US2441351A - Process of producing alkyl aryl sulfonates - Google Patents

Description

May 11, 1948. Lyn. um 2,441,351

` PROCESS OF PRODUCIHG ALKYL ARYL SULFONAT-ES v Filed Nov. 17, 1943 2 Sheets-Sheet 1 Comp/gni? 70 /acuz/m Pump ATTRNEY May l1, 1948.A L. H. FLETT 2,44L351 PROCESS OF PRODUCING:l ALKYL ARYL SULFONATES Filed Nov. 17, -194:5 2 sheets-sheet 2 Patented' May 11,1948

PROCESS F PRODUCING ALKYL ARYL SULFONATES Lawrence H. Flett, Hamburg, N. Y.,` assignorV to Allied Chemical & Dye Corporation, New York, N. Y., a corporation of New York Application November 17, 1943, Serial No. 510,668

13 Claims.

l This invention relates to improvements in the process of producing alkyl aryl sulfonates in which the alkyl groups are derived from petroleum distillates, the term alkyl referring to' non-aromatic radicals and including aliphatic,

larly benzene, and sulfonating resulting mixed alkyl aryl compounds. It relates especially to a method of preparing the mixed alkyl aryl com-A pounds or sulfonation so that upon sulfonation, followed by neutralization and drying, mixed alkyl aryl sulfonates are obtained which can be stored for extended periods of time without developing unpleasant odors to an undesirable degree. (As employed herein the term mixed, when applied to alkyl halides, alkyl aryl compounds, alkyl aryl sulfonates, and the like, denotes mixtures of such substances.)

The mixed alkyl aryl sulfonates with which the present invention is concerned are valuable for use as detergents, wetting agents, emulsifying agents, soap substitutes, and the like. Depending upon the purpose for which they are to be used, these mixed alkyl aryl sulfonates are derived from petroleum fractions within the upper gasoline range, the kerosene range, and higher ranges.

For example, where compositions are desired particularly adapted for use as wetting agents, petroleum distillates may be employed which boil as low as 100 C. In general, however,l a petroleum distillate boiling substantially below the boiling point of any nonane is not employed. Thus a useful petroleum distillate for the manufacture of mixed alkyl aryl sulfonates for use as wetting agents is one boiling within the range 140 to 180 C.

Where it is desired to prepare a composition predominantly of aliphatic and/or allcyclic hydrocarbons which boil Within the range 210 to 290 C.

One process for preparing these mixed alkyl aryl sulfonates involves chlorlnating the selected petroleum distillate, condensing resulting chlorinated hydrocarbons with an aromatic compound, usually in theipresen-ce of a Friedel-Crafts condensation catalyst such as aluminum chloride or zinc chloride, sulfonating the resulting mixed alkyl aryl compounds, treating the resulting sulfonation mass with a neutralizing agent, usually aqueous caustic soda, to convert the sulfonc acids to their salts, and drying the neutralized mixture. It will be understood thisv process is subject to many minor variations, such as the use of a mixture of oleiines corresponding to the chlorinated hydrocarbons, as alkylating agent, and distillation of lthe reaction mixtures at various points. United States Patents 2,196,985, 2,267,725'

and 2,283,199 disclose methods for making mixed alkyl aryl sulfonates of this class.

In making the mixed alkyl aryl sullonates it is advantageous to employ the aromatic compound in amounts in excess of those theoretically required for reaction with the alkyla'ting agent since otherwise poor yields of the desired products are obtained. Thus, in a process for making mixed alkyl benzene sulfonates, for example, involving chlorination of a kerosene fraction of petroleum it has been found to be desirable to employfthe benzene in proportions such that the weight of benzene exceeds the weight of the chlorinated kerosene. This amount of benzene is considerably in excess of that theoretically required ior condensationwith all of the chlorinated hydrocarbons present in the chlorinated l kerosene.

