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2,4113% Patented Nov. 12, 1946 UNITED . STATES’ » PATENT? cam-CE; PROCESS FOR TREATING HYDROCARBONS ' * Alan C. Nixon, Oakland, and David Louis Yabro'fl", vBerkeley, Calif., assignors ‘to 'Shell' 'j Development Company, San' Francisco; Calif‘; a corporation of Delaware No Drawing; Serial Application .No. 506,612. October-16,1943, \ . 10 Claims. ~(Cl. 196—"-30)?= 1 2 solution is then re-used for treatment of further“ This invention deals with a method for improv quantities‘of the original mixture; ingvthe rate of separation of alkaline treating The mixtures. to which-this invention is appli- ‘’ liquids or solutions from hydrocarbons or of facil itating‘steam strippingof the resulting fat alka-~ cable‘are either normally liquid or normally gas- ‘ ' line solution, if the latter is desired,- or both. This eous andip'referably have "an end ‘boiling point of below about 200 C. They are comprised of * inventiontis a continuation-in-part of our. co pendingapplication SerialNo. 394,004 filed May - hydrocarbons sulfate ‘ester acids, and‘ must sulfonic' be substantially 3431618301‘ otherv free'from rela'--“ It .is.we1l known that hydrocarbon ‘oils are I tively strong acids because of the effect‘ of thesev " 10 acids upon the alkaline‘ treating solutionlby per- ‘ manently poisoning or neutralizing it. ' pounds of ma-nyxdi?erent degrees of saturation, ' mixtures of hydrocarbons and may vcontain com Alkaline‘ treating liquids‘ or solution which may such‘as paraf?n's, ole?ns, polyole?ns, acetylenes, i naphthenes; or aromatics. It is also knownthat ~ hydrocarbon :oils frequently. contain-weak acids - be employed‘ must be stable and'inert so as not ' > 10-5, such as hydrogen sul?da'mercaptans, alkyl theyvmustihave a greatersolvent power for some" " to react irreversibly with the components of e. g. havingrdissociation constants below about‘ 15 thei‘mixture‘under'the conditions of the process?” componentsthan for‘ others; ‘and they ‘must be - phenols; etc. :It is often desirable to treat such separable‘from the dissolved components by phys hydrocarbon mixtures :to separate‘the'm .intohy- . ical means such;as,.;by ‘fractional distillation‘ ' ‘drocarbons'vof different ,d'egreesof saturation'for ;. washing out; either while they‘ are in the to purify particular hydrocarbons,:such:.as hen-12:20 and/or form originally’absorbed or else after they’ have zene-,:~.tolue‘ne, xylene, ‘butylenes, buta'dienasiso; been changed chemically by a simple operation" - prene,_ethylene; acetylene, etc.-; or to remove-weak .7 . acids of theztype-mentionedv above .from such: . hydrocarbons or mixtures. ' » Onemethod of carrying outsuch-a separatiorn such as air oxidation. " If employed in liquid ex- ' traction,:they must‘ be only partially miscible with‘ ' 25 inixtur'es'to bejextracted». " They maybe aqueous or non-aqueous; or puri?cation is by extracting one~or more-oi the components with an alkaline solution‘; which , Some ‘speci?c examples'of alkaline treating liq!- ' uids for the ‘separation of unsaturated hydrocar= ' hasv a» preferential lsolvent powerior one‘ or more- ' bons from mixtures containing them are: aniline,‘ ‘ of the components of thelmixture, and there; 30 methyl‘ aniline, toluidine, etc: solution of complex ‘ -' after Isaparating the resulting alkaline ‘solution-‘'7 ~ from vthe dissolved portion of the mixture. ‘The ' - extraction'maybe either-by liquid-liquid_or by" = vapore‘liqui'd contact, including extractive-‘distil- ~ salts 'of univalent heavy metals from groups I and " II of the periodic‘table, such as copper, silver, *' gold,vmercury, etc;; 'chlorides',"nitrates, cyanidesi" lation. "(In order'to achieve separation by eXtrac-" acetates; etc., with ‘anhydrous; aqueous, alcoholic, ’ " eta,‘ ammonia or'lower organic aliphatic-primary; ‘ ' tive distillation thev two“ or more compounds to be saparated‘ from' one another should as a rule boil amines, such as methyl amine, ethyl amine, propyl . ' not'more than ‘about‘20°' C. apart'an‘d preferably ‘ not‘more thanabout=10° C, apart.) These ex- J amine, butyl amine, ‘ethylene diamina-nionon di-, or tri-ethanolamine, or quaternary ammonium‘. bases as tetra methyl, trimethyl benzyl, ‘etci; am"- ' " tractions are normally carried out in apparatus 40 monium 'bases,.etc. In the extraction of weak permitting contact of the alkaline treating solu--' acids normally ' associated ‘with petroleum, oils,‘ tion ‘and the mixture containing the hydrocar alkaline treating solutions; such as tripotassium ‘ phosphate, sodium phenolate, sodium borate,'so- ‘L bons, usually.