PROCESS FOR CONVERTING PETROLEUM AND SIMILAR HYDROCARBONS INTO ACIDS, SOAPS AND COMPOUNDS ANALOGOUS IN CONSTITUTION TO RESINS AND ETHERS to be as follows:
Year: 1884

page_text: to Resins and Ethers.
I, JOHN IMRAY of N° 28 Southampton Buildings, Chancery Lane in the county
of Middlesex, Consulting Engineer and Patent Agent, do hereby declare the nature
of my said invention for "PROCESS FOR CONVERTING PETROLEUM AND SIMILAR
HYDROCARBONS INTO ACIDS, SOAPS AND COMPOUNDS ANALOGOUS IN CONSTITUTION
TO RESINS AND ETHERS to be as follows:-
.
"
When petroleum or hydrocarbons resulting from dry distillation of coal, shale,.
peat &c are subjected to high temperature in a metallic vessel with or without
pressure, in presence of caustic alkalies or alkaline earths, or their carbonates, or
substances of alkaline character, with a current of air or oxygen the hydrocarbons.
become converted into acids which combine with the alkalies, forming soaps. The
same result is obtained when the hydrocarbons finely divided and neutral
substances such as infusorial earth or pumicestone &c, with lime, are subjected to
the action of the air current. The conversion into, acid also results when the
finely divided hydrocarbons, in admixture with neutral substances, are oxidised by
the action of materials that give off oxygen, as, for example by admixture of
chromates, chlorates nitrates, permanganates, with acid sulphates &c, absorbed in
infusorial earth.
The treatment on the large scale is such that, for instance, the hydrocarbons
intimately mixed with alkali flow continuously into a close vessel through which
at times a current of compressed air is passed giving violent agitation, and from
which, at times, the produced soaps are withdrawn.
The oxidation proceeds rapidly and the continuous supply of hydrocarbon can be
regulated to suit the speed of the soap production. Obviously the process might
be carried on discontinuously. Superoxidation, sometimes manifesting itself by
production of acid, can be prevented by adding zinc powder to the alkaline mixture
or by directly treating the acids with zinc powder,

page_text: From all these operations result in the first place soaps, which can partly be
mechanically separated from the superfluous hydrocarbon. These soaps are
themselves mixtures of a set of alkaline salts resulting from the separation of the
different acids by fractional action. The insolublo metal-soaps are decomposed by
mineral acids, and the organic acids are dissolved by benzene, ether, caustic or
common soda &c. The acids capable of distillation can also, for example, be
extracted from the pumice &c, by petroleum. These, that is to say, the acid
mixtures soluble in petroleum, are subjected to distillation in vacuo, by which the
acids can be fractionally obtained, fixed acids or hardoned residues of the distillation
remaining. These as well as the oxidised products insoluble in petroleum, form an
asphalt with lime or magnesia, and also form soaps with alkalies.
The more volatile acids of distillation are by no means simple products, but differ
much, according to the products of the manufacture. Their general character is
however uniform. The acids form soaps and normally those more highly constituted
are nearly allied to oleic acid.
The separate fractional parts of the acid mixtures resulting from oxidation of the
hydrocarbons, may be applied for production partly of resin-acid-ethers, partly of
soaps, partly to be used themselves.
The more volatile acids give with methyl, ethyl, butyl, amyl, alcohol, fragrant
ethers suited for perfumery. With glycerine they form combinations like natural
oils, which can take the place of rape oil &c, and when mixed with acids can be
used even as spindle oil.
The less volatile acids, which resemble oleic acid, produce excellent soaps, and
the ethyl, sugar and glycerine combinations of these oils act like natural oils and
fats. The residues of distillation of the higher resin-acid-ethers can be used in
the manufacture of varnishes and the like.

