-rubber industry was from 

0.156 to 14.1 gallons per pound of finished rubber.

The amount of makeup water for process use ranged from 0.52 to 

14.6 gallons per pound. The minimum water requirements for butyl 

were negligible, for neoprene were 0.52 gallon per pound, for nitrile 

rubber were 0.548 gallon per pound, and for thiokol were 4.78 gallons 

per pound. The minimum amount of process water consumptively 

used in the manufacture of thiokol, neoprene, and butyl rubbers was 

negligible. The amount of process water consumptively used in the 

manfacture of nitrile rubber ranged from 0.05 to 7.1 gallons per pound 

of finished rubber.

The amount of makeup water for boiler feed for special-purpose 

synthetic rubbers ranged from 0.356 to 5.56 gallons per pound of 

finished rubber. The minimum amount of makeup water for boiler 

feed used by thiokol rubber was 0.055 gallon of water per pound of 

finished rubber, and by nitrile rubber was 0.15 gallon per pound. 

Most producers of special-purpose synthetic rubbers return less steam 

condensate than the amount of boiler-feed makeup water, and these
276 WATER REQUIREMENTS OF SELECTED INDUSTRIES

plants reported negligible consumptive use of boiler-feed water. 

Water used for sanitary and other services is used once and discharged 

to waste. The amount of makeup water for these purposes ranged 

from 0.053 to 13.2 gallons per pound of finished rubber.

TREATMENT OF WASTE WATERS

At capacity production, producers of special-purpose synthetic rubbers discharge more than 85 million gallons of water into surface 

streams each day. The largest part of this waste water comes from 

cooling and is given no treatment before discharge. Most plants 

operate settling basins or retention ponds to remove rubber particles 

and other settleable solids from waste water. Where necessary, most 

plants employ oil separators to retain the floatable materials. Generally the sanitary wastes are processed in Imhoff tanks or discharged 

to septic tanks and sanitary sewers.

FUTURE WATER REQUIREMENTS OF THE 

SYNTHETIC-RUBBER INDUSTRY

The styrene, butadiene, SBR, and specialty-rubber industries are 

young, and the production of these industries in the last 20 years has 

increased tremendously. The production of SBR is influenced by the 

imports of natural rubber, which have been decreasing, and by the 

production of special-purpose rubbers, which has been increasing. 

The production of SBR in 1959 was 32 percent higher than in 1958 

(Chemical and Engineering News, 1960a). The U.S. Bureau of the 

Census (oral communication) anticipates that the SBR industry will 

expand production during the next 5 years at a rate of 50,000 tons per 

year. Unless production methods are changed radically, the production of 1.4 million long tons of SBR in 1964 will require a minimum 

of 43.8 million gallons of water daily, and perhaps as much as 1,602 

million gallons. Radical changes, such as the "superf ast polymerizations" predicted by Whitby (1954), would change the water-use requirements. These methods require at least twice as much deionized 

process water and also alter the cooling-water demands.

Since the birth of the SBR industry, the production of butadiene 

has been related closely to the demands of the synthetic-rubber industry. In 1956, the synthetic-rubber industry took 92 percent (85 

percent by SBR) of the butadiene produced. To offset its dependence 

upon the SBR, the butadiene industry is striving for more markets 

in liquid polymers, intermediates, and m-polybutadiene rubbers 

(Chemical and Engineering News, 1957b). Based on estimates of 

Petro-Tex (1958), the production of butadiene in 1964 will require 

378 million gallons of water daily. No anticipated changes in pro-
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 277

duction methods would greatly change the water-use requirements. 

No production of butadiene from alcohol is anticipated except in the 

event of a national emergency.

In recent years, with the introduction of polystyrene plastics, styrene production has been becoming independent of SBR production; 

and in 1965 only about 29 percent of the styrene produced will be used 

in the production of SBR (Chemical and Engineering News, 1959). 

Production of styrene has been expanding and, according to Chemical 

and Engineering News (1960c), will increase another 40 percent by 

1962. The anticipated production of styrene in 1964 (Chemical and 

Engineering News, 1959), will require about 180 million gallons of 

water daily. No anticipated changes in production methods would 

greatly alter the water-use requirements.