‘ by counter-current flow, .either through a packed or a plate column, or through a dium. or potassium carbonate, ‘organic bases, such series-of mixers and settlers, whereby two end 45 as ethanolamine, ‘diamino propanol, piperidine',‘ etc:, or strong solutions of alkaline metal'hydrox- ., phases are produced and separated, one of which is an extract comprising the ‘fat alkaline treating ides,‘ preferably'having concentrations of 25 to ' solution containing theextracted portion of the 50%“, or alkaline solutions containing solutizers ' may be employed. . mixture, and the‘other of which is the 'raf?nate Solutizers are known‘ as organic substances portion of themixturie. These two phases may be 50 which when in the ‘liquid state are solvents for both liquid or one. may be liquid and the‘ other may weak organic acids, are substantially insoluble in . be aJVapor, For‘ reasons of economy, the fat'alka Water-immiscible: liquids, are soluble in aqueous linesolutioh .is' usually regenerated such as by strong bases, are chemically inert to the action‘ steam, stripping, air blowing or washing with a of said bases even at elevated temperatures," and suitable‘ wash liquid, " etc, and the‘regen'erated 2,411,105 3 have boiling temperatures preferably substan It has been discovered that the addition of rel atively small amounts of a stable organic surface active agent which contains at least 8 carbon atoms per molecule and has a molecular weight of below about 1000 (preferably below about 600) and which is dispersable in the alkaline treating iially higher than water. Solutizers are used to enhance the extractive powers of aqueous alkaline solutions for weak organic acids such as mercap ;ans and phenols. The solutizer process and the various solutizers have been described in a series 3f patents and patent applications as well as in ;he general literature, for example, in the Yabroff at al. U. S. Patents 2,149,379, 2,149,380, 2,152,166, liquid, results not only in reducing'foaming and in an improved rate of separation, but also in effective and rapid breaking of emulsions which 2,152,720, 2,152,723, 2,164,851, 2,186,398, 2,202,039; 1O may form between the two phases produced in the process. It is important that the agent be readily applications Serials Numbers 255,684, ?led Feb and completely dispersed through the treating so ."uary 10, 1939; 271,962, ?led May 5, 1939; Re?ner lution so as to be continuously and evenly effec and Natural Gasoline Manufacturer, May 1939, tive throughout ‘the entire zone of contact and pages 171-176, and March 1940, pages 73-76, In the surface-active agents used in the process are: :lustrial Engineering and Chemistry, volume 32, those which form true solutions in the treating: pages 257-262, February 1940, etc. solution or spontaneously form colloidal disper In choosing one of the above alkaline treating sions therein, i. e. form dispersions of at least col liquids, sight must not be lost of the boiling tem loidal dimensions. perature requirements relative to the boiling tem The agents should be reasonably stable toward perature of the mixtures. For example, in vapor 20 the action of oxygen in the presence of caustic. liquid extraction, it is important that the solvent chosen have a boiling temperature higher than alkali and at elevated temperatures of steaming: if steam regeneration is employed as part of the that of the mixture to be treated, and in the spe process. . ci?c case of extractive distillation, it 'is desirable In a regenerative process wherein the spent that the boiling temperature of the solvent be not less than about 50° C. higher than the boiling treated solution is continuously regenerated and temperature of the mixture. Accordingly, the recirculated for further contact with the mixture particular treating agent to be employed neces to be treated, it is desirable that the surface-ac sarily depends upon both the boiling temperature tive agents, in order to be more or less perma-v of the mixture to be treated,- and the: type of nently useful, should not be extracted from the process to be used in the treatment. treating solution when ‘the latter is contacted with the hydrocarbon mixture. ‘ The presence of Unfortunately, processes of this type often pro the agent in either of the separated components duce foam and/ or emulsions which greatly reduce the maximum throughput of a given treating of the mixture may be undesirable, as it may in terfere with their intended uses. Therefore, the unit. Emulsions, if formed, occur in liquid-liquid treating, and foaming may occur in vapor-liquid surface-active agents should be substantially in treating. Foaming may also occur if distillation, steam stripping, air blowing etc. is employed as soluble in hydrocarbon oils. a means for recovering the alkaline treating so lution from the extract or ra?'inate. these agents from the treating solution in which The nature of the substances responsible for difficulties is not de?nitely established. It is be lieved though, that foam and emulsions are pro duced by small amounts of impurities, such as possible such separation. 