containing mixed alkyl aryl sulfonates in which the substituent alkyl radicals contain an average of more than 20 carbon atoms, a petroleum distillate having a boilingl range which reaches a maximum temperature of 300 C. at 25 mm. absolute pressure may be used. For most purposes, particularly for use as a general detergent, products derived from petroleum distillates within the kerosene range are preferred; that is, petroleum distillates which boil for the most part (i. e.,

at least 80 per cent thereof) within the range from 210 to 320 C. and preferably composed At the end of a condensation in which an excess of an aromatic compound has been used, the crude condensation mixture contains, in addition to the desired mixed alkyl aryl compounds, some unreacted aromatic compound, unchlorinated hydr-ocarbons, and a tarry mass which comprises the bulk of the catalyst residue. removed mechanically from the crude condensation mixture, leaving a remainder which is an oily liquid (and which for convenience is referred to hereinafter as ,the crude mixture of alkyl aryl compounds); for example, by allowing the crude condensation mixture to settle by standing,

andseparating' the resulting layers. The crude mixture of alkyl aryl compounds is then distilled to remove the unreacted aromatic compound and other lowl boiling constituents of the mixture, and

The tarry mass is the remaining alkyl aryl compounds are sulfonated. It has been customary to distill the. crude mixture of alkyl aryl compounds in batch stills of the ordinary type wherein the crude mixture of alkyl aryl compounds was maintained at temperatures above the boiling point of the aromatic compound at the existing pressure for relatively long periods of time; for example, of the order of about ten hours when distilling quantities of crude mixtures of the order of 9,000 pounds.

The mixed alkyl aryl sulionates with which the present invention is concerned oier several important advantages over other available synthetic detergents. First, because of the relatively inexpensive raw materials used in their manufacture, they may be produced economically. Also, due to the fact that they consist of not one compound but of a mixture of compounds having varying properties, they are capable of a wider variety of uses than many other synthetic detergents which are usually relatively specific in their action. In view of these facts, the mixed alkyl aryl sulfonates, particularlythe mixed alkyl benzene sulfonates, are the class of products which should be most satisfactory for general household uses. However, these mixed alkyl aryl sulfonates have the property of developing a rancid odor on being stored, a property which would have an adverse eliect upon the popularization oi these sulionates as general household detergents.

The reason for -the development of the odors in the mixed alkyl aryl sulfonates has not been determined. Apparently, the causes for the development are notl the same asv the causes for the development of odors in other materials which have this undesirable property. For example, while it is known that certain impurities in ordinary soaps cause the development of odors, there are no impurities of this type in the mixed alkyl aryl sulfonates. Various means have been found for reducing the rate at which odors are developed in the mixed alkyl aryl sulfonates. These have involved either subjecting the mixed alkyl aryl compounds to an additional odor-removing treatment before sulfonation or subjecting the mixed alkyl aryl sulfonates to an additional treatment or treatments.

. An object of the present invention is to provide an improvement in the process of preparing mixed alkyl aryl compounds of the above type which have been prepared with the use of an excess of an aromatic compound so that upon sulfonation, conversion of the sulfonic acids to their salts, and drying, dry mixed alkyl aryl sulfonates are obtained which can be stored for a relatively long period of time without developing unpleasant odors vto an undesirable degree.

A more particular object of the invention is to provide an improvement in the process of preparing mixed alkyl benzene sulfonates which involve chlorinating a paraffinic petroleum hydrocarbon distillate within the kerosene range, condensing resulting chlorinated hydrocarbons with at least a theoretical excess of benzene with the aid of a Friedel-Crafts condensing catalyst, espelcially anhydrous aluminum chloride, removing the excess benzene and other lower boiling constituents of the resulting condensation mixture by distillation, sulfonating resulting mixed alkyl benzene compounds, converting resultingmixed alkyl benzene sulfonic acids to their salts, and drying, whereby mixed alkyl benzene sulfonates of good storage properties are obtained.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The present invention is based upon the discovery that the development of unpleasant odors to an undesirable degree in dry mixed alkyl aryl sulfonates which have been prepared in the above manner can be traced, at least in part, to the nature of the crude mixture of alkyl aryl compounds subjected to distillation to remove therefrom the excess aromatic compound (which crude mixture contains unreacted aromatic compound, the desired mixed alkyl aryl compounds, petroleum hydrocarbons, and residual aluminum chloride catalyst), and to the duration of the heating period and other heating conditions involved in said distillation. It is based upon the discovery that heating of the crude mixture of alkyl aryl compounds containing residual aluminum chloride catalyst distributed therein at elevated temperatures for more than a short time period leads to the formation of substances which ultimately cause the development of unpleasant odors to an undesirable degree in the dry mixedalkyl aryl sulfonates produced from such crude mixtures.