The production of special-purpose synthetic rubbers has been 

increasing radically. The following are the increases in 1959 over 

1958: butyl, 42.5 percent; neoprene, 34 percent; nitrile rubber, 53.0 

percent (Chemical and Engineering News, 1960a). Because of the 

radical changes in production and the introduction of the new rubbers 

like polyisoprene and polybutadiene, no estimates have been made of 

the future water-use requirements.

SUMMARY

Most of the plants manufacturing styrene, butadiene, SBR, and 

special-purpose synthetic rubbers have adequate supplies of water 

for capacity production. Some plants would not have adequate water 

if their production were greatly expanded or if their water supply 

were decreased. Most plants use more than one source of supply, 

and some plants are exploring for additional water supplies. The 

sources of water supply are summarized in table 20. The salty waters 

from ocean, bay, and estuaries are used only for once-through cooling. 

The municipal sewage waters, after treatment, are used principally for 

makeup for boiler feed and recirculated cooling.

Most makeup waters from streams, lakes, and wells contain less 

than 1,000 ppm of dissolved solids, and most makeup waters used in 

the direct manufacture of SBE contain less than 500 ppm of dissolved 

solids. Salty water from the ocean, bays, and estuaries contain as 

much as 35,000 ppm of dissolved solids. The median hardness of 

the makeup waters used in the manufacture of butadiene, SBR, and 

special-purpose synthetic rubber was less than 80 ppm; the median 

hardness for makeup waters used in the styrene industry was less 

than 120 ppm. The maximum hardness of untreated makeup waters 

used for the production of butadiene was 342 ppm; for styrene, 404 

ppm; for SBR, 495 ppm; and for special-purpose synthetic rubbers, 

618 ppm.
278 WATER REQUIREMENTS OF SELECTED INDUSTRIES

TABLE 20. Sources of water used in the manufacture of styrene, butadiene, SBR, 

and special-purpose synthetic rubbers, in percent

Source

Ground water _ _ _ ______

Surface water __ __ _ ____

Salty water __ __ _ ___

Municipal sewage ___ _ _ _ _

Styrene

2

56

42

<1

Butadiene

6

3

90

<1

SBR

55

45

<1

Special 

rubbers

15

85

Most once-through cooling waters are given a minimum of treatment ; the surface waters are commonly clarified and some surface and 

ground waters are chlorinated. The makeup waters to the cooling 

towers are commonly treated with chromates and phosphates to prevent corrosion, or are softened to prevent scale formation. For the 

most part, the process waters used in the manufacture of styrene and 

butadiene are not treated. The process waters used in the manufacture of SBR and special-purpose synthetic rubbers are softened to 

prevent coagulation of latex. Most makeup water for boiler feed is 

softened and deaerated to prevent scale formation and corrosion.

The makeup water requirements, at capacity production, of the 

industries manufacturing styrene, butadiene, SBR, and special-purpose synthetic rubbers are summarized in table 21. The total of 123 

mgd withdrawn in 1959 for manufacturing SBR and special-purpose 

synthetic rubbers is about 36 percent greater than the 90.4 mgd withdrawn in 1954 reported by the Bureau of the Census (1957).

TABLE 21. Summary of makeup water requirements of industries manufacturing 

styrene, butadiene, SBR, and special-purpose synthetic rubbers during 1959

Industry

Styrene___ ____ __ _ ____

Butadiene. _ __ _ ____ _ _ _ __

SBR___._ ________________ _____________________

Total 

makeup 

for Industry 

(mgd)

158

429

29

94

Percent 

used for 

cooling

98

96

17

90

Percent 

used for 

process

62

The makeup water requirements vary according to the product, 

the process used, and the availability of water. The maximum and 

minimum amounts of makeup water, in gallons per pound of finished 

product, used to make the petrochemicals and rubbers are as follows:

Product

Styrene _______________________

Butadiene ____________________

SBR ________________. 

Special-purpose synthetic rubber.

