This patent from 1939 describes an improved process for producing sulfonated products from mineral oils. The key improvements allow for minimizing undesirable side reactions through carefully controlling the sulfonation reaction conditions, including limiting the reaction time to under 15 minutes. These improved sulfonated products have reduced odor and color while maintaining or enhancing their detergent, wetting, and emulsifying properties. The patent provides details on extracting mineral oil distillates, pre-treating with sulfur dioxide, and sulfonating the extract with sulfuric acid under controlled conditions to produce products with commercial applications.
This patent from 1939 describes an improved process for producing sulfonated products from mineral oils. The key improvements allow for minimizing undesirable side reactions through carefully controlling the sulfonation reaction conditions, including limiting the reaction time to under 15 minutes. These improved sulfonated products have reduced odor and color while maintaining or enhancing their detergent, wetting, and emulsifying properties. The patent provides details on extracting mineral oil distillates, pre-treating with sulfur dioxide, and sulfonating the extract with sulfuric acid under controlled conditions to produce products with commercial applications.
This patent from 1939 describes an improved process for producing sulfonated products from mineral oils. The key improvements allow for minimizing undesirable side reactions through carefully controlling the sulfonation reaction conditions, including limiting the reaction time to under 15 minutes. These improved sulfonated products have reduced odor and color while maintaining or enhancing their detergent, wetting, and emulsifying properties. The patent provides details on extracting mineral oil distillates, pre-treating with sulfur dioxide, and sulfonating the extract with sulfuric acid under controlled conditions to produce products with commercial applications.
2,9,14 SULEPHONATES OF MINEERA, O, EXTRACTS AND RETHOD OF RaAKENG Robert L. Brandt, New York, N. Y., assignor to Colgate-Palmolive-Peet Company, Jersey City, N. J., a corporation of Delaware No Drawing. Application June 4, 1938, Serial No. 21,946 14 Claims. (CI. 260-504) This invention relates to certain improved difficulties, the ordinary sulphonates of mineral chemical compositions and to a method of their oils, even though they appear, when dissolved in preparation, purification, and use. The im Water, to give clear Solutions, may contain rela proved compositions may be generally described tively large quantities of unreacted oil. In addi as products or the salts of products of the spe tion to oil the products are apt to contain unde cially controlled action of sulphonating agents sirable side reaction products such as resins, upon certain portions of mineral oils. The prod polymerized hydrocarbons, coloring matter, oil lucts are particularly useful as deterging, wetting, Soluble sulphonic acids, thio compounds and foaming, frothing or emulsifying agents and, in other materials that may be dark colored and/or 0. general, as modifiers of capillary action and of malodorous and unstable. O Surface tension. They are highly useful as tex Many of these undesirable side reaction prod tile assistants, as flotation agents, as household ucts are highly objectionable in the finished prod detergents, as industrial emulsifying agents and ucts, as they prevent or hinder detersive action, for many other purposes. rapid Wetting-out and rapid solubility. In addi 5 In many instances and in many ways, prior to tion, they are the cause of stickiness in hand 5 this invention, mineral oils and sulphuric acid have been placed in contact and have to a greater washing and of a slight yellow stain or color in Washed goods. or leSS extent been reacted together, but insofar By the process of this invention, it has been as the present inventor has been able to deter found that despite the numerous reactions that 20 mine, none of these products made according to may occur when the process is not under easy 20 the prior art has been satisfactory for household Control and the general complexity of the chem and general industrial use as a deterging, wetting, istry involved, a vastly superior material from emulsifying, or foaming agent or the like. a consideration of odor, color, deterging efficiency, According to Patents 2,149,661 and 2,149,662 emulsifying properties and the like can be pro 25 issued March 7, 1939, on copending applications duced by employing such control. 