US2252957A - Process for producing petroleum sulphonates - Google Patents

Description

remainjn the pretreatedoil, and which m Patented Au 19, 1941 UNITED STATE PATENT OFFICE;

PROCESS FOR PRODUCING PETROLEUM SULPHONA'I'ES John R, Averill, Webster Groves, Mo.,.and Edwin Y E. Claytor, Long Beach,

Calif., assignors to Petrolite Corporation, Ltd., Wilmington, DeL, a

corporation of Delaware No Drawing. Application September 6, 1940,

Serial No. 355,610

1 Claims. (or. 260-504).

This invention relates to a novel process for producingmineral oil sulphonates from petroleum, mineral oil, suitably selected fractions or distillates thereof, or extracts obtained therefrom, by the. use of sulphonating agent, such as fuming sulphuric acid or oleum. The process involves subsequent separation of the petroleum sulphonic acid salts, unreacted oil, and unreacted acid in the form of salts, and is further characterized by the separation of a material commonly known as polymers," "acid sludge," acid, pepper, peppery sludge," etc. This last mentioned product or material is removed in the conventional procedure for manufacturing suphonic acids or sulphonates by pretreatment. with acid such as sulphuric acid.

Our invention is more specifically concerned with the employment of a raw material of the kind characterized by having present polymerizable or sludge-producing constituents of the kind which ordinarily would be eliminated by pretreatment, i. e., adding 2-l0% of sulphuric the production of petroleum sulphonates. To this end we have devised a process in which a single sulphonation step is employed to produce both the sulphonic acids and the polymerized material commonly referred to as peppery sludge, pepper, or the like. As to'a' more com 'plete description of such peppery sludge or similar materials, reference is made to, U. S. Patent No. 1,947,861, dated February 20, 1934, to

Liberthson. Y

Another important object of our invention is to eliminate the peppery sludge as such, without being admixed with accompanying unreacted oil and the like, thus affording an additional economy. 4

Still another object or our invention is to obtain the advantages previously enumerated, to

acid of varying strength, for instance,- 80-100% sulphuric acid, to the raw material, mixing thoroughly, and subsequently permitting settllng to take place. Although pretreatment is facture of mineral oil sulphonic acid or sulphonates, it is objectionable for a number of reasons. In the first place, pretreatment involves a distinct and separate step. 'In the second place, the withdrawal of the acid sludge or [polymers involves'the accompanyi loss of a certainjamount of oil. Thirdly, pretreatment is a t to cause, the formation of a certain amount of oil-soluble petroleum sulphonic acids which at be removed at some subsequent stage. is last statement in regard to oil-soluble sulphonic acids or sulphonates as objectionable impurities in top oil can be readily appreciated when one notes that the production of sulphonic acids or. sulphonates,'whether by conventional procedures. opby the process herein described,-re-

suits in a substantial portion of top oil or unreacted oil, which oil, for purposes of economy,-

must find utilityelsewhere, i; e., as a lubricating 011 stock, fuel oil, or the like; and for this reason'the top oil or theunreacted oil must be substantially fee from oil-soluble sulphonic acids, or sulphonates, even though the amount of the recovered sulphonic acids or sulfonates is relatively small.-' 7

One of the main objects of our invention is to eliminate pretreatment as a .s p rate step in the conventionalmethod employed in the menu wit,"avoid'pretreatmen t and eliminate the peppery sludge subsequently free from accompanying unreacted oil, and at thesame time recover the unreactedoil substantially free from ma-- hogany acids or sulphonates, and for that matter free from peppery sludge, and which accordingly, is readily utilizablejfor any suitable pur- DOSE.

The fourth obiect of our invention is to ac complish the three objectives aforementioned and simultaneously eliminate substantially all peppery sludgeand inorganic salts, so as to yield a suitable solution of sulphonates substantially free from peppery sludge, sodium sulphate or the like. In view of the subsequent description of the procedure employed in carrying out our process, it will be obvious that there are numerous other advantages, hereinafter pointed out, which make the process particularly rapid and economical; l