Minimum Maximum

2.19 123

5.38 221

.883 10.2

8.45 104
STYRENE, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 279

Plants with no once-through cooling and with high recirculation 

rates withdrew minimum quantities of makeup water. Where oncethrough cooling was used and the recirculation rates were low, larger 

amounts of makeup water were withdrawn. The water in cooling 

towers was circulated as much as 83 times in the manufacture of 

butadiene; as much as 160 times in the making of styrene; as much as 

170 times in the making of special-purpose synthetic rubber; and as 

much as 240 times in the SBR industry. Most plants reused the 

boiler-feed condensate less than 5 times.

The aggregate amount of makeup water used to produce a pound 

of SBR is the sum of water used to manufacture the styrene and butadiene in a pound of SBR and the amount of water used in the direct 

manufacture of SBR. The aggregate amount of makeup water used 

to produce 1 pound of SBR is calculated to range from 5.1 to 186.8 

gallons per pound of finished rubber, which is 11,400 to 418,400 gallons per long ton of finished rubber.

At capacity production, the styrene industry consumptively uses 

about 3.1 million gallons of water a day; the butadiene industry, 

about 18.7 mgd; direct manufacture of SBR, about 3.2 mgd; and the 

specialty-rubber industry, about 8.6 mgd.

A large part of the waste water discharged by these industries 

is from once-through cooling and is commonly given no waste treatment. Generally, oils are removed from waste water by gravity 

separation or by steam distillation; settleable solids are commonly 

retained in settling basins; where necessary, effluent waters are neutralized and diluted by waste cooling waters.

SELECTED BIBLIOGRAPHY

Blohm, C. L., and Frazier, H. O., 1950, Don't let this happen to your cooling

tower: Chem. Engineering, v. 57, pt. 2, no. 9, p. 140. 

Borg, E. Leonard, 1945, Water treatment at the Institute, W. Va., synthetic

rubber plant: Am. Water Works Assoc. Jour., v. 37, no. 2, p. 209-213. 

Catalytic Construction Company [No date], Butadiene Key to synthetic rubber,

in Firestone Petrochemical Center Butadiene Plant, Orange, Texas: Philadelphia, Catalytic Construction Co., 12 p. 

Gate, D. W. 1958(?), Handling and storage of FR-S latices, in Synthetic rubber

facts: Akron 1, Ohio, Firestone Rubber & Latex Co., 12 p. 

Cennak, R. W. 1946, Instrumenting the Dow Process for styrene production:

Instrumentation, v. 2, no. 3, p. 7-10, 5 figs. 

Chemical and Engineering News, 1957a, Rubber plants on stream at Odessa: v.

35, no. 43, p. 23,1 fig.

 1957b, Butadiene overexpanded but moving: v. 35, no. 52, p. 76-80, 

7 fig., 2 tables.

 1959, Styrene to break records : v. 37, no. 48, p. 26-27, 2 tables.
280 WATER REQUIREMENTS OF SELECTED INDUSTRIES

Chemical and Engineering News, 1960a, C & EN reviews and previews the chemical world 1959/1960: v. 38, no. 1, p. 45-49,2 figs., 7 tables.

 1960b, Cosden expands styrene, o-xylene: v. 38, no. 6, p. 23, 1 fig.

 1960c, Styrene monomer capacity to rise 40 percent in the U.S.: v. 38, no.

8, p. 30-31. 

Chemical Engineering, 1943, Butyl rubber production at Baton Rouge: v. 50,

no. 7, p. 132-135,10 figs.

 1944, Neoprene: v. 51, no. 1, p. 130-133, 10 figs.

 1954, How to make butadiene: v. 61, no. 9, p. 306-309, 4 figs., 1 table. 

Chemical Engineering Progress, 1960, New slant on cooling-tower treatment: v.

56, no. 5, p. 94. 

Connell, C. H., and Berg, E. J. M., 1958, Practice and potentials in industrial

utilization of municipal waste water, in Proceedings of the Thirteenth Indus.

Waste Conf.: Purdue Univ., Eng. Ext. Dept, Eng. Bull. Ser. 96, p. 227-242,

8 figs., 6 tables. 

DeFlon, James G., 1950, Cooling towers and spray ponds, in Perry, John H.,

Chemical Engineers' Handbook: p. 790-798, figs. 45-62, tables. 