25 of this same inventor, namely, Serial No. 117,096, According to this invention, it is possible to filed December 21, 1936 and Serial No. 138,463, bring about the desired sulphonation reaction filed April 22, 1937, methods are provided by With a minimum of side-reactions by contacting which sulphuric acid-mineral oil reaction prod the Sulphonating agent and extracted material 30 lucts of relatively high purity and effectiveness rapidly without permitting local overheating or a 30 for the purposes mentioned, may be produced. rise in temperature above certain limits, to con Certain improvements in the processes of these tinue the reaction no longer than about 15 mini applications described above have now been dis utes and preferably for a period no greater than covered, and these improvements comprise the 5 minutes, and then to get the products out of 35 present invention. A contact with the strong mineral acid immedi Ordinarily, when the materials extracted from ately. If the reaction is conducted for a period petroleum oils are treated with sulphuric acid, of time appreciably longer than 15 minutes, the polymerization, oxidation, Sulphonation and sul products are perceptibly darker in color, more phation, condensation and other types of reac odorous, and not as good detergents or wetting 40 tions occur in greater or less degree, depending Out agents as those prepared with a shorter re 40 on the strength of acid, kind of oil, temperature, action period. time, oil-acid volume relations, intimacy of con In the process of this, as well as in my prior tact and degrees of mutual solubility, and other invention, rapidity of contact and low operating factors. With all of these reactions taking place v temperature are permitted by the use of liquid 45 and all of these conditions to be controlled, it sulphur dioxide as a solvent for the reactants, is not surprising that difficulty has been encoun and this same liquid sulphur dioxide appears to tered in preventing the formation of unwanted assist the reaction in still another way, which compounds which give the final material both is not completely understood, but it may be con odor and color and detract greatly from its effi sidered that a catalytic effect of the liquid Sulphur Ciency. dioxide on the reaction between the extracted 50 The sulphonated products prepared by the material and the sulphonating agent is to prevent processes used prior to those described in the side reactions while facilitating the desirable re applicant's copending applications were dark in action. One embodiment of the present inven color, of bad odor and of poor quality, and un tion which particularly lends itself to the rapid 55 satisfactory for most uses. In addition to these sulphonation of the mineral oil extract is the ad 55 2 2,179,174 tioned is preferably employed and the yield, mixture of the sulphonating agent, such as fumn deterging, ing sulphuric acid, with liquid sulphur dioxide and wetting, emulsifying efficiency, , odor color of the products have been found to be before treatment of, the mineral oil extract solu materially improved tion with said Sulphonating agent. thereby. Any one of the 5. As a starting material, in either the present steps, however, is of importance and contributes toward a better product and may or may not be proceSS or those of the aforementioned applica tions, it is to be understood that any mineral oil used with the more general method of directly Sulphonating the mineral oil extract in liquid or raw distillate therefrom may be used, but it is Sulphur dioxide to produce materially improved preferred to employ a distiliate from what is products. 0 10 generally known as a naphthene base crude, Such The next step after the pre-treatment of the as a Texas Gulf Coast crude, as distinguished hydrocarbon from, say, a Pennsylvania crude. It has been liquid sulphurextract consists in dissolving it in found that the lower viscosity raw distillates are, being already in sulphuror dioxide dioxide, the extract material solution from in general, to be desired. . the solvent extraction process, the next step may 15 The first step in the processes of the applicant's patents noted above and usually in the present consist in diluting the solution with as much more sulphur dioxide as may be necessary to pre process is an extraction of the mineral oil or pare it for the Subsequent steps in the process. distillate to be used, with a selective solvent such Usually, the extracted material should be dis as liquid. Sulphur dioxide, liquid Sulphur dioxide Solved one-half to two times its 20 20 plus benzol, furfural, phenol, nitrobenzene, di volumeinofapproximately chloroethyl ether, a propane-cresylic acid mix Solution ofliquid sulphur dioxide. The resulting extracted material in liquid sulphur ture, or the like. This operation yields a hydro dioxide is, even at low temperatures (below 0° C.) Carbon oil extract which is characterized by high Specific gravity in comparison with the starting very fluid and non-viscous. 25 oil, extremely low viscosity index, high Conrad rialHaving the desired solution of extracted mate 25 Son carbon, and a high degree of unsaturation. cooledintoliquid a sulphur dioxide, the solution is temperature of about -15° to -20° C., It is generally thought that the extracts so ob and mixed with a sulphonating, agent such as tained are composed of the more aromatic and Strong fuming sulphuric acid also preferably unsaturated of the hydrocarbons constituting the dissolved in liquid sulphur dioxide and at to 30 30 original oil. In general, repeated extractions of -20° C. The temperature is kept below -15° --5° C., the same oil will yield additional extract, but the during the initial mixing and preferably below extract so obtained is not quite so satisfactory -5 C. Agitation should be applied when using for the present purposes as the extracts