Specifically, we have discovered that a solu tion of green acid sulphonates in a tertiary mix ture of ethyl alcohol, isopropyl alcohol, and water has the characteristic property of extracting -sub-. stantially all mahogany acid sulphonates from the unreacted oil, without dissolving any 8% saidoil in. said; sulphonatemixture and without itself. I dissolving appreciably in the unreacted oil, and furthermore, is devoid of any solvent properties in respect to inorganicsulph'ate, such as-am- I monium sulphate and'the like. 'T'A solution of sulphonates of. the. kind described does not" act either as a solvent or suspending agent for the peppery sludge, and the procedure that we employ results in polymers or peppery sludgesubstantially de-oiled, i .je., 'free fromany adherent.- oil in a form which represents-a'feathery interface, suspension, or loose emulsion in the aqueous solutionof inorganic sulphates or the like. I

The effectiveness of the present procedure is made possible primarily by the employment of the aqueous solution of a mixture of ethyl and isopropyl alcohol. The results obtained, and in fact, the application of the procedure herein demuch as 65% of material which can be converted scribed, would be impossible, except by means of a solvent of the kind selected. This may be illustrated by the fact that if one attempts to substitute lsopropyl alcohol, or an aqueous solution thereof, for the alcoholic mixture herein employed, there results an unsatisfactory separation, due to the solubility of unreacted oil in the alcoholic solution of the sulphonates and of alcohol in the unreacted oil. Thus, one "obtains a sulphonate extract which is contaminated with I an excess or objectionable amount of unreacted oil, and which is of an inferior quality, or which must be treated subsequently so as' to separate or extract the unreacted oil. Other solvents which might otherwise work are unsatisfactory,

on account of their higher cost and .greater fire hazard. It will be recalled that one of the principal, objects of the present invention is to apply a single sulphonation step, a single washing step,

and a single separatory step involving a new tralized material; whereas, conventional prorial, i. e., raw material containing polymerizable cedure employing the same kind of raw matecomponents, invariably includes pretreatment and sulphonation, i. e., two distinct steps in which acid or oleum is involved, and usually includes four distinct stepsin regard to separation: the conventional washing operation, neutralization,

hogany acids or salts from' the unreacted oil, or, inversely,- the extraction of unreacted oil from a mixture of sulphonates, and another step in Similarly, an effort to employ a solution of ethyl alcohol is not feasible, for the reason that ethyl alcohol does not yield a substantial or completeseparation of inorganic salts in the form of a highly concentrated solution. Incidentally, the

same is true in regard to methyl alcohol. We

a step involving the alcoholic extraction of maa every instance.

- S03; one necessarily must increase the amount wish it to be understood that references herein to ethyl alcohol, are intended to include, for example, denatured alcohol, and particularly, the type which is essentially a mixture of 90 parts of ethyl alcohol and 10 parts of methyl alcohol.

In view of what has be said, it will be appreciated that the present pr cess involving a single sulphonation step, a singlewashing step,vanda single separatory step, involving neutral or substantially neutral material, yields a mixture of sulphonates of unusual purity and'alsofa resultant top oil or unreacted oil of unusual purity. Indeed, in these three principal steps, we-accomplish substantially the same results thathereto fore have been accomplished by four or five sen-"l aratesteps. a i i v, The actual operative steps employedin practising our. process are obvious, in view of what has been said previously. The-first step is to ployed is not. critical. catedf by conventionalsulphonation procedure.

larly desirable raw materials are exemplified by non-pretreated Gulf Coast lubricating distillate having a Saybolt Universal viscosity at 100 F. of about 400 seconds; or one may employ any suitable petroleum crude, such as Peruvian, Colombian, Russian, Californian, Ranger Burbank, Mid-Continent, etc. When employing crude oils, rather than any distilled fractions thereof, our preference is to employ Gulf coastal crude of the type which is essentially naphthene in nature. once is made to the aforementioned patent to Liberthson, and also to U. S. Patent No. 2,115,847, dated May 3, 1938, to Gohr; U. S. Patent No. 2,084,506, dated June 22, 1937, to Rosen, and U. S. Patent No. 2,188,770, dated January 30, 1940, to Robertson. 1

The actual step of sulphonation, or rather, the combined sulphonation-polymerization step, is

identical with the conventional sulphonation step employed in the sulphonation of pretreated materials obtained from the same source; but it is to be remembered that in the present instance such pretreatment is eliminated and the sulphonation step simultaneously involves polymerization, 1. e., the production of pepper or peppery sludge. The-four patents previously referred to describe suitable conditions for sulphonation; but it is our experience that the most desirable conditions for sulphonation may be indicated by the following approximate range:

' Our preference is to use oleum in substantially The oleum will vary from 10% excess S03, to 35% excess S03; and we preferably use commercial oleum, representing approximately 20% excess S03. The amount of oleum employed per unit weight of hydrocarbon material depends upon the percentage of material to be sulphonated in the total, its molecule weight 'and-ease of sulphonation. Needless to say, as the strength of oleum decreases below 20% free employed to obtain the same result; and if one employs an oleum of a higher concentration, for instance, 30% oleum, one may employ alesser amount. On weight'basis, the oleum may vary 7 from 20%.or less to 300%, or even more.