page_text: оница Пуигосагроп
into Acids, Soaps, and Compounds Analagous in Constitution
to Resins and Ethers.
I, JOHN IMRAY of No. 28 Southampton Buildings, Chancery Lane in the county
of Middlesex, Consulting Engineer and Patent Agent, do hereby declare the nature
of my invention for "PROCESS FOR CONVERTING PETROLEUM AND SIMILAR HYDRO-
CARBONS INTO ACIDS, SOAPS AND COMPOUNDS ANALOGOUS IN CONSTITUTION TO
RESINS AND ETHERS and in what manner the same is to be performed to be
particularly described and ascertained in and by the following statement:-
23
When petroleum and hydrocarbons resulting from dry distillation of coal, shale;
peat, etc, are mixed with caustic alkalies, their carbonates, alkaline earths or other
substances having alkaline reaction and are treated in a metal vessel, at high
temperature, with or without pressure, with a current of air or oxygen, the
hydrocarbons are converted into acids which combine with the alkali to form
60apя
Example. The fractions of the hydrocarbons that boil at from 150° to 400° Cent.
are mixed in the first instance with a small percentage of a finely powdered mixture
of about equal parts of calcium oxide, sodium hydrate and soda or only of calcium
oxide or sodium hydrate with or without soda, carriers of oxygen and other alkalies,
and is heated to violent ebullition in a high metal vessel, filled to about two thirds
of its capacity, and provided with a stirring apparatus and with a long reversed
current cooler, compressed air or oxygen being at the same time led through the
mass from a gasometer or by means of a pump under continual stirring. By means
of a cock on the reversed current cooler, the pressure can be increased to several
atmospheres.
The heating of the vessel may be effected by superheated steam or by hot gases
or by direct fire heat, which should however only be in contact with the side of
the vessel. If direct fire heat be employed, a considerable addition of common
salt will afford some security against the burning of the mass:
After a time a further quantity of alkali is added, preferably so that the alkali
is automatically incorporated by suitable apparatus with the hydrocarbon that
flows back, in order to lead it continuously and in a finely state into the boiler.
It is also advantageous to lead gaseous ammonia through the mass. The quantity
of alkali is calculated according to the average equivalent weight of the hydro-
carbon. The oxygen converts the hydrocarbons into acids, that combine with the
alkali to form soap and are mostly deposited in insoluble form on the bottom of
the boiler, whence they are removed from time to time. If the soaps produced are
only soluble in water, they may be removed by the addition of water to the slightly
cooled mixture.
The boiler may advantageously be made of the form shewn on the accompanying
drawing. a is the heated boiler; the soaps descend into the recess c in b and are
removed by suitable scoops while the process is continued in a

page_text: In the above.described manner various kinds of petroleum, coal and lignite oils,
and shale oils have been oxidised with success. These constituents that are
oxidised with greater difficulty are tilised as lubricants and burning oils, having
little odour.
The same result is obtained if the above named bydrocarbons are mixed in a
finely divided form with about 20 per cent of caustic alkalies, or their carbonates,
alkaline earths, or other alkaline compounds, and in some cases with oxygen
carriers, such as copper salts etc, and with neutral substances auch as pumice stone,
infusorial earth, common salt, glauber salts, etc, the mixture being such that a dry
powder is still obtained which is left for some time in intimate contact with the
air. This may be effected in a rotating drum containing a reversed current cooler
either with or without pressure and proferably with careful heating by means of
steam. A higher temperature considerably accelerates the operation, but even at
ordinary temperatures the formation of acid takes place after lengthy treatment.
The process is continued until a sample gives a considerable yield of acids.
If materials soluble in water are used the salts are first dissolved out in a small
quantity of water, and are then dried and used again; by the further addition of
water the goaps become dissolved. When using. lime, coppar Balts, pumice stone,
infusorial oarth etc, the metallic oxides must first be removed. by means of hydro-
chloric acid; the liquid acids dissolved in excess of petroleum can then be removed
by pressure and be extracted from the solution by means of alkalios, the solid
acids boing separated from the disseminating medium by means of alcohol, ether,
Boda, etc.
Some hydrocarbons are also converted into acids by means of chloride of lime.
For this purpose, it is proved by experiment whether a hydrocarbon is oxidisable
by means of chloride of lime, whereupon the hydrocarbon is mixed gradually,
under stirring, with the proper amount of chloride of lime, the mass being cooled if
the action be too violent, or heated carefully up to 125° Cent., if the reaction does
not set in. At this temperature there frequently onsuos a violent reaction. Many
hydrocarbons oxidise with chloride of lime very readily, others not at all.
If the added chloride be not altogether consumed, which is easily ascertained by
means of indigo, more bydrocarbon is added and the mass is hented for some time
to from 130° to 200° Cent.
The lime is then removed by hydrochloric acid; the acids produced are extracted
by alkalies and the remaining oil compound is by preference melted for some hours
with about 50 per cent of caustic soda at from 200° to 300° Cent. A tolerably large
quantity of intermediate products are converted into acids by these means.
Many hydrocarbons are readily oxidised by means of strong nitric acid.
This oxidation is preferably conducted in such manner that a number of glass.
earthenware or stone vessels are filled to from to with the hydrocarbon and are
connected together by gas pipes in the known manner. Into the first vessel is then
introduced from one half to an equal quantity of nitric acid, or this is developed
from nitre and sulphuric acid, or it is introduced in gaseous form and together with
it a strong current of air at a temperature of about 100° Cent. The first vessel
frequently becomes very much heated in consequence of which the addition of
nitric acid must be effected very carefully; afterwards it is heated like the others
to about 150° Cent., until the nitric acid is all used. Vessel 1 is now omptied and
is filled afresh and the requisito quantity of nitric acid is now added to vessel 2,
while vessel 1 now becomes the last vessel in the system and so on.
Acids aro thus formed as also nitrogenous products and intermediate products.
The acids are romoved from the compound by means of soda lyo. The undissolved
constituents are melted with about 50 per cent of caustic soda for some hours at a
temperature of from 200° to 300° Cent, and a large quantity of acid free from
nitrogen is thus obtained.
The acids obtained by those various methods are mixtures which nil form soaps
and which can be separated by distillation, fractional precipitation or extraction.
The simplest way of proceeding is to extract the acids with benzine or petroleum,