obtained a batch method in order to rapidly dissipate the by less exhaustive extraction, and it has been heat generated to the cooling surfaces of the re 35 found that the extracted hydrocarbon material action vessel. most desirable for the present process is that The quantity of acid used, and its strength, will which is readily soluble in liquid sulphur dioxide depend on the type of extracted material, the re at low temperatures, as for instance, at 0° C. OE action temperature, liquid sulphur dioxide dilu even lower. tion, and the characteristics desired in the fin 40 40 The hydrocarbon oil extract obtained by the ished product. Funning Sulphuric acid (commer above processes may be used directly for sul cial 20% oleum), in a quantity about equal in phonation. It has further been found, however, that considerable improvement in the final prod weight to the extracted material to be treated and dissolved in liquid sulphur dioxide, has been lucts can be effected by additional processing of found the material to be sulphonated, which processing. phonc satisfactory. acid or other Sulphur trioxide, chlorsul sulphonating agent soluble preferably takes place after solvent extraction but in liquid Sulphur dioxide may also be used. By may be accomplished either before or after the dissolving the Sulphonating agent in liquid sul extraction and/or by carrying out the extraction phur dioxide, it is possible to add this agent to under particular conditions. The further processing mentioned may com the oil liquid sulphur dioxide solution of the mineral extract over a much shorter period of time prise further narrowing of the boiling range of without excessive temperature increase such as the portion of the oil to be sulphonated, by addi Would result if the Sulphonating agent were add tional fractionation of the material after solvent ed directly extraction or by additional or more specific frac Furthermore,to itthepermits mineral oil extract solution. extremely rapid reac 5 5 tionation prior to extraction. It may also com tion rates and physically permits more rapid prise treatment of the material to be used for Sulphonation, with caustic soda to remove certain dissipation and removal of the heat of reaction. undesirable acidic constituents, treatment with which preventisorcarried The reaction out at low temperatures minimize oxidation, polymeri Sulphuric acid to remove asphalt-like and highly zation and other undesired reactions that aiways 60 60 reactive bodies and water, and treatment with occur at the usual sulphonation temperatures. contact clay to assist in the sludge removal. Upon completion of the original mixing of acid Probably the most important factor determin with the extracted materials and after the initial ing the quality and quantity of the extract ob evolution of heat of reaction has been dissipated, tained in the solvent extraction process is the the reacting mixture is raised to a temperature of 65 operating temperature. In general, the lower the about --5° C. by control of cooling apparatus. temperature the more selective are the solvents. The original mixing is accomplished in a few For extracting light lubricating oils with liquid minutes. The reaction is permitted to continue sulphur dioxide, a temperature between -15 with agitation for a period not greater than fif and -15° C. is quite satisfactory. For lower vis teen minutes from the initial mixing of the re 70 cosity oils even lower temperatures are advan actants and preferably no longer than five min tageously employed, and when solvent extracting the lower boiling hydrocarbons such as crude uteS. naphtha, very low temperatures are of advantage ingTreatment with the sulphonating agent hav been completed, the reaction mixture is di (-60°. F.). A combination of all of the treatments men luted with cold water to stop further action of 75 2,179,74 3. the sulphonating agent. After water dilution water and of increased wetting, emulsifying and the next step is to separate any unreacted mineral deterging efficiency. hydrocarbon from the mixture. Several alterna A more detailed understanding of the prin tives are possible. One is to hold the liquid Sul ciples of this invention may be achieved by a 5 phur dioxide solution of sulphonation products consideration of the following specific examples 5 and acid under pressure and add enough Water of the process of making the improved compo to form two layers. One layer, consisting of the Sitions. bulk of liquid sulphur dioxide containing most of Eacample I the unreacted hydrocarbon oil in solution, may 10 be directly separated. The second layer, con The extracted material used was obtained by sisting of the sulphonic-sulphuric acids in aque the Edeleanu process from a Texas Gulf Coast :0 ous solution, may be further extracted with fresh crude distillate of the naphthene base type, hav liquid sulphur. dioxide, and after removal of the ing a Saybolt viscosity at 100 F. of about 100 residual dissolved sulphur dioxide, the aqueous seconds. One volume of the extracted material 15 layer may then be neutralized with a basic com was mixed with half its volume of liquid Sull pound such as caustic soda, Soda ash, ammonia, phur dioxide and cooled to -15° C. A quan