Thus I have found, even though crude condensation mixtures of the type above referred to are permitted to stand quiescent so as to form a layer of the tarry material (comprising the bulk of the catalyst residue) and an oily layer of the remainder of the condensation mixture, and the layer of tarry material is mechanically separated from the remainder of the condensation mixture (for example, by decantation), the resulting crude mixture of alkyl aryl compounds contains small amounts of residual aluminum chloride catalyst distributed therein (for example, in the form of a solution of organic aluminum chloride condensation products dissolved in the oily mixture of alkyl aryl compounds, or in the form of a dispersion of aluminum chloride and/or of organic aluminum chloride condensation products in the oily mixture) which residual aluminum chloride catalyst produces a deleterious efect during ordinary heating of the crude mixture of alkyl aryl compounds at elevated temperatures, which eiect does not make itself evident in the resulting mixed alkyl aryl compounds themselves, but only after they have been converted to dry sulfonates by sulfonation, conversion to salts, and drying, and the dry mixed alkyl aryl sulfonates have been stored. Although the nature of the deleterious eiect is not known, it manifests itself by the development of unpleasant odors to an undesirable degree during storage of the dry mixed alkyl aryl sulfonates produced from such crude mixtures, even in the case of dry mixed alkyl aryl sulfonates which when freshly prepared are odorless.

In accordance with the present invention, mixed alkyl aryl sulfonates of improved storage characteristics are obtained from a petroleum distillate of the type referred to above by introducing alkyl groups corresponding to hydrocarbons of the petroleum distillate into an aromatic compound by a procedure including a Friedel- Crafts condensation with the aid of an aluminum chloride catalyst, in which condensation an excess of the aromatic compound is employed whereby a crude mixture of higher alkyl aryl compounds is formed which contains unreacted aromatic compound, separating the crude mixture of higher alkyl aryl compounds from the condensation reaction mixture, removing the aromatic compound present in the crude mixtures a,441,ss1

aromatic compound at the pressure at which it isto be vaporized, which temperature is below the boiling point ofthe mixed higher alkyl aryl compounds at said pressure, vaporizing the aromatic compound Without substantially vaporizing the mixed higher alkyl aryl compouii s, separating the vapors of the aromatic compound from :the

mixture and forming mixed higherY alkyl aryl sulfonates from resulting mixed higher alkyl aryl compounds. In order to effect rapid heating of the crude mixture .of alkyl aryl 'compounds it is preferably subjected, in relatively small portions at a time, to the inuence of a heating means which is at a temperature above the boiling point of the aromatic compound at the pressure at which it is to be vaporized, while the crude mixture is in a form which exposes a large surface,y

relative to its volume, to the heating means. It has been found that this step preferably should be carried out so that the mixture, or the portion of it being heated, remains for ,a period of less than minutes at a temperature sulciently high to vaporize the aromatic compound, and in -order to achieve especially valuable results it is desirable that the condensation mixture should be subjected to a high temperature of this order for no longer than 5 minutes, preferably for not more than about one minute.

Rapid heating of the'r crude mixture in the process of the present invention can be accom-l plished and the unreacted residue of the aromatic compound can be removed eiliciently from the crude mixture by causing the crude mixture to ilow in heat exchange relationship with a heating medium, which is preferably a hot surface but which may be a source of radiant heat or a current of a heated gas, while the crude mixture of 'alk'yl aryl compounds is in a form such that a .large surface, in relation to the volume thereof,

is in heat exchange relationship with the heating medium; for example, in the form of a thin lm. The same result may be achieved by spraying the mixture into a heated gas. The rate of flow of the crude mixture, the temperature of the heating medium, and the nature of the heat exchange relationship between the heating medium and the crude mixture are correlated so as to heat the crude mixture rapidly to the temperature required to eiect the vaporization of the aromatic compound, but the temperature of the heating medium and the time during which thecrude` 6 and avoids to an additional degree undesirable heating of the mixed alkyl aryl compounds.

