Patented Oct.

15, 1940 2,218,174

UNITED STATES PATENT OFFICE
2,218,174
PREPARATION of suLPHONIC ACIDs
Arthur Lazar and Paul Moritz Ruedrich, Berkeley,
Calif., assignors to Tide Water Associated Oil
Company, San Francisco, Calif., a corporation
of Delaware
Application March 30, 1938, Serial No. 98,976
8 Claims. (C. 260-504)
This invention relates to the preparation and benzol-sulphur dioxide, phenol, cresylic acid, di
purification of sulphonic acids. chlorethylether, or by other well known solvent
An object of this invention is to provide a proc refining processes, whereby an extract is re
ess whereiby hydrocarbon oils may be sulphonated moved therefrom. The material which is in
5 and the sulphonic acids thus produced separated Soluble in the selective solvent will hereafter be
from the residual oil. termed rafflinate, and is an oil which is preferably
A further object is to provide a process where the raw material used for sulphonation.
by the crude Sulphonic acids may be purified to For the Sulphonation of the base oil concen
enable the recovery of sulphonic acids Substan trated sulphuric acid is recommended, however,
10 tially free of contamination products. other sulphonating agents may be used. For O
Another object is to prepare substantially pure example, chlorosulphonic acid, or sulphuric acid
sulphonic acids which are especially adapted to in conjunction with certain water absorbing in
form metal soaps of a high degree of compati gredients, such as phosphorus pentoxide, may be
bility with hydrocarbon oils. used to aid the sulphonation process. By con
5 . An object of this invention is to treat a hy- . centrated sulphuric acid, 66° Bé. up to 50% fum 5
drocarbon oil in such a manner that an isola ing Sulphuric acid is meant; however an acid
tion of classes of chemical constituents is ac strength of 5 to 20% fuming sulphuric acid is
complished. preferred.
Other objects of invention will be apparent In the Sulphonation of the raffinate the acid
20 as the Subject is more fully disclosed. is preferably added in increments of from 5 to 20
The usual processes of preparation and puri 10 pounds per barrel of oil. The first few in
fication of Sulphonic acids involve the Sulphona crements attack oil constituents which are eas
tion of reactive hydrocarbons in oils. With fum ily sulphonated, oxidized or polymerized and re
ing sulphuric acid, the neutralization of Sulphonic move them as a tarry mass in the acid sludge.
acids formed with an alkaline reagent and the Through the initial removal of such constitu 25
Separation and purification of such acids Over ents, acid used in subsequent increments is not
their metal salts. Spent in side reactions, but is directed in sub
By this is meant that the Sulphonic acids are stantially full strength towards the sulphona
extracted as water soluble alkali Salts, the lat tion of hydrocarbons to yield sulphonic acids.
ter being converted to less soluble alkaline earth By the use of acid in increments therefore acid . 30
metal salts, which then can be purified by either Sludges can be produced in which the concen
recrystallization or any other conventional tration of acid tar progressively decreases while
means. From the purified salts, the pure sul the concentration of sulphonic acids which re
phonic acids then can be isolated by acidification main dissolved in the oil increases.
35 with mineral acids. To illustrate the increase in concentration of 35
This invention provides a process of prepara sulphonic acids which remain dissolved in the
tion, extraction, and purification which may be oil, with progressive applications of increments
applied to the production of all types of sul of acid, the following data, are given.
phonic acids. One of the advantages of Such
40 process is that it permits the preparation of sub Percent Sul
stantially pure sulphonic acids utilizing only Increment phonic acids 40
standard metal equipment. number Quantity of acid used by weight
dissolved in
The type of hydrocarbon oil, which may be the oil
used as the starting point of the sulphonation
process, is governed commercially solely by the 2.----------------
1------------ 10 lbs. per barrel of 15% fuming H2SO4.
do------------------ - - - ? ? ? - - - - - - - - -
2.63
45
necessary qualification that appropriate yields
of Sulphonic acids can be obtained therefrom by
sulphonation, but the process is broadly applica The percent of sulphonic acids which remains
ble to the production of Sulphonic acids from in the Oil increases with the increments of acid.