lime, triethanolamine, or the like. tity of 20% commercial oleum equal in weight Alternatively, the liquid sulphur dioxide Sol to the extracted material and dissolved in a vent may be evaporated off immediately on dilu volume of liquid sulphur dioxide equal to that 20 tion of the reaction mixture with Water, and the used to dissolve the extract, was added to the quantity of water may be controlled to give either solution with agitation, the addition being made a dilute solution of sulphonic-Sulphuric acids in about one minute. The operation was per . (one phase), or, with a lesser proportion of Water, formed in a jacketed autoclave, provided with such a concentration of sulphuric acid that a a stirring device, thermometer and pressure 26 two-phase system results, consisting of an upper gauge. Considerable evolution of heat occurred layer of sulphonic acids and a lower layer of during and immediately after the addition of .25 diluted sulphuric acid. The latter may be with the acid. Temperature control was maintained drawn directly and discarded. In this manner by circulating a cooling fluid through the jacket a substantially sulphuric acid free sulphonic acid and the temperature was at no time permitted 30 solution is obtained. This layer may be washed to rise above -5° C. during the mixing. After with an insoluble low boiling hydrocarbon in order the acid addition, the temperature was raised to 30 to free it from any unreacted extract that it may --5° C. and maintained at that point for about, contain. Ordinarily it is best to dilute this layer three minutes, the agitation being continued. with water before extraction with the solvent. At the end of this period the material was im 35. It has been discovered that if the washing is mediately mixed with twice its volume of ice performed after dilution with water but before Water. W .35 neutralization, certain difficulties due to the for During dilution with water the liquid sulphur mation of emulsions are avoided and for that dioxide was removed by evaporation and the reason, the step is best performed at that time. aqueous layer was heated to 45° C. to remove 40. The water solution of the reaction product may any residual Sulphur dioxide. The aqueous so or may not be boiled before neutralization to de lution was then batch-washed several times with stroy any unstable sulphates present. After neu 20% of its volume of gasoline, (end boiling point tralization, the solution may be boiled in an ex below 250 F.). The aqueous solution of sul cess of caustic soda, or the acid solution may phuric-sulphonic acids mixture was neutralized 45 trated be run caustic into a calculated amount of hot concen by pouring into a calculated quantity of very soda, to decompose unstable COm strong caustic soda and brought to a boil. The 4 pounds. The solution of neutralized sulphuric neutralized solution was then taken to dryness acid reaction product, which may also contain on the soap-drying rolls at a roll temperature a considerable proportion of the sulphate of the of about 250 F. 50 neutralizing material as a result of its reaction The above operations yielded a substantially with the excess sulphuric acid present may be dry powder almost white in color, having no 50 used in this state for many purposes, or it may Odor in the dry state. Aqueous solutions, when be further concentrated by extracting with iso rubbed into a lather on the hands, give no odor. propyl, butyl or with substantially water-insol Dilute solutions of varying concentration were excellent foamers (comparing favorably with is uble alcohols in which the active ingredient is soap), soluble, to free. it from the by-product sulphate excellent washing and detergent mate formed in the neutralizing process. rials, and also powerful wetting-out and emulsi-- The final material, either with or without the fying agents. by-product sulphate, may be formed into beads, Eacample II 60 flakes, chips, powders, solutions, liquid or plastic According to the preferred process, a distillate 60. emulsions or other forms into which soap or from a Texas Gulf Coast crude boiling between other detergent or emulsifying materials are Or 130° C. and 350° C. at 5 mm. pressure and hav dinarily made, either with or without the ingre ing a Saybolt viscosity of 80 seconds at 100 F., dients commonly used in such combinations, for was countercurrently extracted with approxi 65 example active or inert soap fillers, water sof mately an equal volume of liquid sulphur dioxide 65 teners, perfumes, abrasives, soap and other de by the usual Edeleanu process, the Sulphur di tergents, fats, oils, waxes, and glycerine. The oxide separated from the extract and the ex Sulphonate product can be incorporated with tract then fractionally distilled, in vacuum, in the usual fatty acid soaps and the composition the presence of about 0.1% of its weight of formed into bars, flakes or powders. The last caustic soda. The fraction boiling between 220 to C. and 240° C. at 5 mm. pressure was pretreated combination yields an inexpensive detergent with about 1% of its weight of 92% sulphuric Composition possessing all the desirable prop acid by mixing it thereWith for about forty-five . . erties of the ordinary soaps and the additional minutes. Most of the acid-sludge settled out 5 advantages of operativeness in hard and sea at once, but a remainder, which is known as is 4. 