Although the principal advantage flowing from vthe present process A`is the improvement in the storage. properties o! the mixed alkyl aryl sulfonates prepared from the purified mixed alkyl aryl compounds, theprocess has the additional important advantage that it can be, and preferably is. carried out in a continuous manner.

'I he presentinventio'nis preferably employed in the productionk of mixed alkyl benzene sulfonates, but it may also be employed in the production of the other mixed alkyl aryl sulfonates of the benzene series, and of the naphthalene and diphenyl series. In addition to the alkyl group (i. e., aliphatic, cycloaliphatic, or aralkyl group) derived from the petroleum distillate, and the sulfonate group attached to the aryl nucleus, these compounds may contain substitutents-such as other alkyl groups, halogens, and. hydroxyl.

,alkoxy,` phenyl, and phenoxy groups, although the compounds Acontain no Ymore than three and preferably only one such substituent. Thus, the mixed alkylaryl sulfonates may be derivatives of such compounds as phenol, cresol, chlorbenzene, toluene, xylene, resorcinol, phenetole, diphenyl, hydroxydiphenyl, and naphthalene. The sulfonates are usually prepared in the form of the sodium salts, but they may also be prepared in the formof their other alkali metal, ammonium, and organic base salts,l such as the alkyl ammonium and hydroxyalkyl ammonium salts.'

In the drawings there are disclosed in more or less diagrammatic form apparatus suitable for carrying out the heating operation forming a part of the present process. Figure 1 represents apparatus adapted to operation on a small scale, Figure 2 represents apparatus adapted to operation on a commercial scale.

Referring to Figure 1 of the drawing, the numeral I represents a suitable vessel for retaining the crude mixture of alkyl aryl compounds. As shown, this vessel is a dropping funnel equipped with a stop cock 2. The dropping funnel is arrangedv so as to feed the crude mixture of alkyl aryl compounds to a tube 3 which is inclined at an'angle so that the mixture may ilow at a predetermined rate down the tube and into a ask mixture is in heat exchange relationship with the heating medium are limited so as to av'oid substantial vaporization of the mixed alkyl arylv compounds. The vapors of the aromatic compound evolved from the crude mixture` of the -5 alkyl aryl compounds are removed from the remaining mixture, preferably substantially as rapidly as formed, to facilitate additional vaporization and to permit cooling of the remaining mixture of alkyl aryl compounds soon after vaporization of the aromatic compound. yBy this procedure the heating of the mixture of alkyl aryl compounds may be brought to an early end, thereby avoiding a change taking place inthe mixture and lalso condensation 0f the vapors in contact with the mixture.

It is sometimes desirable, particularly when the aromatic compound present in the mixture has a relatively low vapor pressure, to carry out thev 5. The tube 3 is surrounded over a portion of its length with a steam jacket l which is adapted to Aheat the flowing stream of the crude mixture.

Leading to the bottom of the ilask 5 there is an air inlet tube 6 equipped with a stop cock 6a and a capillary portion 1. As 'will appear from the Afollowing discussion, this tube with its apertures functions under the pull of vacuum in the apparatus to permit the slow introduction of air. The apparatus also comprises a tube 8 which is a vertical extension of tube 3. Tube 8 passes through a cooling vjacket Si and leads into a flask I0 immersed in a cold water bath I I. Leading from the side of the flask I0 there is a tube I2 which passes through acooling jacket I3 and thence to a means for creating a reduced pressure in' the apparatus such as a vacuum pump, not shown.