It is understood that reference to various amounts of oleum is'not intended to indicate that experimentation is necessary, in order to find some critical conditions of sulphonation that make the presentprocess possible. The strength or amount of oleum or sulphonating agent em- It is the amount indi- However, as is readily understood by those skflled in the art, the use of excessive amounts of oleum is costly. because of 1 04a) The expense select a suitable raw material. Raw, materials suitable for carrying out this'process are charbypresence of a' significant amount of 5 0 Z5 matilafi which produce a sludge or .0: the oleum itselfwith a creased yield onv the basis of oleum used; r (b) A longer time required to add the-oleum; (c) A greater tendency towards oxidatiom- (d I[ncreased cost due to amount of wash water required and increased amount of waste ,acid'to be'disposed of.

Thus, forpurposes of-econoinyQone uses the As to suitable raw materials, refernomical.

. washihsfstep,

" kind previously-l indicated, scribed in detail. 'I'he' "bility of minimum amount justified "on the yield of sulphonate. In other wordagthe use of an increased amount or oleum might yield a larger amount of sulphonate; but such procedure might beuneco- 7 As has been repeatedly emphasized, the novelty of the invention herein described lies in the'puriflcation steps subsequent to sulphonation. Although'polym'erlzationis included with sulphonation, the amount of acid used in the step of sulphonation is not altered by use of ,the method described herein.

The temperature employed during reaction a may vary from any suitable temperature which permits sulphonation to'take place at a'suitable rate and in suitable yield, for instance, F., to

I any temperature. short of the point where rapid oxidation takes place, as indicated by the liberation of excessive amounts of sulphur dioxide or the like. Generally spealiing, the upper range for. the. sulphonating temperature is roughly 205-210 F., i. e., Just short 0! the boiling point of water. This, varies somewhat with the particular raw-stock selected, strength of oleum,

' ratio of oleum to raw stock, etc.; and in some instances, .onemay even employ a temperature exceeding the boiling point of water. Roughly speaking, TO-110 FL, appears to be a very suitable temperatureoi' sulphonation, it being understood, 01 course, that polymerization is simultaneously involved. 5

The time of reaction is directly related to the batch size, container employed, mixing device, temperature of sulphonationl etc. Generally "speaking, the time employed automaticallyis determined by the addition of a sulphonatlng agent at such a rate as not to exceed a predetermined temperature range; for instance, one addsthc oleum at such a rate as not to exceed a temperature of TO-110 F., if this has been predetermined as the most suitable temperature. Here again, the time of sulphonation would be directly affected by the presence or absence or cooling coils, the effectiveness of such cooling coils, etc. As has been previously suggested, this particular item represents nothing more than conventional sulphonation procedure employed in connection with similar pretreated stock.

The step of washing'thesulphonated mass, 1. e.,

treating the sulphcnated mass .with wash water or with a saline solution inorder to separate un- -reacted acid, is conducted in the conventional manner to leavebehind as little uncombined acid as possible and not yield an excessive amount of draw-oil waste or acidwater. 'Generally speakins, the rule is to addsumcient water or saline solution so as'tmdilute the draw-oil! acid to a strength of approximately -80% H2804. This again, is the, conventional step employed in sulphonating similar material after pretreatment." -E Atterflsuch sulphonation involving simultaneous polymerization, fiand after theconventional washing step; weeihploy the novel step of the and which isnow dewashed acidic mass obiained in the manner above described is next neutralized with any suitable base, such as,

caustic potash, ammonia, or an caustic soda, amine, which forms a-water-soluble salt. A base of the kind described may be indicated as a "base forming a water-soluble salt." For purposes of economy and in view of increased soluthe resulting salts, we preterto use ammonia, i. e., ammonium hydroxide of commerce,

or 28 B. strength. The amount added under suitable conditions of agitation is sui'llcient to make the acidic mass just neutral to methyl orange. One might neutralize to a lesser degree; i. e., free acidity may bepresent, provided there is complete separation from the sulphonate oi inorganic salts and free mineral acid. Thenext phonates dissolvedin the unreacted oil.