page_text: The liquid acids by this method mostly enter into solution, while the solid ones
remain insoluble; also by distillation in vacuuo, the volatile liquid acids can be
separated from the non-volatile solid ones.
Super-oxidation, which sometimes occurs with the liquid acids, apparently by
formation of dry-acids can be brought back again by treatment with zinc powder in
alkaline solution, or directly by treatment of the acids with zinc powder. The liquid
acids are now subjected to distillation in vacuno at a temperature up to 360° Cent.
Resinous portions remain which are similar in their properties to the acids that
are insoluble in petroleum. These solid acids yield soap on treatment with
alkalies; with lime and magnesia they give asphalt-like masses. Their esters are
more or less hard resins, which can be employed in the manufacture of varnishes or
as substitutes for wax, pitch or asphalt. The volatile distillable acids are of course
no uniform compounds, but differ according to the original materials employed.
The general character of the same is however very similar. The acids all form
soaps and in particular those of a higher constitution are very nearly related to
oleic acid. The separate fractions of the acid mixtures resulting from oxidation of
the hydrocarbons may be used partly for the production of ester like bodies, partly
for soaps, and may partly be themselves used as such. The most volatile acids
give, with methyl, ethyl, butyl and amyl alcohols, useful aromatic ethers suitable
for perfumes. The next following ones form, with ethyl alcohol and glycerine,
combinations similar to natural oils, which may be employed in place of rape seed
oil and when mixed with the acids themselves may be used as tournante oil
(a thick olive oil used in dyeing).
Example. The liquid or solid acids are dissolved in a suitable quantity of a
strong alcohol mostly from 1 to 1 parts, and from to part of sulphuric acid-
salts etc., is gradually added and the mixture boiled for some hours; or dry hydro-
chloric acid is led into the alcohol solution until saturation ensues and the mixture
is allowed to stand for some time.
In both cases, the ester will soon separate. By distilling off the superfluous
alcohol, or by mixing with water, fresh quantities of ester are obtained. Alcohols
of high boiling point or that are not volatile may be advantageously combined
with these acids by lengthened heating under pressure with or without dehydrating
substances. The alcohols and acids are mixed in their equivalent proportions and
the mixture is heated according to its character, from 120° to 800° Cent., at a
pressure of several atmospheres until a combination is effected; also by heating the
mixture and passing through neutral gases, for instance carbonic acid, ester
formations may be effected. With glycerine ether, the temperature can be carried
to 250° Cent.
With ether, it is advisable not to go higher than 150° Cent. The esters are
purified in the well known manner by washing with water and soda and by
distillation in vacuuo in so far as they may be distilled without being decomposed.
Having now particularly described and ascertained the nature of my inven-
tion and in what, manner 'the same is to be performed I declare that what
I claim is
1. The conversion of petroleum and hydrocarbons resulting from distillation of
lignite, coal, peat, shale etc, into organic acids by treating the hydrocarbons in the
presence of caustic alkalies, alkaline earths, alkaline carbonates, or other bodies
with alkaline reaction, with a current of air or oxygen, with or without pressure,
at a raised temperature, and decomposing the soaps formed, the free acid being
removed from the compound which is then separated into single.fractions by
fractional distillation or by taking advantage of the unequal solubility in petroleum
or similar solvents,
2. Converting petroleum and hydrocarbons derived from the distillation of
coal etc, into acids by mixing them intimately with neutral bodies such as pumice
stone, infusorial earth, salt, glauber salts, salts of copper and alkalies and treating

page_text: the same with a current of air, either cold or hot and either with or without
pressure, the soaps obtained being treated as set forth in the preceding claim.
8. Converting petroleum and hydrocarbons resulting from the distillation of
coal etc., into acids by incorporating the same intimately with chloride of lime,
then heating the same, the mixture being freed from lime by means of hydrochloric
acid and the organic acids produced being separated by means of alkalies, while
the residual oleagenous mixture is melted with caustic soda, the soaps being treated
´as set forth in the first claim.
4. Converting petroleum and hydrocarbons resulting from the distillation of
coal etc., into acids by introducing the same into a system of vessels connected by
gas conduit pipes and at the same time acting thereon by means of nitric acid with
air under heating and lastly by removing the organic acids produced by means of
alkalies and melting the residual oleagenous mixture with caustic alkalios, the
soaps formed being treated no set forth in the first claim.
5. The conversion into soaps and ester-liko compounds of the acids obtained by
oxidation of petroleum and similar hydrocarbons as set forth in the preceding
claims, as also the acids obtained by oxidation with air without alkalies, and even
by acidulation as also the acids obtained from the monochloride and monosulpho
combinations of petroleum &c by melting with caustic alkalies, the said acids being
previously purified and separated; the ester-like compounds are partly applicable
for perfumery, partly as substitutes for natural oils and fats, and partly as
substitutes for wax, asphaltum, pitch and varnish resins.
6. The employment of the isolated liquid acids obtained according to claims 1
to 4, as also the sulpho-acids and acid-esters obtained according to claims 1 to 5
(the acid esters being in combination with liquid petroleum acids) as substitutes
for tournante-oil.