50 all sulphonatable hydrocarbon Oils, such as may It is found, however, that as the concentration
initially be obtained, for instance, from a lubri of Sulphonic acids in the oil is increased, the sul 50
cating oil fraction from petroleum. Such a frac phonating action of the sulphuric acid gradu
tion may be from naphthenic, paraffinic or mixed ally decreases. In other Words, the sulphona
base crudes, and the preferred viscosity range tion process slackens and the efficiency of the
55 is from 45 to 350 viscosity Saybolt Universal at treating reagent decreases, in proportion to the 55
100° F. · accumulation of Sulphonated components in the
Such base oil fraction may be sulphonated di oil. For this reason it is often preferred to re
rectly or may be first Subjected to treatment by move the Sulphonic acids, after their concentra
a solvent refining process, such as is well known tion has reached about 5% by weight, as an in
60 in the use of liquid sulphur dioxide, furfural, termediate processing step. Such removal can 60
 2 .. 2,218,174
be accomplished by neutralization with an alkali, tamination of the sulphonic acids is avoided and
thus converting the sulphonic acids into soaps. occlusion of certain impurities, discussed later in
It is preferred, however, to accomplish such re detail, is minimized. Modern refining practice,
moval by the process shown in the accompany incidentally, may include the centrifuging oper
ation, following as a normal procedure the me- is
? drawing, which will be described in detail chanical
OW acid contacting step. In other words,
By using this step procedure of alternate sul the added precaution of centrifuging mentioned
phonation and removal of sulphonated products, above is specifically recommended for such oils,
the advantages are: which are obtained by the old batch treating
1. Better utilization of the treating agent.
10 2. method in air blown agitators. O
Increased yields of sulphonic acids. The extraction of sulphonic acids from the
3. A segregation of sulphonic acids according acid oil. may be accomplished by the use of or
to types, as explained in detail below. ganic solvents or aqueous solutions thereof. Or
This procedure is highly recommended in the ganic solvents which are completely water soluble
5 manufacture of technical white oils and medici are preferred. The proportion of solvent used 15
nal type oils, or any other type of highly refined varies with the content of sulphonic acids but is
mineral oil. As an example, it is possible to ob usually in the range of 1 to 10% by volume of
tain a water white odorless and non-fluorescent the oil. The preferred method of extraction is
oil by treatment with considerably less acid by a countercurrent treatment with the solvent.
this step procedure, than by the procedure in By the use of countercurrent extraction 20
which the intermediate removal of Sulphonated methods it is found that the efficiency of extrac- .
products is omitted. . tion is tremendously increased. Further, it is
Our process, however, is so flexible that it may possible to use aqueous solutions containing high
be applied to acid oils containing sulphonic acids concentrations of organic solvents and minimize
25or acid sludges irrespective of the means Or man the quantity of mineral oil which is occluded with 25
ner of adding the sulphonating agent. The use the Sulphonic acids in the solvent extract. It is
of increments of acid is preferred largely for ease also possible to use organic solvents undiluted,
of operation in that it effects a partial prelim for extraction, an operation which has not been
inary isolation of chemical constituents. . . found practical heretofore. KnOWn extraction
30 The total quantity of acid which may be used methods usually employ aqueous solutions of cer 30
may vary up to 100 percent by volume but in tain organic solvents to remove the sulphonic
most instances 1.5 to 20 percent by volume is acids. The separation of the aqueous solvent
used. After several increments of acid are ap from the sulphonic acids, in subsequent process
plied the acid produces sulphonic acids which are ing is more difficult than the separation of the
35 predominately of the oil soluble type. pure solvent only from the sulphonic acids. For 35
The temperatures employed in the above de example, the step involving the dehydration of
scribed application of sulphuric acid are regu the sulphonic acids is eliminated and organic
lated to produce the desired sulphonation. When solvents can be used which distill at relatively low
relatively low rates of acid are employed the temperatures, thus facilitating the recovery of
maximum sulphonating temperature is held to the pure solvents.
below about 130 F. After an initial application Organic solvents, like mono and polyhydric
of acid and withdrawal of sludge the Sulphona alcohols, ketones, oxides, halogenated alcohols,
tion of the residual oil may be performed at tem acetates, ethers, esters, or aldehydes can be used
peratures up to 350 F., but temperatures should in our process either undiluted or in aqueous
45 be avoided at which the sulphuric acid usually Solutions. A few of those which are suitable are: 45
acts as an oxidizing agent.