'In some cases, it may be desirable to remove case they should have a property which makes compounds related to gasoline gums or similar ~ The organic surf ace-active agents of this inven tion are organic compounds containing at least one atom of sulfur and/or oxygen. More’speci?-v cally they are members of the following groups: resinous materials formed by reaction of some of sulfonic or sulfuric acids having at least one alkyl the components of the hydrocarbon mixtures radical of more than 4 carbon atoms, naphthenic acids ‘having molecular weights between about 250/ and 500, fatty acids having between 8 and 14 car bon atoms per molecule, and the corresponding alkali and alkali-earth metal salts of each of the above free acids. Such surface-active compounds with themselves or with the alkaline treating so lution or a component thereof, particularly in the presence of oxygen. In many cases it is impos sible to keep air away from such mixtures, since small quantities easily leak vthrough joints of _ pumps and valves, etc.. Thus, most hydrocarbon ails contain small but de?nite amounts of dis may be generally represented by the formula RY, solved oxygen. .In the case of treating solutizer . solutions with alkaline solutions containing ohenolates, a phenol type resin- may be formed, for instance, by the interaction of mercaptans, aldehydes or other impurities in the mixture ;reated. Accordingly, it is the purpose of this invention ;0 provide means for improving, the rate of sepa cation of aqueous alkaline treating liquids from ;he hydrocarbons which are being treated. An ither purpose is simultaneously or independently ;0 reduce the foaming tendency of the treating wherein R is an organic radical and Y is a polar radical containing an atom selected from the group consisting of oxygen and sulfur. - Some of these agents are known to be‘ more effective for breaking or settling emulsions, others are more effective for breaking or reducing foams, while still others are effective for both. . Agents which are generally effective to prevent or break both foams and emulsions are the alkali and alkali-earth metal salts or free acids of sul fonic and sulfuric ester acids (containing an alkyl radical of more than 4 carbon atoms) ,.of naph thenic acids (having a molecular weight between iquid, for example, when it is being regenerated 250 and 500), and of fatty acids. (having between )y steam stripping. Still another purpose is to 8 and 14 carbon atoms per molecule). provide means for preventing the formation of The sulfonates and sulfates may, if desired, zmulsions caused by the presence of emulsi?ers 70 contain non-functional radicals such as halogen, n_ the treating liquids, particularly those con vaming impuritieswhich readily react to form emulsi?ers. It is yet another purpose to provide t remedy for breaking emulsions formed in such reating processes. - ether, amino, imino, hydrosul?de, sul?de, ester, carboxyl amide, etc, radicals. Free carboxyl radicals should preferably be absent in the sul fates and sulfonates since some sulfated or sul 75 fonated fatty acid soaps cause violent foaming. 224113.105 5 ‘ Speci?c sulfonates which we have found to be suitable for our purpose are, for example, water soluble alkali metal salts of petroleum sulfonic acids such as the salts of “green acids” produced in the manufacture of medicinal oils by acid treatment; or of the products of treating kero sene or lube oil extracts with strong sulfuric acid, etc.; or of various aliphatic or alicyclic sulfonic acids such as fatty sulfonic acids, fatty aromatic sulfonic acids, naphthene sulfonic acids; or of sulfonic acids of various alkylated (containing an alkyl radical of more than 4 carbon atoms) ‘ten zenes, diphenyls, xylenes,‘ diphenyl methanes, naphthalenes, anthracenes, phenanthrenes, tet thenic alcohols obtained in the catalytic reduc tion of fatty