Esso Research and Engineering Company, 1957, Butadiene from butenes: Petroleum Refiner, v. 36, no. 11, p. 224, 1 fig., 1 table. 

Forbath, T. P., 1957, Three-in-one process gets butadiene and avgas: Chem.

Eng., v. 64, no. 10, p. 224-227, 7 figs. 

Gorman, A. E., 1943, Administrative policies of the Water Division, Office of

War Utilities: Am. Water Works Assoc. Jour., v. 35, no. 7, p. 846-852. 

Hebbard, George M., Powell, Sheppard T., and Rostenbach, R. E., 1947, Rubber

industry : Indus, and Eng. Chemistry, v. 39, no. 5, p. 589-595, 5 figs., 5 tables. 

Houdry Process Company, 1957, Butadiene from butane: Petroleum Refiner,

v. 36, no. 11, p. 223,1 fig., 1 table. 

Johnson, C. R., and Otto, W. M., 1949 Monomer recovery in GR-S manufacture:

Chem. Eng. Prog., v. 45, no. 6, p. 407-414, 4 figs., 3 tables. 

MacKichan, Kenneth A., 1957, Estimated use of water in the United States,

1955: U.S. Geol. Survey Circ. 398, 18 p., 6 figs., 12 tables.

Madigan, J. C., and Adams, J. W., Latex incorporated carbon black for synthetic rubber: Chem. Eng. Prog., v. 44, no. 11, p. 815-820, 14 figs., 1 table. 

Martin, Arthur E., and Rostenbach, Royal E., 1953, Industrial waste treatment

and disposal at the Government synthetic rubber plants: Indus, and Eng.

Chemistry, v. 45, no. 12, p. 2680-2686, 5 figs., 2 tables. 

McCormick, E. B., and Wetzel, O. K., Jr., 1954, Water supply from sewage

eflluent: Petroleum Refiner, v. 33, no. 11, p. 165-167, 1 fig., 1 table. 

Meyer, R. R., and Turcan, A. N, Jr., 1955, Geology"and ground-water resources

of the Baton Rouge area, Louisiana: U. S. Geol. Survey Water-Supply Paper

1296, 137 p., 40 figs., 6 tables. 

Mitchell, J. Ernest, 1946, The Dow process for styrene production: Am. Inst.

Chem. Engineers: v. 42, p. 293-308, 7 figs. 

Moore, E. W., 1940, Progress report of the committee on quality tolerances of

water for industrial uses: New England Water Works Assoc. Jour., v. 54,

p. 263-270. 

Mussey, O. D., 1961, Water requirements of the copper industry: U. S. Geol.

Survey Water-Supply Paper 1330-E, 4 figs., 22 tables.

Neches Butane Products Company, [No date], Design capacity 100,000 tons butadiene per year demonstrated capacity 150,000 tons butadiene per year:

Port Neches, Tex., Neches Butane Products Co., 17 p., 5 figs., 4 pis.
STTKENB, BUTADIENE, AND SYNTHETIC-RUBBER INDUSTRIES 281

Nordell, Eskel, 1951, Water treatment for industrial and other uses: New York,

Reinhold Publishing Corp., 526 p., 126 figs., 162 tables. 

O'Connell, W. J., Jr., and Gregory, T. R., 1944, Study on the problem of handling

industrial waste: U. S. Rubber Reserve Corp., 32 p., 10 pis. 

Olive, T. R., and Shreve, R. N., 1947, Chem. & Met.'s chemical engineering flowsheets : Chem. Engineering, 150 p. 

Petro-Tex Chemical Corporation, 1958, Butadiene its present and potential

uses: Houston, Texas, Petro-Tex Chemical Corp., 44 p., 6 figs. 

Powell, Sheppard T., 1954, Water conditioning for industry: New York, McGrawHill Book Co., Inc., first ed., 548 p. 

Rainwater, F. H., and Thatcher, L. L., 1960, Methods for collection and analysis

of water samples: U. S. Geol. Survey Water-Supply Paper 1454, 301 p.,

17 figs., 3 tables. 

Reidel, John C., 1957a, What's happened to butadiene since private industry

took over?: Oil and Gas Jour., v. 55, no. 45, p. 166-171, 4 figs., 2 tables.