In the practice of the invention, the prepara Alcohols:Methyl alcohol
tion of sulphonic acids and other by-products Ethyl alcohol
may often be profitably combined with the re Propyl alcohols
50 fining of a lubricating oil fraction. In so doing Ethylene glycol 50
just sufficient acid is employed to suitably refine Glycerol
the oil and produce an equivalent quantity of Hexahydric alcohols
sulphonic acids. When such treatment is per KetOnes:
formed there is produced (1) an acid oil con Acetone
55 taining free sulphonic acids (2) acid sludges iso DiacetOne 55
lated in increments. These products are proc
essed separately and the treatment of the acid Oxides:
oil is described in detail below, and illustrated in Ethylene oxide
the accompany drawing. The processing of the Dioxan
acid sludges is made the subject of our copending Esters: 60
60 Ethylene glycol acetate
application Serial Number 268,490, filed April 18, Diethylene glycol acetate
1939.
Treatment of acid oil Ethers:
Methyl ether of ethylene glycol
When acid oil is treated by the conventional Ethylether of ethylene glycol
65 method, referred to hereinbefore, it is first neu 65
Ether-esters:
tralized with an alkaline reagent and the Sul Ethyl ether of diethylene glycol acetate
phonic acids converted to metal sulphonates. In Aldehydes: V
the present process, however, this neutralization Formaldehyde
step is avoided and the sulphonic acids extracted Acetaldehyde
directly from the oil in which they are dissolved. Chlorhydrins: 70
Prior to the extraction of the Sulphonic acids Ethylene chlorhydrin
from the acid oil it is often found advisable to Diethylene chlorhydrin
centrifuge the oil for complete removal of sus
pended acid sludge. This intermediate step fa When Organic solvents are employed to extract
75 cilitates further handling, inas much as the con the Sulphonic acids from the oil, those solvents 75
 2,218,174 3
which possess low oil solubility characteristics are to isolate sulphonic acids from acid treated min
particularly adaptable to our process. Of such eral oils, it was stated that solvents are pre
solvents, methyl alcohol, ethyl alcohol, and ace ferred, which are relatively insoluble in mineral
tone are preferred as they are more easily re oil. However, small amounts of solvents will re
covered by distillation due to their low boiling main in the oil after the extraction is completed,
pointS. and will require recovery by conventional means
Any water soluble oxygen containing Organic such as Water Washing or distillation.
Solvent can be used and Suchare preferentially used, We have shown up to this point (1) the step
but other solvents which are insoluble in Water of countercurrent extraction of sulphonic acids
O and do not contain oxygen may be used to ex from oil with organic solvents Or aqueous solu O
tract the sulphonic acids provided they are in tions thereof, (2) the step of removing occluded
Soluble in the hydrocarbons. hydrocarbon oil by diluting the solvent extract
As Stated above aqueous solutions of organic (aqueous or not) with more of the Organic sol
Solvents may also be employed, e. g. aqueous Went,
5 ethyl alcohol. The ratio of alcohol to Wateris USU The extract, now Substantially freed of unsul 5
ally held in the range of 1:1 to 1:3 with a ratio of phonated hydrocarbon oil and containing the Sull
1:1 being preferred. It has been observed that phonic acids, also contains undesirable contam
Some of the Solvents when used in acqueous Solu inants such as Sulphonates of iron and lead. The
tions as extraction media have the property of formation of these organic iron and lead sul
20 occluding more hydrocarbon oil than others. For phOnates is the result of the action of the Sul
such reasons, and also in view of economy of op phonic acids on the metal of the refinery equip
eration it is advisable to use aqueous Solutions ment with which they come in contact during
of methyl and/or ethyl alcohol, as the latter ex processing. The Complete removal of such im
tract a maximum quantity of sulphonic acids purities is essential in the preparation of pure
25 and occlude a minimum quantity of hydrocarbon Sulphonic acids, Sulphonic salts, and other de 25
oil. rivatives of sulphonic acids where purity of prod
After extraction of the Sulphonic acids, the luct is of prime importance.
aqueous solvent extract under certain conditions An illustration of the need for pure products
may have the following composition: is in the use of Soaps of sulphonic acids in the
30 al Percent dry cleaning industry. If iron and lead soaps are 30
by volume present in the soaps employed, such as sodium,
Sulphonic acids---------------------------- 40 potassium, and ammonium sulphonates, very un
Hydrocarbon oil-------------------------- 30 desirable results are obtained and fabrics seri
Alcolnol ????????--------????????????----------------- ???--?? 15 Ously injured.