In the/operation of the apparatus, the vacuum pump is started and the stop cock 6a is adjusted so as to cause a regulated /ilow of air through the apparatus and to keep the pressure below atmospheric. Then the crude mixture, of alkyl aryl compounds is fed from the dropping funnel I into the inclined tube 3 where, during its ilow, it is heated rapidly in a thin illm' above the vaporization point of the aromatic compound. As the aromatic compound is vaporized it is swept up the tube 3 by the air stream and into the tube 8 where it is largely condensed and ilows into the ask I0. The vapors that are not condensed in the tube 3 pass into tube l2 and most of them are there condensed by the action of the cooling water in jacket I3. The mixed alkyl aryl compounds from which the aromatic compound and other low boiling constituents have been removed ilow from tube 3 into iiask 5 where they are collected. It will be understood that the rate of feed of the crude mixture of alkyl aryl compounds and the angle of inclinationV of tube 3 are such that the mixture is subjected to the heating action of the steam in steam jacket 4 for only a short time, preferably of the order of about one minute. In this way prolonged heating of the mixture is avoided and the mixed alkyl aryl compounds obtained as a result of the process are in such condition that upon sulfonation, neutralization, and drying they are converted to mixed alkyl aryl sulfonates of good storage properties.

Referring to Figure 2 of the drawing, the numeral 2l represents a storage Vessel for holding the crude mixture of alkyl aryl compounds. It is connected through a valved vpipe 22 with' a preheating chamber 34. The outlet of the preheating chamber leads to a distillation tube 23 which is inclined at a suitable angle to provide for the ow of the mixture at a predetermined rate down through the tube and into a receiver 25. 'I'he tube 23 is surrounded over a portion of its length with a steam jacket 24. As in the case of the apparatus shown in Figure l, the receiver 25 is provided with an air inlet tube 26, having a valve 26a and a capillary portion 21. Within the upper portion of the preheating chamber 34, an entrainment separator 38 is provided through which vapors generated in tube 23 pass on the way to pipe 39 which leads to a cooling coil 28 immersed in a cooling bath 29. Liquid entrainment removed by the separator 38 is returned to tube 23 through a pipe 36. The exit end of th'e cooling coil 28 leads to a receiver 30. The receiver 30 is provided with a cooling jacket 3| and with a pipe 32 leading to a vacuum pump or other system, not shown for maintaining a reduced pressure.

In the operation of this apparatus, ay vacuum is created in the system by means of the vacuum pump or other suitable apparatus, and the valve 26a is opened, providing a regulated iiow of air Athrough the apparatus under subatmospheric During its flow through the tube 23 the mixture of alkyl aryl compounds is rapidly heated above the vvaporization point of the aromatic compound,

which vaporizes and as it is vaporized is swept up the tube 23 by the air stream. The vapors and air pass through the preheating chamber 34 and entrainment separator 38 into y cooling coil 28, where the vapors are largely condensed. The

condensation of aromatic compound with or withv alkyl aryl compounds, from which the aromatic compound and other low boiling constituents, if

present, have been removed, flow from tube 23 into the receiver 25. Any liquid caught in en- 8 trainment separator 38 is returned to tube 23 by connecting tube 36. As in the case of the apparatus shown in Figure 1, the rate of ilow oi' the crude mixture of alkyl aryl compounds and the angie of inclination of tube 23 are such that the mixture is subjected to the heating action o the steam in the steam jacket 34 for only a short time, thereby avoiding extended heating of the mixture.

In order that the invention may be understood more fully the following example is given, This example has to do with the preparation of mixed alkyl aryl benzene compounds from kerosene, and for convenience the condensation product is referred to as keryl benzene." In the example the parts are by weight:

Example 1, part 1.-To 2,000 parts of a Pennsylvania kerosene (boiling range 185 to 275 C. at atmospheric pressure) agitated in a glass vessel, 0.80 part of iodine was added and dissolved. The temperature of the solution was raised to 60 to 62 C. and this temperature was maintained While a steady stream of chlorine was run into the agitated kerosene. After about three hours the introduction of chlorine was stopped. At this point the specific gravity of the kerosene had increased from 0.791 at 24 C. for the unchlorinated kerosene to 0.925 at 24 C for the chlorinated batch, the increase in specic gravity being due to the organically combined chlorine. The increase in weight due to the chlorination was about 438 parts.