or naphthenic acids, alcohols ob, tained by condensation of ketones or aldehydes followed by a hydrogenation; or alkyl aromatic mono esters of sulfuric acid, etc. A convenient source for many of the active sulfate ester acids are the sludges obtained in the acid treatment of cracked distillates, or the spent acids obtained in the polymerization of ole?ns or in the alkyla tion of isopara?ins with ole?ns with sulfuric acid. The alkali or alkali-earth salts of naphthenic acids having a 'molecular‘weight between 250 and 50,0,may, be derived’ from petroleum and‘ may comprise a mixture of salts having molecule ralines; phenols (derived from petroleum or coal 15 weights within this range. tar distillates) ; chlornaphthalenes, diphenyl ox The salts of the fatty acids containing between ides, chlorinated diphenyl oxides, diphenyl sul ?des, diphenyl amines, phenyl naphthylamines, dinaphthyl oxides, sul?des or amines, pyridines, quinolines, isoquinolines, pyrroles, pyrrolidines, piperidine, thiophenes, thiophanes, etc.; or of various sulfonic acids of carboxylic acid esters or amides, such as for example, of the ester sulfo carboxylic acids or sulfonate amides having the general formulae: (0:41-01? )n , O=(|J—R’ 8 and 14 carbon atoms per molecule such as sod ium or potassium caprylate, pelargonate, caprate, undecylate, sabinate, laurate, tridecylate, myris tate, etc., are effective both as demulsi?ers and defoamers. However, the salts of lower fatty acids, those having less than 8 carbon atoms and those having more than 14 carbon atoms such as stearic acid, are substantially ineffective. . ' Amounts of the surface-active agents which need to be added to improve the rate of settling or breaking vof the emulsion or foam or both, are insufficient to materially affect the action of , respectively, wherein the R radicals are organic radicals of more than 4 carbon atoms such as all phatic or cyclic hydrocarbon radicals, M is an alkali metal and n is an integer normally not the treating agent. This amount, may vary, be tween about .001% and 1%, and preferably be tween about .001% and .1% by volume of the treating agent. The different types of treating agents are capable of dissolving different amounts of the surface-active agents and different mix 35 tures may require different amounts to reduce While the carboxylic acid esters and amides foaming and/or emulsi?cation. This is probably listed above are very effective for our purpose, due to the difference in reactivity of the ions of many of them have the disadvantage of being the respective agents and their effect on the hy susceptible to hydrolysis during steam regenera tion of the treating liquid forming free carboxy 40 drocarbon'mixtures treated. Therefore, actual laboratory tests within the above limitations may lic acids upon decomposition, the salts of which be required to accurately determine the‘ amount may cause foaming unless they have 8 to 14 ca of the agent or combination of agents for the bon atoms. ~ most effective separation of the given mixture It is of interest to note that the alkali metal with a given alkaline treating solution. salts of sulfonic acids possessing at least one It is desirable that the bene?cial effect of the alkyl radical of more than 4 carbon atoms, are salt shall‘not be restricted to and be dependent in general far more effective than the salts ‘of on a speci?c range of concentration substan corresponding sulfonic acids not possessing them. tially narrower than the limits indicated aboVe— For example, the alkali metal salts of naphtha that is to say, there should not be a sudden re greater than 2. g V > > lene or anthracene sulfonic acids such as mono-‘ or dibutyl phenyl phenol sodium mono- or di sulfonates, sodium tetrahydro naphthalene sul fonate, i-sopropyl naphthalene sulfonate, etc., are only mildly bene?cial if at all in carrying out the purpose of this invention, whereas the cor responding salts of higher alkylated naphthalene versal of the bene?cial effect, 1. e., an increase in the emulsi?cation or foaming tendencies or both, of the extracting solution upon addition of a slight excess of the salt over the optimum quan tity. On the contrary, the bene?cial effects should extend over substantially the entire range of concentration indicated, and changes in the sulfonic acids are highly effective. - effects due to-deviations from the optimum con The sulfonates may be prepared in various ceh'trati'on should be only matters of degree. ways. Aliphatic sulfonates may be obtained Many