2,179,174 'pepper' Sludge, had a tendency to remain sus ene dichloride, dichlor ethyl ether, ether, mono chlorbenzene, carbon tetrachloride and other pended in the oil and was removed by treating suitable solvents. the oil with about 0.2% of its weight of contact The products made according to this inven clay and heating to 130 to 150° C. excluding tion are of the type described and claimed in air. After hot filtration, the oil was found bright the Copending application of this inventor, Se and clear. Centrifuging may be employed in stead of, or in addition to, the contact clay rial No. 117,096, filed December 21, 1936; now matured into Patent 2,149,661. They are some treatment. The desired fractions of the extract may be what improved over the products described in the examples of that patent for by virtue if individually or collectively sulphonated. The pre-treated extract was dissolved in an equal the short reaction time the initially sulphonated 0. Volume of liquid Sulphur dioxide and cooled to hydrocarbons are removed from the sphere of reaction with the oleum almost as soon as they -20° C. Over a period of one minute a liquid are, formed and therefore side reactions are to Sulphur dioxide solution of 20% oleum was this extent reduced and so polymerization, oxi added. The quantity of oleum used was equal 15 in weight to that of the hydrocarbon material dation and overSulphonation prevented. The process hereinbefore disclosed as a batch to be sulphonated and was dissolved in half Inethod may be carried out continuously or in its volume of liquid sulphur dioxide and cooled termittently in Suitably arranged apparatus. to -20° C. The reaction mixture was agitated 2C 20 in a jacketed autoclave provided with stirrer, I1.claim: The process of preparing sulphonic acids pressure gauge and thermometer and cooling which comprises treating a hydrocarbon mate means. Considerable heat was evolved upon the rial removed from a mineral oil by solvent ex addition of acid. Temperature control WaS traction with a preferential solvent that tends maintained by circulating a cooling fluid through to dissolve certain constituents of the oil and 2 25 the jacket. The temperature during mixing was not to dissolve others, the constituents which not permitted to rise above --5 C., and was the Solvent tends to dissolve being generally maintained at that point for about ten minutes, those of an unsaturated nature including those the agitation being continued. At the end of of an aromatic nature, with a sulphonating this period, ice-water was added and the Sul agent while in Solution in liquid sulphur dioxide 3. 30 phur dioxide was separated as a vapor, by re for a period not exceeding fifteen minutes. leasing the pressure at a temperature below 2. A process of preparing sulphonic acids from --10° C. mineral oil which comprises treating a mixture The aqueous solution or dispersion was imme of liquid Sulphur dioxide and the material re diately batch-washed several times with 20% of moved 35 its volume of gasoline, endpoint 250 F. It was With a from a mineral oil by solvent extraction neutralized with caustic soda, and finally dried certain preferential solvent that tends to dissolve constituents of the oil and not to dis on soap-drying rolls at a roll temperature of 250° F. Solve others, the constituents which the solvent The above operation yielded a substantiallytends to dissolve being generally those of an dry powder even better in color than the produnsaturated nature, including those of an aro ucts described in Example I and likewise hav matic nature, with liquid sulphur dioxide having 40 dissolved therein a sulphonating agent for a ing practically no odor either in the dry state or when rubbed to a lather on the hands. period not exceeding fifteen minutes. Many uses for the new products will become 3. A process of preparing sulphonates that immediately apparent. To mention but a few comprises solvent extracting mineral oil with a 45 possibilities, they are useful in the flotation of preferential solvent that tends to dissolve cer ores, in shampoos, in dye baths, and for many tain constituents of the oil and not to dissolve detergent purposes. They may be used either others, the constituents which the solvent tends alone or in admixture with soaps and/or soap to dissolve being generally those of an unsatu rated nature including those of an aromatic na 50 fillers, such as Sodium silicate, sodium carbonate, ture, Separating the extract and raftinate, treat bentonite, calcium carbonate, talc and pumice. ing the extracted material while dissolved in The final products may take the form of pow liquid Sulphur dioxide with a solution of a sul ders, beads, bars, solutions, emulsions, creams, phonating agent dissolved in liquid sulphur di orInsalves, or any other forms desired. this specification, the term sulphonation oxide for a period not exceeding fifteen minutes, 5 55 has been used in its broad sense to mean the removing the sulphur dioxide, and thereafter reaction of Sulphuric acid upon the oil products Washing the product with a low end point