Over a period of 20 minutes, 304 parts of this chlorinated kerosene were run into an agitated mixture of 608 parts of benzene and 27.4 parts of anhydrous aluminum chloride at room temperature. The temperature of the mixture was then raised to 45 C, and the mixture was agitated at about this temperature for an hour and a half. It was then allowed to settle for about l5 hours during which period it separated into a black lower tar layer and an upper layer which was the crude mixture of alkyl benzene compounds (i. e., crude keryl benrene) The black lower tar layer was drawn oi and discarded. The recovered crude keryl benzene was an oil which weighed 746 parts and contained a considerable quantity of unreacted benzene as well as other 10W boiling constituents. It also contained a small amount of residual aluminum `chloride dispersed therein in the form of insoluble, tarry particles.

Part 2.--The crude keryl benzene was then heated to remove the benzene therefrom employing 'the Iapparatus disclosed in .Figure 1 of the drawing. Thus, the crude keryl benzene was placed in the dropping funnel I, by means of a vacuum pump the absolute pressure inside the apparatus was reduced to 27 to 30 millimeters lof mercury and was kept at that point during the operation of the process, and air was allowed to now into the apparatus through stop cock 6a, tube into the tube 3 at the rate ofabout one drop per second, and it owed down the tube 3 into the portion surrounded by steam jacket 4 which contained steam at a. temperature of about C. (i, e., at atmospheric pressure). In this portion of the tube 3 the benzene'was quickly vaporized and the vapors were swept bythe air flowing through the apparatus out of the tube 3 and into the tube 8 where they were largely condensed. The purified keryl benzene, on the other hand, flowed down the tube 3 into flask 5 where it quickly cooled to room temperature. All of the l' was agitated with 18.3 parts of 10o per cent sulbenzene vapors were not condensed in tube .8

v and a part of the remaining portion was condensed by meansl of the action of the cooling water passing through cooling jacket I3. The puriiied keryl benzene was then agitated for a few minutes with "activated clay and was filtered to remove residual aluminum chloride catalyst dispersed therein.

'- Part y.2.-100 parts'of the purified keryl benzene furic acid at room temperature for about 45 minutes. After permittin'g'the acid mixture to stand for about one-half hour it separated into two u layers, the lower of which was an acid layer which was drawn of! and discarded. The-recovered upvper layer was then sulfonated by running in grad-` .l

'I ually, during a period of 10 minutes, 183 parts of.

^ 100 per cent sulfuric acid while agitating. Sulf fonation was thenl completed by agitating the' `sulfonates (sodium keryl benzene sulfonate) was mixture for one hour at a temperature of55to 60 C. The sulfonation mixture was allowed to stand in a separatory device fory one hourwhen it separated into three layers. The middle layer,

. which was constituted largely of the desired sulfon'ic acids, was separated from the others and neutralized with 50 per cent caustic soda solution. The resulting neutral aqueous solution was then drum dried. By this procedure 230 parts of a product containing mixed sodium alkyl benzene product preparedvby the process including the improvement of the present invention.

, When .operating in the manner described in the above example, to remove benzene from a. crude product prepared from a kerosene ofthe type employed in the example, vaporization of materials other than benzene does not occur to any considerable extent. However, when treating crude mixtures of alkyl aryl compounds derived from a higher boiling aromatic compound, such as phenol or -diphenyl, the conditions under which the excess aromatic compound can be removedfrom the mixture will be such that a certain amount of unreacted petroleum hydrocarbons are also vaporized. Petroleum hydrocarbons will also be removed from crude mixtures ofalkyl benzene l compounds when the mixture has been prepared from a low boiling distillate. I'

