Патент USA US2412916код для вставки
2,412,916 Patented Dec, 17, 1946 UNITED STATES PATENT OFFICE 2,412,916 PROCESS FOR PREPARING PETROLEUM SULFONATES - Jere C. Showalter, Goose Creek, Tex., assignorto Standard Oil Development Company, a corpo-g ration of Delaware ‘Application August 21, 1944, Serial sq. 550.395 3Clahns. (on. was”). 1 recoveryoi the solvent employed and that ‘the extract indicated asebeing removed from the unit ‘ The present invention is directed to a process for. preparing water-soluble alkali metal sul‘fo vi'aiine ll 'willbe substantially free mm‘ selective notes. More particularly, it is directed to the preparation of petroleum suli‘onates which may be solvent. the petroleum fraction to be sulfonated, by con trolling the conditions of sulfonation and by em ploying a particular sequence oi steps in cleans ing the sulfonic acids. By‘ the careful control of 'the'steps of the process. I am able to obtain a ’ _ V -..' the extract and sulfuric acid initially at atmos treating mineral or petroleum oils with sulfuric acid of sulionating strength and subsequently neu tr‘alizing the sulfonic acids with an alkali to ob taln sulionates suitable for use as detergents and 15 ionates having novel characteristics by selecting _ suli'onatlng' step ls‘preferably carried out with It is well known to produce sulfonic acids and salts, of sulfonic acids of varying properties by In accordance with the present invention, I '- 300 to 400 pounds of acid per barrel of extract. In the acid treating step approximately 50% of the extract is converted ‘to sulfonated oil. The as a. shampoo. propose to prepare water soluble salts of sul ‘ ‘In Y-‘acld treating unit IS‘ the extract is admixed with "98%~ sulfuric acid in amountsranging irom useciin‘soit or hard water or in sea water. These sulfona-tes do not leave a deposit of gummy resi "dues or foreign bodies on the object being cleansed, and are particularly suitable for use cleansing agents. " " pheric temperatures, and Lie maximum temper ature of the reactants increasing to a temperature in the range of 120" to 170° F. as the sulfonation reaction proceedsv From unit l5 the mixture of reactants is with drawn by line I] to ‘settler i8, where the react ants separate into a lower sludge layer, which is removed via line l9,’ and an upper layer or su1~ 20 fonated oil, which is removed through line 20. To the sulfonated oil flowing through line 20 is added water via inlet 21 in ‘an amount ranging from 3% to 5% ,0: thesulfonated ollkand the two‘comppneints are;the_n passed through ‘mixing metal salt of sulfonic acid readily soluble in water 25 deyice 9 to ‘cause the thorough admixture oi ,wa ter with the 'suli’onated oil and the mixture is and appearing as a clear, light colored, aqueous then passed through line ill to a second settling solution. free from contaminating solid bodies and vessel 22. The addition of the water to the mix capable of being used as a detergent without leav turecausesa separation to take place in‘settler lngan undesirable residue on the object being 30 22 witl'isulfi'onidacids andwater, in addition to cleansed. entrained oil, settling as a bottom layer and un The present invention will now be described in converted oil separating as a top layer; The un conJunction with the drawing, in which the sole converted oil is withdrawn from the upper por ?gure is in the ‘form oi a flow sheet diagrammat tion oi‘ settler 22 via line 23 and discarded from ically illustrating the process of the present in the system'. The suifonic acids, water and oil vention. entrained therein settling in the lower portion of A distillate fraction having a viscosity in the vessel 22 are withdrawn via line 24. range of 75 to 85 seconds Saybolt at 100° F. and To the mixture flowing in line 24 is added an obtained by fractionation of a naphthenic crude alkali metal hydroxide via inlet 25 in an amount oil is passed via inlet Ii into a solvent extraction unit l2, where it is contacted with phenol as the 40 sui?cleht to neutralize the sulionlc acids. It is preferred to employ either sodium or potassium selective solvent under conditions to form 8. ref hydroxide and to add an amount Just su?icient ?nate fraction and an extract fraction. The step to neutralize the suli'onic acids and convert them of solvent extraction with selective solvents is well to suli’onic soaps‘ It will usually be found desir known to the art. and for this reason the oper ating conditions in this unit will not be described 45 able to pass the mixture of sulionic acids and al kali metal hydroxide through mixer 26 in order in detail. It will be suiiicient to say that usually to insure a thorough admixture of the compo the extract will have approximately 35% of the nents. While a series ofbafiies have been indi volume of the original