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.