In the above example the temperature of the heating medium with which thev crude keryl benzene was brought into heat exchange relationship; i. e., the heated portion of tube 3, was at a temperature above the boiling point of benzene at the existing pressure but below the 65 boiling point of the mixed alkyl aryl compounds. It is possible also to operate the present process. by bringing the crude mixture of alkyl aryl oompounds into heat exchange relationship with a heating medium which is above the boil-ing point offl` the m'ixed alkyl aryl compounds. When operating inr this way the other conditions, including the nature of the heat exchange relationship between the heating medium and the crude mixture, such as the conductivity of the heat transthe mixture is permitted to rise. j the mixture is permitted to reach a temperature approaching the boiling point of. the mixed alkyl lo i'erring surfaces, the thickness of the body of the crude mixture of alkyl aryl compounds, and the rate at which the mixture is caused to move into and out of heat exchange relationship with the medium, must be so selected and adjusted that the crude mixture does not take up sumcient heat to reach a temperature at which appreciable amounts of the mixedalkyl aryl compounds are vaporized. In this connection it should be noted ll0 .'that the permissible period of time during which lthe crude mixture may be heated is dependent i in some measure upon the temperature to which Thus, where aryl compounds it is desirable to adjust conditions so that the mixture remains at this temperature for Vas short a time as possible.

While the present process .is preferably carn ried out in a manner similar to that described in the example, which includes passing a thin lm of a mixture of the alkyl aryl compounds containing excess aromatic compound into'a heat Y.

exchange relationship with a heating medium, as indicated above, the process may be carried out in other ways. Preferably, however, the crude mixture is in a form'such that it possesses a large Ysurface in relation to its volume. When these conditions are met the vaporization of the aromatic compound takes place rapidly and vheating of the mixed alkyl aryl compounds is required only for a short time. l

Since certain changes may be made in-y the above-described process without departing from the scope of the invention it is intended that all matter contained in the above description should be interpreted as illustrative and not in a limiting sense. l

.- This application is a continuation-in-part of 40 my application Serial No. 350,983, led August 3, 1940, which has been abandoned.

I claim: l

1.- The process of producing a mixture of 'higher alkyl benzene sodium sulfonates having 5 good storage properties in the dry form, which o with the aid of anhydrous aluminum chloride,

the benzene being employed in an amount in excess of the weight of the chlorinated hydrocarbons, stratifying the resulting condensation reaction mixture whereby there is obtained an oily layer comprising a mixture of higher alkyl benzenes and the excess benzene, and a sludgelike layer, separating the layers, continuously passing the oily layer, containing residual aluminum chloride catalyst, vin contact with a heated surface which is at a temperature of at least 100 C. but below the boiling-point of the mixture v any portion of the oily layer with the heated surface to a period of about one minute, separating the benzene vapors from the unvaporized higher alkyl benzenes, forming a mixture of higher alkyl benzene sulfonic acids from resulting higher aliq'l benzenes,v converting the higher alkyl benzene suli'onic acids to their sodium salts, and drying the resulting sodium salts.

1l 2. The process of producing a mixture of higher alkyl benzene .sulfonates having good storage properties which comprises chlorinating a parainic petroleum hydrocarbon distillate sulting condensation reactionvmixture whereby there is obtained an oily layer comprising a mixture of higher alkyl benzenes and the excess medium, regulating the rate of'ow of the mixuct comprising essentially a crude higher alkyl aryl compounds of the benzene series `mixture of and the excess varomatic hydrocarbon, said condensation product containing residual aluminum chloride catalyst, passing the condensation product. containing residual aluminum chloride catalyst, in heat exchange relationship with a heating ture, the temperature of the heating medium,