 1957b, Butylene dehydrogenation by the steam-dilution method: Oil and 

Gas Jour., v. 55, no. 48, p. 87-95, 2 figs., 3 tables.

 1957c, Butadiene dehydrogenation today employs fixed-bed method:

Oil and Gas Jour., v. 55, no. 49, p. 115-122, 5 figs., 7 tables.

Russell, R. P., Murphree, E. V., and Asbury, W. C., 1946, The production of butadiene by the dehydrogenation of normal butylenes: Am. Inst. Chem. Engineers Trans., v. 42, p. 1-14, 5 figs., 2 tables.

Sanders, Howard J., Keag, Harry F., and McCullough, Howard S., 1953, Acetophenone: Indus, and Eng. Chemistry, v. 45, no. 1, p. 2-14, 6 figs., 4 tables.

Smith, A. A., 1947, Los Angeles styrene plant: Chem. Eng. Prog., v. 43, no. 4, 

p. 152-154, 3 figs.

Soday, Frank J., 1946, The preparation and properties of GR-S: Am. Inst Chem. 

Engineers Trans., v. 42, p. 647-665, 1 fig., 3 tables.

Stein, Paul J., 1945, Cooling water and effluent treatment in butadiene manufacturing : Natl. Petroleum News, v. 37, no. 14, p. R-273, R-274, R-276, R-278, 

2 figs.,1 table.

Sullivan, Thomas F., 1958, Sewage effluent used for industrial water: Sanitary 

Eng. Div. Jour., Am. Soc. Civil Engineers Proc., Paper 1679, p. 1-15.

Thayer, C. H., Lassiat, R. C., and Lederer, E. R., 1942, The Houdry combined 

two-stage dehydrogenated catalytic process for the manufacture of butadiene: Automotive and Aviation Industries, v. 87, no. 8, p. 30-32, 1 fig., 4 

tables.

United Nations, 1958, Water for industrial use: New York, United Nations, Dept. 

Econ. and Social Affairs, 44 p., 16 tables.

U.S. Bureau of the Census, 1957, Industrial water use: U.S. Bur. Census Bull. 

MC-209 (1954 Census of Manufacturers separate), 52 p., 1 fig., 7 tables.

U.S. National Production Authority, 1952, Materials survey Rubber: 82 p.

Whitby, G. S., 1954, Synthetic rubber: New York, John Wiley & Sons, 1044 p.

Youker, M. A., 1947, Continuous isolation of GR-M from latex : Chem. Eng. Prog., 

v. 43, no 8, p. 391-398,2 tables, 9 figs.