35 Water----------------------------------- 15 Pre Sulphonic acids are demanded also in the 35
but even when the solvent extracts contain rela lacquer and Warnish industry and the tanning
tively high Concentrations of hydrocarbon oils a industry. When metal sulphonates, such as
means of separation of Such oil_is included ?n those of lead, cobalt and manganese, are used as
this process. To separate such occluded hydro drying catalysts in the compounding of lacquers
40 carbons from the mixture the ratio of alcohol to and Warnishes, iron sulphonate, if present, would 40
Water is increased to about 3:1, whereby the hy Seriously interfere with such action. In the tan
drocarbon oil rises to the top to form an upper ning industry the leather is subjected to the ac
layer. Normally the solubility of oil in the Sol tion of a solution of sodium or potassium sul
went is quite low and the quantity of oil in solu phonates in a solvent. When iron or lead sul
45 tion is usually influenced by the concentration ofphonates are present these may precipitate on
sulphonic acids in the mixture. The higher the the leather as a gummy deposit. Such deposits 45
Sulphonic acid concentration the greater the sol CauSe discoloration and have deleterious effects
ubility effect exerted by the acids for the oil. On the fine texture and smoothness of the leather.
Through the further addition of alcohol. Such an In time the metal Sulphonates may be hydrolized
50 influence is minimized and the hydrocarbon oil into metal oxides and free acid, the latter in 50
liberated. juring the leather through chemical attack.
In contradistinction to the example of aqueous Further, it is noted that ammonium and cer
Solvents, given above, the use of substantially tain organic base sulphonates have insecticidal
anhydrous solvents will give superior results, in properties. Iron and lead sulphonates, if pres
55 aSmuch as the hydrocarbon Content of the ex ent in the Sulphonic acids used to prepare the 55
tracted portion is greatly reduced. As an ex above products, e. g., the combination of an or
ample in the case of anhydrous methyl alcohol ganic amine and Sulphonic acids, would be re
the composition of the extracted portion under tained in the insecticidal solution to eventually
certain conditions is as follows: precipitate out as undesirable and harmful de
60 Percent posits.
Sulphonic acids--------------------------- 45 The Solvent extract, containing the sulphonic
Hydrocarbon oil------------------------- trace acids and impurities, is subjected to the action
IMethyl alcohol------------------------------------ 55 of a strong acid which is capable of separating
In the above cited example, it is apparent that out the metal contaminants as inorganic metal
65 the Step requiring additional use of Solvent for salts. By strong acid is meant one which has a 65
removal of occluded hydrocarbons has become high hydrogen ion Concentration and Sulphuric
unnecessary. However, if hydrocarbons should acid is preferred for this operation, although
be occluded in the extracted portion, their sep other strong acids such as hydrochloric, phos
aration can be effected by further dilution of the phoric, and the like may be used.
70 extract with anhydrous solvent, whereby the hy - When using a strong mineral acid the highly 70
drocarbon oil will be thrown out of solution and Soluble metal Sulphonates are converted into in
can be withdrawn by the usual method of gravity organic metal salts which are insoluble in the
separation. Sulphonic acids. Concentrated Sulphuric acid,
In the process described, which involves the which is preferred, serves another important
5 use of a substantially anhydrous organic solvent, function in also accomplishing a substantially 78
 4. 2,218,174
complete dehydration of the sulphonic acids. raftinate were examined and the following
The organic solvents or aqueous organic solvents physical and chemical characteristics deter
are soluble in the acid layer, whereas the sul mined:
phonic acids are substantially insoluble and are Molecular weight--------------------- 404
salted out of Solution. In order to obtain such a Specific gravity GD 60 F.-------------- 10890
salting out effect it is necessary for the sulphuric Refractive index at 20 F.-------------
15120
acid layer to be at least of 50% acid strength,
the preferred concentration being 60'75% sul Composition:
phuric acid. The lower layer containing the sul Percent
0. phuric acid, alcohol, Water and metal sulphates Carbon------------------------------ 70.33 0
is withdrawn and the upper layer centrifuged *ydrogen --------------------------- 9.21
to obtain pure sulphonic acid. Sulphur----------------------------- 8.34