Thus, the next step is to decide on the proper alcoholic solution and ratio'to be employed in combination with the neutralized or substantially neutralized mass. As has been previously indicated, the alcohols employed are isopropyl alcohol and ethyl alcohol, the expression ethyl alcohol being intended to include denatured alcohol which may. contain approximately 10-15% of other materials of the kind commonly employed as denaturants, provided that such denaturants are compatible with the procedure outlined. For purposes of economy, we prefer to use denatured alcohol containing ethyl alcohol and 10% methyl alcohol. For practical purposes, this will be considered as if it were ethyl alcohol.

The mixture employed :consists of approximately one-third-each isopropyl alcohol, ethyl alcohol, and water. The actual percentages of any individual component is within the ratio of 20% and 55%. It must be remembered that the ratio of the alcohols to each-other is approximately 1-1, or within the ratio oi approximately 60-40 and 40-60. Ordinarilyapeaking, the per- Tcentage of water in the neutralized mass approximates 15-20%. If, however;'onef obta ns a neutralized mass with an fexcessive amount of water, for instance. 25-35%; obviously one would make an appropriatereduction in the amount-oi water added to the alcohol mixture. It is to be noted that the process as indicated-removes-inorganic salt in the form of a solution and not as undissolved crystals, 1. e., as an insoluble liquid bottom layer. Obviously, one must; attempt to obtain the most concentrated solution possible, without the presence of undissolved crystals. For this reason, the amount or inorganic salts to be removed as a concentrated solution and the amount of water present, are factors in determining the amount and ratio of aqueous alcohol solution to add to the neutralized mass. Use of too little water has the dual disadvantage of causing the alcohols to throw inorganic salts out as solids and to allow excessive solution of the alcohols in the unreacted oil. It is to be noted that the ratio of alcohols to each other and the percentage of water to be added must be predetermined with reasonable. accuracy: but when once determined, such procedure can be employed indefinitely without iurtherchange. provided that sulphonation conditions and subsequent steps'remain the same. Actually. a person skilled in the tions. 1 However, even at the expense oi verbosity,

such directions for predetermination are included. 7

It is our preference to make mixtures of senatured ethyl alcohol and isopropyl tained these three binary mixtures, we prefer tov alcohol in the ratios 01 40-80, 50-50, and 60-40.. Having 'obmake solutions in water form of each binary mixture in the following ratios:

Alcohol mixture Water Percent Percent 80 76 70 66 60 65 46 50 50 sulphonates may be employed as is, or may be 1: e al to twice such weight.

Thus, having obtain'e the 21 solutions aforementioned, one simply-makes a series of cut and try experiments with representative samples of neutralized mass, using an equal volumeand also 50% excess. The first series of such 42 tests,

.will immediately and conclusively indicate substantially the best mixture of alcohols in relation to eachother, the best dilution with water and approximately the best ratio to use in proportion to the neutralized mass. Subsequent minor.

variations can be made to indicate optimum conditions for any specific set of conditions.

Experime be conducted in any convenient man'ner. Visual examination readily reveals conditions which eliminate the bulk of inorganic salt brine along with the peppery sludge. Qnreacted 'oil can be examined. in the conventional manner for the presence of mahoganysulphonate salts. The middle layer of sulphonates can readily be examined forthe presence of either inorganic salts or unreacted oil. Experiments which appear to indicate the best conditions or minor variations thereof can readily be repeated in large size separatory funnels or centrifuge tubes and rechecked with greater accuracy and convenience. The methodsfor examination oranalyses of petroleum sulphonic acids and their salts are well known; but for convenience, reference is made to Sulphated Oils and Allied Products, by Bur-' I ton and Robertshaw, 1940, Chemical Publishing 00., Inc., page l'et seq.