INDEX

Page

Acknowledgments_______________ F222 

Alcohol, butadiene from___________ 245

Bay water, number of plants supplied with. 231,246 

Bays, source of makeup water. __ _____ 245 

Brazos River, quality of water withdrawn

from_________________ 246 

Butadiene industry, future water requirements. .---___.._______ 276 

Boiler-feed make-up water, amounts withdrawn

and consumed_________ 238-239, 

250-251,263,264,275

chemical properties____________ 233,260 

definition--_-_._._._._____ 222,223 

quantity used__..._._-_ 238,250,263,275 

sources.-..-_____________ 231,246,259,272 

treatment-__...-_._.__ 237,249,262,274 

Butadiene manufacture, chemical quality of

makeup water__- ______ 246-248 

cooling water________________ 249 

dehydrogenation, Houdry process___ 241,244 

steam-dilution method... ___ 240,241,244 

feed preparation_________ ____ 240 

flowsheet_______________ 240,242 

from alcohol_________________ 245 

from petroleum______________ 239 

process water___________ ____ 253 

processes and products..._______ 224,225 

purification, CAA process.________ 244 

distillation towers.._______.. 244 

quantity of water withdrawn and consumed-.__________________ 248 

recovery of butadiene and styrene___ 252,253 

use of salty water_____________ 249 

sources of makeup water____ ____ 245,246 

survey findings_____________ 245-251 

total water used_______ ____. 225,250 

treatment of makeup water.._____ 248,249 

treatment of waste waters.-_______ 251 

use of steam___ ____ ______. 240 

water requirements___________ 225,265 

water use________________ 239-245 

Butyl, uses. ______._______ 223 

Butyl rubber manufacture, flowsheet____ 270 

plants visited-_______________ 225 

quantity of water withdrawn and consumed________________ 274 

water use in...______._______ 269

Calcium ions in makeup water________ 232 

Carbide and Carbon Chemicals Corp., styrene

process-______________ 226

Page

Carbide and Carbon process, water requirements._______________ 230 

Carbon-black crumb... ..... ... 252,257

oil-extended.___ .. ___ 257 

Carbon-black slurry, process water requirements.______________ 224 

Chemical constituents of water, significance.. 246 

Chemical quality of makeup water._232,246,260,272 

Chloride anions in makeup water _ .... 233

Clarification of makeup water. __ 237,249,262,274 

Cold rubber, cooling-water requirements..... 224

Cooling and process water, untreated, chemical properties _ . 260 

Cooling towers, makeup water to_ 235,237,248,275 

Cooling water, definition_ 222 

once-through, quantity used. _. 238,250,275 

sources... 231,246,259,272

treatment----.____-_ 237,249,262,274

recirculated, quantity used. 238,250,263,275 

sources 231,246,259,272

treatment.. 237,249,262,274

untreated, chemical properties 233 

use 230,235-237,240,248,261,263

Corrosion and scale, preventive treatment 233, 

234,237,249,262,274

Cosden Petroleum Co., styrene process. 226 

Cosden process, water use in 230-231

Dehydrogenation, water use for. . 227, 

230,231,239,240-242

Disinfection of makeup water. 237,249,262,274 

Dissolved solids in makeup water. -.. 232 

treatment.... .... - --- 237 

Dow Chemical Co., styrene process - 226,237 

Dow process, water use in.. 226-230

Estuaries, source of makeup water ... 231,245,246 

Ethylbenzine, formation and dehydrogenation of -_-_____-____ 226-227

Feed preparation,. 240,252 

Findings of the survey - 231,245,259,271 

Furfural, use in butadiene purification.. 244-245,250 

Future water requirements, synthetic-rubber

industry 276

Gulf of Mexico, quality of water withdrawn.. 247

source of makeup water 245,247

Ground water, source of makeup water 245

Hardness in makeup water____ 232-233,261,262 

History of synthetic rubber in United

States.. 223-224

Houdry process of dehydrogenation. . 241,244,251

283
284 INDEX

Page 

Institute, W. Va., makeup water required for

SBR. ... __.............. 285

Iron in makeup water. _.__._______ 234

Kobuta, Pa., makeup water to butadiene

plants - . -. 248,249,250

Latex, conversion to dry rubber________ 257

treatment-_-_ ____________ 237

water consumed.-.-..__________ 264

Latex formation..._.____.____ 251,252,253

Latex plants, makeup water required_...... 264

Magnesium ions in makeup water______ 232

Makeup water, chemical properties. 233,247,260,273 

classification.....-- _________ 222

future requirements, at maximum production...... . ____....._ 278

quantity used.. . 238,250,263,265,267,275 

recirculated...._ ___________ 239

sources... 231,245,246,259,271,272,278 

to cooling towers..__________ 235,237,248 

total requirements..________ 250,265,267 

treatment.... .... .... 235,237,249,259,262

types used in styrene manufacture____ 235