An alternate procedure for separating pure Oxygen ----------------------------- 12.12
sulphonic acids from the extract (aqueous or The above composition corresponds to the
5 not) is to remove the initial Solvent by distillation formula
preferably with vacuum whereby the crude sul CMH35SO3H
phonic acids and small amounts of sulphuric Or in general
acid remain a.s.? residue in the still. This still
residue is then treated with strong acid, sulphuric
20 acid being preferred. As in the previous illus In the description of the initial steps of the 20
tration of the purification procedure the final sul process, e. g., the Sulphonation step, it was stated
phuric acid concentration must be a minimum that a partial separation of chemical constituents
of 50% strength. This minimum concentration resulted from the addition of the sulphonating
is necessary to insure complete removal of unde agent in increments. Through such use of in
25 sirable metal contaminants and at the same time Crements it is possible to produce acid oils and 25
to prevent sulphonic.acids from going into solu acid sludges which contain a preponderance of
tion in the Sulphuric acid layer. One type of reaction products. Further by such
In this procedure it is advantageous to use acid preliminary segregation subsequent processing
in excess of 90% concentration, as, for example, steps and the recovery of by-products, are facili
30 66° Bé. or 98% sulphuric acid. The upper sul tated. It is also found that while sulphonating, if 30
phonic acid layer may be isolated and purified the temperature as well as acid concentration is
also by Centrifuging. The preferred method in controlled, acids of different molecular weight
this case, however, is to extract the sulphonic may be isolated. .
acids with an organic solvent preferably hydro To illustrate: The base oil is treated with sul
35 carbon Solvents, such as propane, butane, petro phuric acid of from 93% H2SO4 up to 50% fumi. 35
leum ether, which dissolve the sulphonic acids ing acid at normal temperatures, starting at say
and leave the Sulphuric acids and metal impur 70 F., and the temperature maintained within
ities undissolved. The more volatile solvents, e. a range of about 20 F. by suitable control means.
g., propane, or butane are preferred because after After the first two or three increments the acid
decanting the extract from the sulphuric acid oil is treated as described, in the drawing, to re- 40
the sulphonic acids may be isolated in a substan. move Sulphonic acids contained therein. The oil
tially pure state by the removal of the solvent by is again treated with fuming acid and the sul
distillation at low temperatures and further the phonic acids extracted from the oil. In this
preferred solvent is preferably of such boiling manner a series of acid sludges and a series of
range that there will be substantially no reaction Solvent extracts of Sulphonic acids is obtained,
45 with the Sulphonic acids at the temperature of thus accomplishing a selective Sulphonation of
distillation. the hydrocarbons. For example, the first few
The extraction of Sulphonic acids from the acid acid sludges will contain a good proportion of acid
oil. With non-aqueous Organic solvents has the foll tar and only a relatively Small amount of sul
50
lowing advantages over the use of aqueous or phonic acids. The later sludges will have higher
ganic solventS: concentrations of Sulphonic acids. Of these
(1) In view of the fact that the extract is sub sludges the first in which Sulphonic acids predom
stantially water-free, corrosion to metal equip inate will yield acids of a different average molec
ment is reduced to a minimum. ular Weight than Sludges produced Several acid in
55
(2) The presence of relatively dilute aqueous crements later. Such a feature is due to the fact 55
sulphuric acid during any distillation step is that the first sulphonic acids are produced from
avoided. hydrocarbons which are more readily attacked
(3) Due to the absence of Water, lower distill whereas after removal of such hydrocarbons the
lation temperatures are possible. acid must then attack the more difficultly sul
(4) Low distillation temperatures are desirable phonated hydrocarbons. In the two cases the 60
60 to minimize reactions of Sulphuric acid with sol sulphonic acids produced will be of different type
WentS. With respect to the structure of the Organic rad
(5) The Sulphuric acid is recovered for reuse in ical. Similarly the various solvent extracts, con
practically original concentration. taining sulphonic acids which had been removed
(6) Continuous processing is facilitated as con from the oil after each acid treat, will have differ- 65
65 stant control of solvent concentrations, e. g., al ent types of Sulphonic acids in solution.