surface-active salts. particularly the ordi under some conditions by treating ole?ns 'or di (ii) nary soaps such as sodium stearate, sodium ole?ns with strong sulfuric acid; or by treating oleate, etc., effect de-emulsi?cation in certain organic acid sulfates with sodium sul?te so as speci?c amounts. However, when present in to eliminate sodium sulfate; or by oxidation of slightly larger amounts increase, rather than de mercaptans with nitric acid, etc. crease, the emulsion tendencies of the extracting Sulfate ester acids, the alkali salts of which (if) solution. For example, sodium stearate in a con are suitable for our purpose are, for example, the centration of .06% effectively broke a semi-stable fatty sulfates, such as mono‘ lauryl, cetyl, stearyl, etc., sulfate acids; or mono esters of sulfuric acid _ obtained by treating with strong to moderately strong sulfuric acid Various olefins or alcohols such as the long chain olefins obtained in the vapor phase cracking of wax at about 350‘°-560° C., polymers obtained in the polymerization of normally gaseous ole?ns with inorganic polyoxy acids or Friedel-Crafts catalysts, fatty or naph solutiz‘er emulsion; while in .08%‘ concentration a stable emulsion remained. v p’ ' ‘ Example I In the table below, effects of a number of repre sentative surface-active ‘agents-are shown in a spent or contaminated aqueous copper am monium acetate solution which when fresh had thefollowingcomposition: .25 mol/liter of cupric 2,411,105 7 8 ions, 2.93 mols/liter of cuprous ions, 10.4 mols/liter of ammonia, and 4.0 mols/liter of acetic acid, plete separation was noted, and whether'or not at the end of the settling time a rag was left at the Samples of this spent solution were subjected to interface. ‘ 'Other samples of the same solution were sub an emulsion test in which they were agitated with an equal amount by volume of tertiary o jected to a distillation test in which their rela amylenes at a temperature of about 25° F. The tive foaming tendencies were observed. Results resulting emulsion was then allowed to settle and were as follows: Addition compound Ooncentra~ ‘on, Settling cross-time in mg./l00 cc. minutes None __________________________________________________________________________ _. Sodi sulfate of higher secondary alcohol _______________________ __ Foaming 30 50 6 100 ' Rag Moderate. d 5 Mildly positive. 500 6 Negative ______ __ 67 6 134 375 6 5 Sodium lauryl sulfate ____________________________________________ __ Sodium sulfonate ethyl methyl oleoamide _______________________ ._ ' D0. No improvement. 67 Sodium sulfonate ethyl oleoamidc _________________ ._ 67 Sodium petroleum sulfonate _______________________ ._ Sodium hydrocarbon sulfonate ______________________ __ 67 67 Improved. Do. Very much improved. Slightly improved. Sodium alkyl aryl sulfonate ____ _._ _____ __ 67 Much improved. Dioctyl ester of sodium sulfo sucemate _______________ _. 67 Mildly improved. Sodium sulfonate of complex stearyl alkyl compounds. 67 Sodium salt of green acids _______________________________________ _. the time required for substantially complete sep- We claim as our invention: aration was noted and whether or not at the end 25 1. In a, process for treating a mixture com of the settling a residual rag (large globules of hydrocarbon surrounded by thin ?lms of solution) Was left at the interface between the solvent phase’ and the hydrocarbon phase. The results were as follows: 30 Organic surface-active agent Fresh solution ..................................................... .. Spent solution _____________________________________________________ .. Do. 100 prising predominately hydrocarbons with an aqueous alkaline treating liquid to effect the sep aration of components of said mixture which are soluble in the .treatirvT liquid from components which are not soluble therein, in which process Gone. in‘ gin/100 cc. Settling time in Vol. of residual solvent minutes rag 0 0 1% 35 Remarks 0 9 No foam. Stable foam. 2 No foam. I. Salts of organic acids: A. Sulfonic acids— Produced from transformer oil extract ___________________ _. 0 ____________________________________________ _. Commercial petroleum sulfonates __________________ __ 0 ____________________________________________ __ “Green acids” _____________________________________ __ Sodium amyl alkyl poly-ether sulfonate ___________ __ Dioetyl ester of sodium sulfo succinic acid _________ __ D0 _________________________________________________ __ B. Sulfuric ester 'acids— .l 1% .01 9 2 Do. . 