We are il1lly aware that the procedure herein described'may be ofdefinite value in refining procedure where the primary-nbiect is not. to obtain sulphonates, but to obtain a suitable refined. pe-

troleum P duct in which theremoval ofr e sulphonates is an incidental step, rather than the primary object. The sulphonate's herein deof the kind above described may scribed may, [of course, be used for any purpose for which this type of material ,is conventionally employed, for-instance, resolution of water-in oil type emulsions, the manufacture of oil-inwater emulsions, wetting agents, spray oils, cuttingoils, road oils, and the like. 1 In employing such procedure; whether experimentally in laboratory glasswareor in plant operation, as will be illustratedby subsequent Q example, one obtainsa' separation in whichfthe unreacted oil is ubstantially free'from'fpeppery sludge and fromsulphonicfacid or sulph'onates; pne an lalcol cli c-gsolutionhof asettlement are unsatisfactory; g I A the preparation of these, 'mixedsulphonates ofgood grade,- is illustrated added.

green and mahogany sulphonates, with the green acid sulphonates predominating substantially free from (a) unreaoted oil; (b) peppery sludge;.

and (c) inorganic sulphates. The peppery sludge appears in the draw-01f brine either as a feathery layer, or suspension, or as a loose emulsion. The unreacted oil is separated and employed for any suitable purpose; the draw-oil? brine is withdrawn and may be used for some other purpose, if desirealole; i. e., if it consists primarily of ammonium sulphate, it might be freed from sludge and used for fertilizer or other purposes. An alcoholic solution of the green and mahogany freed from alcohol and excess water by the usual distillation procedure. I The alcohol solution,

which is recovered, of course, may be employed in a subsequent cycle. It is to be emphasized that previous reference to a sulphonating agent, such as oleum, is for purpose of illustration only, and that any suitable sulphonating agent, such as 100% sulphuric acid,'SOa, or the like might be employed. Similarly, chlorosu'lphocnic acid or other suitable sulphonating agents may be l employed. Oleu'm is. however, most desirable from thestandpoint of rapid sulphonation and 'low cost.

It need not be remarked" that the previous step followed by dilution with the may beivaried in the respect of neutralization, alcoholic solution, that the alcoholic solution may be added first and the neutralizing agent afterwards, or both might be added simultaneously. .In other, words, neutralization and addition together with agitation required for extraction,

may conveniently be considered as a single step.

It is understood that the hereto attached claims are not intended to be limited inregard to whether neutralization i's'emp loyed first'or dilu--' procedures are employed" tion first, or if the two simultaneously, unless such claims recite specific conditions involving such procedures. I

It is to be emphasized that the addition of the, aqueous alcoholic solution isnot nierelydilution, but is in essence an extraction process in which J the alcoholic solution with the dissolved green acid sulphonate extracts the mahogany ,sulpho-' nates present in the unreacted oil. .For this reason, both in the laboratory procedure outlined and in actual plant operation, the additional the aqueous alcoholic solution must be followed by thorough and vigorous mixing treatment of such duration as to-permit extraction to take place. In'other .words, mere dilution and, immediate v A suitable procedure for in the following example:

. i sample-'1" .4,000 lbs. 0 crude for 45 minutes after-the last of the acid-has been the acid water settled out at 80 layer, the re acids mo r to 40, c. and then neutralized with ammonia w methyl orange while keeping the temperature below 50 of solvent solution,

I naphth'ene base Gulf Coast oil are mixedJwith 2,0 0Q Q 1bS." of 20%,0191111 while keeping the temperaturebelow-w -C. Thistakes 2% hours approximately. The batch is stirred,

Then" this non-'homo'genous mass .is i washed with 1,000 lbsrof water, stirrifig well, and H p v C. in 3 hours. -After withdrawal of the" 3 bottom mainder, consistingiof a layer of I green acids and, .a :layerofiunreacted oil containing mahogany C. The impure sulpho-' A nate mixture is thereupon pumped into a large permits.

- troleum,

ization step; aqueous ve file nd subsequent separation of tank which contains a mixture of 840 lbs. de-

natured alcohol, 840 lbs. isopropyl alcohol, and

night. The bottom layer containing the inor-.

ganic sulphates and water (sp. gr. 1.18-1.19) together with the semi-emulsified or "polymers is drawn off. The middle layer which contains the ammonium salts of the green acids and the mahogany acids is sent to a still, where about 48% of the charge by weight is distilled oil. The material remaining in the still after distillation is a commercial standard prodnot which has various uses, amongwhich' is its wide applicability for resolving petroleum emulsions.