cohol-water ratios, is not required. When the yield of Sulphonic acids at the first
The various processes of purification described controlled temperature and SO3 concentration
are adaptable to the purification of all Sulphonic becomes Small, the treating temperature and/or
acids, the solubility characteristics of which allow SO3 concentration are raised and the process re
such a procedure. In a novel and simple manner peated, again controlling the temperature within 70
such acids are purified and their value and field about 20 F. range. By such temperature and
of utilization broadened through such purifica concentration control and by the addition of acid
tion. in increments progressive sulphonation of hydro
Sulphonic acids which have been isolated from carbons takes place. Hence by the isolation of
the sulphonation of a 95 Wisc, S. U. GD 100' F. acid sludges and solvent extracts in steps and the 7
 2,218,174 ?
separate recovery of sulphonic acids therefron sludge is removed from the oil after each in
sulphonic acids of different average molecular crement while leaving the sulphonic acids pro
weights and different structures can readily be duced dissolved in the oil, that combination of
obtained. steps which comprises: progressively increasing
We claim: the temperature of the oil after each increment
1. The process of preparing sulphonic acids of acid and withdrawing acid sludge after each
from hydrocarbon oils, which comprises: treating increment. r
a petroleum oil with a sulphonating agent to pro 5. In a process of preparing Sulphonic acids
vide sulphonic acids dissolved in the oil, removing from hydrocarbon oils in which the oil is treated
10 the spent sulphonating agent, mixing the treat with sulphuric acid in increments and the acid O
ed oil with an oil insoluble organic solvent to ex sludge is removed from the oil after each in
tract said dissolved sulphonic acids, separating the crement while leaving the Sulphonic acids pro
oil from said solvent, adding an acid of high duced dissolved in the oil, that combination of
hydrogen, ion concentration to said solvent to steps which comprises: progressively increasing
5 effect separation of the sulphonic acids contained the temperature of the oil after each increment 5
therein, and separately recovering said sulphonic of acid and holding such increased temperature
acids. within a range of about 20 F., and Withdrawing
2. The process of preparing sulphonic acids acid sludge after each increment.
from hydrocarbon oils, which comprises: treat 6. The process according to claim 1 in which
20 ing a petroleum oil with a sulphonating agent to the acid of high hydrogen ion concentration is 90
provide sulphonic acids dissolved in the oil, re sulphuric acid.
moving the spent sulphonating agent, mixing the 7. The process of preparing Sulphonic acids
treated oil with an oil insoluble organic Solvent from hydrocarbon oils which comprises: treating
to extract said dissolved sulphonic acids, separat a petroleum oil with a sulphonating agent in a
ing the oil from said solvent, separating said series of increments to provide Sulphonic acids 25
solvents and contained sulphonic acids by distill dissolved in the oil, increasing the temperature
lation, adding sulphuric acid to the separated Sul of treatment with each increment, removing the
phonic acids to separate impurities, and Separate spent sulphonating agent after the addition of
ly recovering said sulphonic acids. each increment, extracting said Sulphonic acids
3. The process of preparing sulphonic acids with an oil insoluble organic solvent after each
from hydrocarbon oils, which comprises: treating increment, and recovering the Sulphonic acids
a petroleum oil with a sulphonating agent to pro from said solvent.
vide sulphonic acids dissolved in the oil, remoV 8. The process of preparing sulphonic acids
ing the spent sulphonating agent, mixing the from hydrocarbon oils which comprises: treat
treated oil with an oil insoluble organic solvent ing a petroleum oil with a sulphonating agent in 35
to extract said dissolved sulphonic acids, separat a series of increments to provide Sulphonic acids
ing the oil from said solvent, separating said sol dissolved in the oil, increasing the temperature
vent and contained sulphonic acids by distillation, of treatment with each increment, removing the
adding sulphuric acid to the separated sulphonic spent sulphonating agent after the addition of
to acids to separate impurities, diluting said mix each increment, extracting said Sulphonic acids
ture of sulphuric acid and sulphonic acids with a with an oil insoluble organic Solvent after each
low boiling hydrocarbon solvent to separate said increment, adding an acid of high hydrogen ion
sulphonic acids, removing said hydrocarbon sol concentration to said solvent to effect separa
vent, and separately recovering said Sulphonic tion of the Sulphonic acids contained therein, and
separately recovering said Sulphonic acids.
4. In a process of preparing sulphonic acids
from hydrocarbon oils in which the oil is treat ARTER, AZAR.
ed with sulphuric acid in increments and the acid PAUL MORITZ RUEDRICE.