1 2% 0 Do. . O1 3 5 Do. .1 .l .1 1A 1% 31/1 0 0 0 No foam, refused to emulsify. No foam. Hydrolyzes rapidly. No foam. .01 5 0 .1 3 0 _ Glyceryl rieinoleyl sulfate (Turkey red oil) ______________ __ Do. Do ____________________________________________ __ .01 2 0 Do. Do ____________________________________________ __ . 001 8 5 Do. Alkyl sulfate-i-NazSOi ______________________________ _ _ Do __________________________________________________ __ . l .01 1% 4 (C4H9)CH<O2H5>C2H4?HC2H4CH(C2H4)2 ______________ ._ . 01 10 . 1 4 3% Do. .1 3 0 Do. Trace 8 Do. Do. Trace DO. (|) SOaNa Sodium alkyl sulfate ____________________________________ ._ 0. Naphthenic acids- ' Cyclic carboxylic acids __________________________________ _Do ______________________________________ __ Naphthenic acids (equiv. wt. 332) _________ _. Do __________________________________________________ ._ . 01 5% 2 Do. .1 4 0 Do. .01 7 0 Do. -1 9 0 .01 l 5 D. Fatty acids Larvic acid ______________________________________________ _Do ___________________________________________________ __ No foam. Do. Example 11 60 two phases are produced, a ?rst phase compris ing predominately hydrocarbons and a second The following table discloses the effects of a phase. comprising predominately aqueous alka number of representative surface-active salts line treating liquid and at least a substantial por covered by this invention when employed in a tion of components of said mixture which are solutizer solution having the following composi soluble therein, in which process a relatively sta ble dispersion of one phase in the other is pro tion: KOI-I ___________________________ __ 6 normal duced, the improvement comprising the method of reducing the stability of such a dispersion which comprises e?eoting said treatment in the Samples of the solution containing various 70 presence of from about 0.001% to about 1% by volume of said treating liquid of an organic sur ones of the surface-active salts were subjected to an emulsion test in which they were agitated with face-active agent which forms a dispersion itself a cracked gasoline under standardized conditions, of particles at least as small as of colloidal di and the resulting emulsion was then allowed to mensions in said aqueous treating liquid, which is settle. The time required for substantially com 75 substantially insoluble in said mixture and which Potassium isobutyrate ____________ __ 1.5 normal Potassium phenolate _____________ __ 1.0 normal 2,411,105 is a salt of a naphthenic acid having a molecu 10 fraction containing substantial proportions oi lar weight between about 250 and 500. 2. The process of claim 1, wherein said mix hydrocarbons with di?erent degrees of satura ture is a gasoline distillate. 3. The process of claim 1, wherein said mix ammonium acetate solution, whereby two phases tion and unsaturation with an aqueous copper are produced, a ?rst phase comprising predomi ture contains a substantial proportion of 04 di nately hydrocarbons of a higher degree of satu ole?nes. ration and a second phase comprising predomi 4. The process of claim 1, wherein said treat nately said aqueous solution and dissolved there ing process is a liquid-liquid phase separation in a substantial proportion of the hydrocarbons process. 10 of said fraction which have a higher degree of 5. The process of claim 1, wherein the treat unsaturation, in which process a relatively sta ing process is a vapor-liquid phase separation ble dispersion of one phase in the other is pro process. duced by the action of impurities formed as a 6. The process of claim 1, wherein said mix result of reactions of unsaturates in said mixture ture contains diole?ns and said alkaline treating 15 with each other and with oxygen, the method of solution is an aqueous copper ammonium acetate preventing such a dispersion which comprises ef solution. 7. The process of claim 1, wherein the amount of the said surface-active agent is between about .001% and .1% by volume of said mixture. 20 8. The process of claim 1, wherein said sur face-active agent is an alkali metal naphthe mate. 9. The process of claim 1, wherein said dis persion is a foam. 25 10. In a process for contacting a hydrocarbon fecting said treating in the presence of from about 0.001% to about 1% by volume of said aqueous solution of an alkali metal salt of a petroleum naphthenic acid dispersable in said aqueous copper ammonium acetate solution, said ‘naphthenate having av molecular Weight be tween about 250 and 500. ALAN C. NIXON. DAVID LOUIS YABRO'FF.