This invention is not to be limited by the example or specific description which has been presented herein solely by way of illustration. It is our intention that the invention be limited. only by the appended claims, in which we have em deavored to claim all novelty which our process In the claims where the term "alkali is used, it is intended to embrace ammonium and peppery sludge substituted ammoniums, as well as the alkali metals.

Having thus described our invention, what we claim as new and desire 'to secure by Letters Patent is:

- oil substantially vent addition-extraction step involving neutralq ization by means of an inorganic soluble saltiorming base and the addition of a predetermined amount of an ethyl alcohol-isopropyl alcohol-water mixture in which the percentage composition or the components has been predetermined, said percentage composition in regard to each. component being within the range of not less than. 20% and not more than 55% by volume and said addition being made so that theadded aqueous alcohol solution is not less than one-half the weight and not more than twice the weight of the neutralized sulphonate; (d) permitting said previously agitated diluted mass to separate into a three-layer system consisting of (A) unreacted free from mahogany acid sulphonates and peppery sludge; alcohol solution of petroleum sulphonates substantially free from unreacted oil, inorganic acid salts, and peppery sludge; and (C) a substantially concentrated inorganic salt brine containing loosely commingled p ppery sludge; and (c) withdrawing said aforementioned (A) layer and (C) layer. 1

3. A process for pr ducing sulphonates, char acterized by subjecting non-pretreated crude petroleum containing a significant amount of poly- -merizable constituents to the following procel. A process for producing petroleum sul--.

phonates, characterized by subjecting a member of the class consisting of non-pretreated crude petroleum, non-pretreated mineral oil, non-pretreated petroleum mineral oil extract containing a significant amount of polymerizable constituents to the following procedure; (a) a sulphonation-polymerization step; (b) a washing stepv involving an aqueous vehicle and. subsequent separation of dilute acid; (0) a neutralization-alcoholic solvent addition-extraction step involving neutralization by means of a soluble salt-forming base and the addition of a predetermined amount of an ethyl alcohol-isopropylalcohol -water mixture in which the percentage composition of the components has been predetermined, said percentage composition in regard to each component being within the range of not less than 20% than by volume and 'said addition being solution is not less than one-half the weight and not more than twicethe .weight 'oi the neutralized suland not more made so that the added aqueous alcohol phonate; (d) diluted mass to separate permitting said previously agitated from mahogany acid sul I sludge; (B) an aqueous acohol solution of petroleum sulphonates substantially free from unre acted oil, inorganic acid salts, and peppery sludge; and (C) a substantially concentrated salt brine containing loosely sludge; and (e), withdrawing said a ioremen tioned (A) layer and (C) layer. v

2. A process for producing petroleum sulphothe class consistin significant amount of polymerizable constituents to .the ioldistillate, and non-pretreatedinto a three layer system commingled p pp ry dure; (a) a sulphonation-polymerization step; (b) a washing step involving an aqueous vehicle and subsequent separation of dilute acid; (0) a neutralization-alcoholic solvent addition-extraction step involving neutralization by means of an 55 consisting 01: (A) unreacted oil substantially tree 'honates and Pepp r? riates', characterized' by merizable constituents; to

inorganic soluble salt-forming base and the addition of a predetermined amount of an ethyl alcohol-isopropyl alcohol-water mixture in which the'percentage composition of the components has been predetermined, said percentage composition in regard to each component being within the range of not less than 20% and not more than 55% by volume and said addition being made so that the added aqueous alcohol solution is not less than one-half the weight and not more than twice the weight of the neutralized sulphonate; '(d) permitting said previously agitated diluted mass to separate into a three-layersystem consisting of: (A) unreacted oil substantially free from mahogany acid sulphonates and peppery sludge; (B) an aqueous alcohol solution of petroleum sulphonates substantially free from unreacted oil, inorganic acid salts, and peppery sludge; and (C) a substantially concentrated inorganic salt brine containing loosely cominingled (e) withdrawing said aforeand (C) layer.

peppery sludge; and mentioned (A) layer 4'. A process ion-producing petroleumsulphosubjecting non-pretreated, Gult coastal naphthene base, crude petr'oleum containing a significant amount of polythe following procedure: (a)- a -sulphonation polymerization step; (b) a washing step involving an aqueous vehicle and subsequent separation of dilute acid; (0) a lowing, procedure: (a) a sulphonation-poiymer,