satu- . and not merely the formation of one class of rated hydrocarbon and neutralizing. chemical compounds. Furthermore, the details 4. A process of preparing sulphonic acids that comprises treating a material removed from a 60 of the process, such as the quantities of the mineral oil by solvent extraction with a prefer reagents, their concentrations and temperatures ential Solvent that tends to dissolve certain con for the reactions are but examples of satisfac stituents of the oil and not to dissolve others, tory constants for a particular type of oil. As the constituents which the solvent tends to dis the type of oil is varied, as it may be within Solve being generally those of an unsaturated tile scope of this invention, these various factors nature including those of an aromatic nature, will necessarily vary, but the application of the with a sulphonating agent while the extract is general principles set forth herein, and the vary dissolved in liquid sulphur dioxide for a period. ing of these factors in accordance with the not exceeding five minutes. needs of the particular situation are within the 5. A process of preparing sulphonic acids from 70 concept of this invention. mineral oil that comprises treating liquid sulphur Where I have hereinbefore disclosed gasoline dioxide solution of the material, removed from a for the purification of the aqueous solution of mineral oil by solvent extraction with a preferen the reacticn products, I may employ in its place tial solvent that tends to dissolve certain con aromatic and aliphatic chlorinated solvents such stituents of the oil and not to dissolve others, 5 as dichloroethylene, ethylene dichloride, propyl 2,179,174 V 5. the constituents which the solvent tends to dis Solvent tends to dissolve being generally those Solve being generally those of an unsaturated na of an unsaturated nature, including those of an aromatic nature, fractionally distilling the ex ture, including those of an aromatic nature, with a mixture of liquid sulphur dioxide and a sul tracted material in vacuum over caustic soda, phonating agent for a period not exceeding five discarding fractions at least at one end of the, 5 minutes. boiling range, treating the remaining fractions 6. A process of preparing sulphonic acids thatwith a small proportion of sulphuric acid to re comprises. solvent extracting mineral oil with amove asphaltlike and highly reactive bodies an preferential solvent that tends to dissolve cer water therefrom, separating the sludge formed, tain constituents of the oil and not to dissolve dissolving the resultant material in a substan. others, the constituents which the solvent tends tial proportion of liquid sulphur dioxide and treaf- " to dissolve being generally those of an unsatu ing the Solution with a Sulphonating agent for rated nature, separating the extract and rafflinate, a period not exceeding five minutes. and treating for a period not exceeding five min 9. A proceSS of preparing Sulphonic acids that 5 utes, One part by Volume of the extracted ma Comprises Solvent extracting mineral oil with a 5 terial while dissolved in liquid sulphur dioxide preferential Solvent that tends to dissolve cer with approximately one part by volume of fuming tain constituents of the oil and not to dissolve sulphuric acid which has been mixed with liquid others, the constituents which the solvent tends Sulphur dioxide before adding to the extract. to dissolve "being generally those of an unsatu 2 7. A process of preparing sulphonates that rated nature, including those of an aromatic na- 30 comprises solvent extracting nineral oil with a ture, dissolving the extract in liquid sulphur di preferential solvent that tends to dissoive certain Oxide, cooling the solution to about -5° C. and quickly mixing therewith a mixture of liquid sul constituents of the oil and not to dissolve others, phur dioxide and a sulphonating agent while the constituents which the solvent tends to dis 25 Solve being generally those of an unsaturated maintaining the temperature during mixing be- 25 nature, including those of an aromatic nature, low about -5° C., and after mixing below about separating the extract and raffinate, treating the --5 C., the entire time of treatment with the extracted material while dissolved in liquid sul Sulphonating agent being not greater than five phur dioxide With a mixture of a Sulphonating minutes. . 30 agent and liquid sulphur dioxide for a period not 10. The product prepared according to the g exceeding five minutes, removing the sulphur di process of claim i. oxide, and thereafter washing the product with 11. The product prepared according to the a low end point saturated hydrocarbon and neu process of claim 3. . tralizing. 12. The product prepared according to the 8. A process of preparing sulphonic acids that process of claim 4. 35 comprises solvent extracting a material of the 13. The product prepared according to the 8. group consisting of mineral oil and mineral oil process of claim 7. distillates with a preferential solvent that tends 14. The product prepared according to the to dissolve certain constituents of the oil and not process of claim 8. 40 to dissolve others, the constituents which the ROBERT L. BRANDr.