distillate and the rai’?nate cated in the schematic mixer shown in the draw will comprise the remaining 65% of the distillate. ing, it will be understood that a "essel provided The ra?inate may be discarded from the solvent with a mechanical stirrer may be employed and extraction unit via outlet l3 and the extract may the mixture maintained in the vessel until the be withdrawn through line 14 to acid treating sulfonic acids have been neutralized with the hy unit I5. It will be understood that the unit des droxide. ignated by numeral [2 as the solvent extraction The solution of sulionic soaps is withdrawn unit will include suitable distillation columns for 2,412,91s 3 4 from mixer 28 and is treated for the removal of impurities thereirom. These impurities will usually include unreaeted oil and water-insoluble sulionates, as well as foreign bodies which may have been present in the feed or may have been such use it is desirable to employ a mixture com prising 15% of the alkali metal sulionates and 85% water. The water content of the solution may, of course, be readily controlled, but for pur poses of illustration the addition of water thereto picked up in the apparatus. The material from mixer it passes through line 21 and isopropyl al cohol is added thereto via line 2!. It is desirable for controlling the concentration of the solution is indicated by inlet line IS. The aqueous solution oi water-soluble alkali to use isopropyl alcohol commonly known as 50% metal suifonates has a pH 01' 'l and is free from alcohol, that is, 50% of the alcohol diluted with 10 contaminating materials and solids which would 50% of water, and in an amount of one volume 0! be undesirable in a detergent material. The al the alcohol solution to one volume of the sulionic' . kall metal salts oir thesuiionates are readily soluble soap solution. The constituents in line 21, are in water, audit is, therefore, unecessary to em then passed into mixer 29, where they are thQre ploy a vehicle or solvent, such as alcohol, in the oughly admixed. The mixture is removed by line 15 solution in order to maintain the sulionate salt 30, where light hydrocarbon material is added by in solution. inlet II and then passed through a mixer 32' and It is to be emphasized that the washing steps line I3 into settling vessel 34. A number of light and settling steps in the described process are hydrocarbon fractions are suitable in the use of necessary in order to obtain a detergen-t'material this extraction step. For example, lique?ed pro 20 having the characteristics given above. The omis pane, butane or pentane fractions may be used sion of any of these steps results in a product as well as higher boiling fractions, such as hexane which is not free from solids and gummy con or light naphtha or liquid mixtures including these constituents. It will usually be desirable to stituents and is unsuitable for use as a deter gent in shampoos and like compositions. As employ a light naphtha as the light hydrocarbon 25 stated above, the dual ?ltering step illustrated and to employ one volume of the light hydrocar is optional and may be omitted in case satis bon to two volumes of the alcohol-sulionic soap factory settling is obtained in the preceding solution. The addition of the isopropyl alcohol vessel. and light hydrocarbon to the aqueous sulfonic Having fully described the present invention, soap solution causes the segregation of the oil and what I desire to claim is: light hydrocarbon as one fraction and the alcohol l. A method for producing a detergent suitable and aqueous soap solution as another fraction, for use as a shampoo comprising the steps of and these two fractions are separated by settling extracting a naphthenlc distillate having a vis in unit M. The oil and light hydrocarbon sepa cosity in the range of 75 to 85 seconds Saylbolt rates as an upper layer and is removed from unit 35 at 100° F. with a selective solvent under condi 34 via outlet 35, and may be discarded. The tions to form a raillnate and an extract, contact lower layer, comprising alcohol and sulionic soap ing the extract with concentrated sulfuric acid solution, is withdrawn through outlet 36 to a dis in the range oi’ 300 to 400 pounds of acid per bar~ tillation column 31, where the alcohol is vapor reel 01’ extract under conditions to lorm a sludge ized and removed as overhead via outlet ll. 40 layer and a suli’onated oil layer, separating the The alcohol-tree sulionlc soap solution is with sludge layer, adding from 3% to 5% ct water to drawn from the lower portion of the distillation the sulionated oil layer and settling .to produce an tower 31 through line 38 and sent to a settling oil layer and a sulionlc acid layer, withdrawing vessel 40, where it is allowed to settle for a sub the sulionic acid layer