(b) a washingstep involving an dilute acid; (c) a neutralization-alcoholic sol- L.neutrallzation'-alcoholic .solvent-addition-extraction step. involving neutralization by means of an inorganic soluble salt-forming base and the addition of a, predetermined amount of an ethyl alcohol-isopropyl alcoholewater mixture i i-which the percentage composition of the components has been predetermined, said perc'entagecomposition in regard to each component being within the range oi not less than one-halt the weight and not more than (B) an aqueous less than 20% and not more than 55%by volume andsaid addition being made so that the added aqueous alcohol solution is not twice the weight oi the neutralized sulphonate; (d) permitting said-previously agitated diluted mass to separate into a three-layer system consisting oi: (A), unreacted oil substantially free from mahogany acid sulphonates and peppery sludge; (B) an aqueous alcohol solution of petroleum sulphonates substantially'free from un-- reacted oil, inorganic acid'salts, and peppery sludge; and (C) a substantially concentrated inorganic salt brine containing loosely commingled peppery sludge; and (e) withdrawing said ai'orementioned (A) layer and (C) layer.

5.- A process for producing petroleum sulphonates, characterized by subjecting non-pretreated, Gulf coastal naphthene base, crude petroleum containing a significant amount of polymerizable constituents to the following procedure: (a) a sulphonation-polymerization step; (b) a washing step involving an aqueous vehicle and subsequent separation of dilute acid; a neutralization-alcoholic solvent additlon-extraction step involving neutralization by means of ammonium hydroxide and the addition of a predetermined amount of: an ethyl alcohol-isopropyl alcohol-water mixture in which the percentage composition of the components has been predetermined, said percentage composition in regard to each component being within the range of not less than 20% and not more than 55% by volume and said addition being made so that the added aqueous alcohol solution is not less thanaone-half the weight and not more than twice the weight of the neutralized sulphonate; (d) permittingsaid previously agitated diluted mass'to separate into a three-layer system con-- sisting of: (A) unreacted oil substantially free from mahogany acid suliongates and peppery sludge; (B) an aqueous alcohol solution oi. petroleum sulionates substantiallyiree from unreacted oil, inorganic acid salts, and peppery, sludge; and (C) a substantially concentrated inorganic salt brine containing loosely commingled mentioned (A) layer and (C) layer.

6. A process for producing petroleum sulphonates, characterized by subjectingnon pretreated, Gulf coastal 'naphthene base, crude petroleum containing a significant amount 01' dure: (a) a sulphonation-polymerization step; (b) a washing step involving an aqueous vehicle and subsequent separation of dilute acid: (0)

a neutralization-alcoholic solvent addition-ex- .dure:

centage composition of the components has been predetermined, said percentage composition in regard to each component being within the range of not less than 30% and not more than by volume and said addition being made so that the added aqueous alcohol solution is not less than one-half theweight and not more than twice the weight of the neutralized sulphonate;

(d) permitting said previously agitated diluted (b). a washing step involving an aqueous vehicle and subsequent separation of dilute acid; (0)

a neutralization-alcoholic solvent-addition-extraction step'involving neutralization by means of ammonium hydroxide and the addition of a predetermined amountof an ethyl alcohol-isopropyl alcohol-water mixture in which the percentage composition of the components has been predetermined, said percentage composition in" regard to each component being within the range of not less than 30% alcohol solution is not less than oneehalf the weight and not more than peppery sluge; and (e)-withdrawing sald aforereacted oil, inorganic acid polymerizable constituents to the following .procetraction step involving neutralization by means of ammonium hydroxide and the addition 01 a predetermined amount of an ethyl alcoholiam:

5c propyl alcohol water mixture in which the perv 7 eppery slud ."mentioned (A) layer and (C) layer, and subsequently employing distillation procedure to separate the alcohols in the (0) layer from the wa-' twice the weight of the neutralized sulphonate: (d) permitting said previously agitated diluted mass to separateinto a three-layer system consisting of; (A) unreacted oil substantially free from mahogany acid sulphonates and peppery 'sludge; (B) an aqueous alcohol solution of petroleum sulphonates substantially free from unsalts, a d pep e y sludge; and (C) a substantially concentrated inorganic salt brine'containing loosely commingled (e) withdrawing said aforeter and sulphonate mixture.

" some mavmmn an aqueous alcohol solution of peamount of poly. following proceandnot more than 40% by volume and said addition being made so' that the-added aqueous mwm E. 'CLAYTOR. v