Manufacturing processes, makeup water requirements, summary______ 278 

source of water used...._________ 231,278 

waste-water disposal ___________ 279

Municipal sewage, number of plants supplied

by...._. _________._ 231 

treatment for use in styrene manufacture.. 237

Mussey, D. D., quoted____________ 222

Neoprene manufacture, flowsheet of water use. 270 

plants visited________________ 225 

quantity of water withdrawn and consumed _____________ 274 

useof water in manufacture of_____ 269,271 

uses of.____________________ 223

Nitrile manufacture, plants visited______ 225 

preparation of. _______________ 268 

uses...___________________ 223

Ocean water, number of plants supplied ___ 231 

Oil-extended carbon-black crumb___ 224,256-258 

Oil-extended SBR, process water on water requirements___________ 224,256-257

Pacific Ocean, source of makeup water____ 245 

Petroleum, butadiene from___________ 239 

Plants visited.,..________________ 225 

Potassium salts in makeup water______ 234 

Process water, definition....__________ 222

quantity used. _______.._ 238,250,263,275 

sources_ . _____ 231,246,259,272 

treatment_....._._....... 237,249,262,274

use - . 224,238, 239,252,275

Production, special-purpose synthetic rubbers. 277

Page 

Quantity of water used, totals.- 238,

250,263,265,267,275 

Quantity of water withdrawn and consumed . 238,

248,262,264,271,274

Salty waters, use for once-through cooling. 248,

249

Sanitary and service water, definition.. : 222 

quanity used______._._ 238,250,263,275 

sources. 231,246,259,272

treatment-...__-_-___ 237,249,262,274 

use 237,239,246,264,276

Scope of investigation 222 

Selected bibliography. . . .. 278 

Silica in makeup water 234 

Sodium pentachlorophenate, in treatment of

makeup water_ 237

Sodium salts in makeup water 234

Sources of makeup water, for butadiene . 245-246

for special-purpose synthetic rubbers..... 268

for specialty-rubber plants. 271 

for styrene - 231-232

for styrene-butadiene rubber 259 

Specialty-rubber industries, future water requirements- ___ 277 

Specialty-rubber manufacture, butyl rubber. - 269 

chemical quality of makeup water... 272,273 

flowsheet, butyl and neoprene ... 270 

neoprene...-___ . 269,274 

nitrile rubber.. . 268,274 

plant visited_... 225 

quantity of water withdrawn and consumed..__._._ __ . 274,275 

sources of makeup water . 271 

survey findings 271-276 

thiokol _ 271,274

total water used. 275

treatment of makeup water... 273

treatment of waste waters __ 276

water use._._. . ... - 268-271

Steam, use of - 224,239,240,250,251,252,254

Styrene industry, future water requirements- 276

Styrene manufacture, Carbide and Carbon

process, water use.... 230

chemical quality of makeup water 232-235 

Cosden process, water use. 226-230 

Dow process__ 226 

formation and dehydration of ethylbenzene __._-___-_ 226,227 

flowsheet of water use.- _ 228 

future water requirements 278 

history- --_ -- -- - 223,224 

processes and products.-.. 225 

purification of styrene_ ......- 226,227,230

sources of makeup water_ 231 

total water used. . 225,238 

percent consumed. 238 

treatment of makeup water 235 

treatment of waste waters.... 239

water use_ . 226
INDEX 285

Page

Styrene-butadiene rubber, uses. 223 

Styrene-butadiene rubber, industry, aggregate

water use_.. __.___ 225 

future water requirements. .. ___ 276 

Styrene-butadiene rubber manufacture, aggregate quantity of water required for 

production...... .... 255,262,265,267

carbon-black crumb.__________ 252,257 

chemical properties of makeup water._ 260 

feed preparation ___ 252 

flowsheet of water use___.. ______ 254 

latex. ___._._._____..__ 224,252 

conversion to dry rubber ..___ 257 

flowsheet of water use__._______ 254 

oil-extended carbon-black crumb...___ 257 

oil-extended SBR......_....__.._.. 257

recovery of butadiene and styrene from

latex- .._.__._-----__ 253-257

sources of makeup water . .- 259 

total water used....___________ 262

percent consumed. __._______ 263

Page

Styrene-butadiene rubber manufacture Con. 

treatment of makeup water______ 261,262 

treatment of waste water. .. 264 

survey findings______.______ 259-265 

water use___.... . 251-259 

Sulfate anions in makeup water.... -. 233 

Summary.... 277 

Surface water, number of plants supplied with. 231 

Synthetic rubber, types of.. ., 223 

Synthetic-rubber industry, future water requirements. 276

Thiokol manufacture, plants visited 225 

quantity of water withdrawn and consumed- 274 

water use_...- 271 

Thiokol, uses of..___...-_________- 223 

Treatment of makeup water 235,248,261,273 

Treatment of waste water_...- 239,251,265,276

Water use, basis for reporting_ 225-226 

Well water, number of plants supplied with- 231

o