and contacting it with a stantial interval of time to separate a minor wa solution of an alkali metal hydroxide to form ter-lnsoiuble soap fraction from the remaining a soap, mixing the soap with isopropyl alcohol, portion oi the solution. It will be iound desirable extracting the mixture with a light hydrocarbon, to allow the solution to remain in settler 40 in distilling the extracted soap to remove alcohol a quiescent state for an interval of time of the order of 24 hours, After the mixture in unit 40 has settled to form an insoluble soap traction and a soluble soap fraction, the soluble soaps may be withdrawn as indicated through outlet Ii and the insoluble soaps may be withdrawn from the bot tom of the vessel through outlet 42. Under some conditions the settling step in unit 40 may not re move all of the solids from the soluble soaps, and under such conditions it may be desirable to pass the water-soluble soaps via line ‘I through ?lter 43 in order to obtain a puri?ed water~soluble sul fonate solution, However. the settling step may separate substantially all of the solid materials from the water-soluble soaps, and if such be the case the ?lter may be bypassed by line H. Valve I3’ is indicated for controlling the flow through filter '3 and valve 44' for controlling the ?ow through bypass line H. The puri?ed aqueous so lution of alkali metal salts of sulfonates may be passed either through ?lter 43 or bypass line 44 into outlet line 45. from which they may be with drawn to suitable storage facilities, not shown. The aqueous solution is line ‘5 is free from harsh alkalies and solid materials and is suitable for use as a detergent. The aqueous solution has and light hydrocarbon therefrom and settling to to form a layer of water-insoluble soap and a layer of water-soluble soap and removing the water soluble soap as product. 2. A method for producing a detergent suitable for use as a shampoo comprising the steps of extracting a. naphthenic distillate having a vis cosity in the range of '75 to 85 seconds Saybolt at 100° F. with a selective solvent maintained under conditions to form a ra?lnate and an extract, separating the extract from the rafilnate and con tacting it with 98% sulfuric acid in the amount of lrom 300 to 400 pounds of acid per barrel oi oil and at a temperature in the range of atmos pheric to 170° F. to form a sludge layer and a suiionated oil layer, removing the sludge layer, adding from 3% to 5% or water to the sulionated oil layer and settling to obtain an oil layer and a sulfonlc acid layer, withdrawing the sulionlc acid layer and contacting it with a solution or an alkali metal hydroxide to form a soap, adding iso propyl alcohol to the soap to form an admixture, extracting the admixture with a light hydrocar bon, distilling the extracted mixture to remove alcohol and light hydrocarbons therefrom, and subsequently settling to form a layer of water been found suitable for use as a shampoo, and for 76 insoluble soap and a layer of water-soluble soap 9,412,916 5 and removing the water-soluble soap as product. 3. A method for producing a detergent suitable for use as a shampoo comprising the steps of ex tracting a naphthenic distillate fraction having a viscosity in the range of '15 to 85 seconds Saybolt at 100“ F. with a selective solvent maintained un der conditions _to form an extract having approxi mately 35% of the volume of the original distil late and a ra?inate, separating the extract from the rafi‘lnate and admixing therewith 98%~sul (uric acid in amounts ranging from 300 to 400 pounds of acid per barrel oi.’ extract and at a temperature inthe range of atmospheric to 170° F’. to form a sulfonated oil portion comprising ap proximately 50% oi.’ the extract and a sludge por tion, settling to form a sludge layer and a sul tonated oil layer, removing the sulfonated oil layer, adding from 3% to 5% water thereto and settling to iorm an oil layer and a sulionic acid 6 layer, withdrawing the sulfonic acid layer and contacting it with a solution of alkali metal hy droxide in an amount sufficient to neutralize the sulfonic acid layer and form a soap. mixing the resulting soap with an equal volume of isopropyl alcohol, adding to the mixture of soap and iso propyl alcohol a light hydrocarbon in the amounts of 2 volumes of soap alcohol mixture to 1 volume oi’ a light hydrocarbon and subsequently settling to obtain a light hydrocarbon layer, an alcohol aqueous and soap solution layer, removing the al cohol and aqueous soap solution layer and dis tilling to remove alcohol therefrom, removingal cohol-free suli'onic soap solution from the dis tillation step and settling to form a layer 01 water-insoluble soap and a. layer of water-soluble soap and removing the layer of water-soluble soap as product. JERE C. SHOWALTER.