benzene. and a sludge-like layer, separating the layers. continuously passing the -oily layer, having residual aluminum chloride catalyst distributed therein. in contact with a heated surface which is at a temperature above the boiling point of benzene, vaporizing the benzene, adjusting the alkyl benzene sulfonates having good storage4 properties which comprises chlorinating a par` ailinic petroleum hydrocarbon distillate boiling for the most part within the range 210 to 320 C.. condensing resulting chlorinated hydrocarf bons with .benzene with the aid of anhydrous aluminum chloride as a condensation catalyst, the benzene being employed in an amount in excess of the weight of the chlorinated hydrocarbons. mechanically separating from thel resuting condensation reaction mixture an oily product comprising a crude mixture of higher albi benzenes. the excess benzene. and residual aluminum chloride catalyst, continuously passing the oily product. containing residual aluminum chloride catalyst. in contact with a heated surface which is at a temperature above the boiling point of benzene but ,below the boiling point of the mixture of higher alkyl benzenes and which has a large areal relative to the volume of oily product in contact therewith. vanorizing the bennene without substantially vaporizing the mixture of higher alkyl benzenes. limiting the time of contact of any portion ofthe oily product with said heated surface to a period of not more than 5 minutes, separating the benzene vapors from the unvaporized higher alkyl benzenes. and vforming a mixture of higher alkyl benzene sulfonates from resulting higher alkyl benzenes.

4. The process of producing a mixture of higher alkyl aryl sulfonates having good storage prop-V erties which comprises chlorinating a paramnic' petroleum hydrocarbon distillate boiling for the most part within the range 210 to 320`C., con- (lensing resulting chlorinated hydrocarbons with an aromatic hydrocarbon of the benzene series capable of condensing with an alkyl chloride by' aluminum chloride catalystthe aromatic hydro- Aa Friedel-Crafts condensation with the aid-of an carbon being employed in anamount in excess of that theoretically required for condensation with all of the chlorinated hydrocarbons, me`

chanically separatingirom the resulting V'con-f' densation reaction mixture a condensation prodand the nature ofthe heat exchange-relationship between the heating medium and the condensation product to heat the condensation product rapidly above the boiling pointsof the aromatic hydrocarbon, vaporizing the aromatic hydrocarbon without substantially vaporizing the mixture of higher alkyl aryl compounds by limiting the temperature of the heating medium and the time `during which the condensation product is in heat exchange relationship with the heating medium, separating the vapors of the aromatic hydrocarbon from the unvaporized mixture of higher alkyl aryl compounds, and forming a mixture of higher alkyl aryl sulfonates from resulting higher alkyl aryl compounds.

5. The process of producing a mixture of higher alkyl aryl s ulfonates having good storage properties which comprises chlorinating a parafiinic petroleum hydrocarbon distillate boiling for the most part "within the range 210 to 320 C., condensing resulting chlorinated hydrocarbons with an aromatic compound -of the -benzene series capablev of condensing with an alkyl chloride, by a Friedel-Crafts condensation with the aid of an aluminum chloride catalyst. the aromatic compound being employed in an amount in excess of that theoretically required for condensation with all of the chlorinated hydrocarbons, mechanically separating from the Vresulting condensation reaction mixture a-condensation product comprising essentially a crude mixture of higher alkyl aryl compounds of the benzene series and the excess aromatic compound, said condensation product containing residual aluminum chloride catalyst, passing the condensation product, containing residual aluminum chloride catalyst, in heat exchange relationship with a heating medium. regulating the rate of flow of the mixture, the temperature of the heating medium, and the nature of the heat exchange relationship between the heating medium and the condensation product to heat the condensation product rapidly above the boiling point of theV aromatic compound. vaporizing the varomatic compound with-v.

' compounds.

, 6. The process of producing -a mixture of higher alkyl aryl sulfonate'shaving good storage properties which comprises 'chlorinating a parailinic petroleum hydrocarbon distillate boiling for the most partwithinthe. range 210 to 320 C., condensing resulting 'chlorinated hydrocarbons with an aromatic hydrocarbon of the benzene series capable of condensing-with an alkyl chloride, by a Friedel-Crafts condensation with the aid of an aluminumchloride catalyst,rthe aromatic hydroaiomatic compound oi the benzene series, separating the crude mixture of higher alkyl aryl lict comprising essentially a crude mixture of 'nigher alkyl aryl compounds of the benzene series lamd the excess aromatic hydrocarbon, said con-- densation product containing residual aluminum chloride catalyst, bringing the condensation product, containing residual aluminum chloride catalyst, in heat exchange relationship with a heating medium which is at a temperature above theboiling point of the aromatic hydrocarbon, vaporizing the aromatic hydrocarbon, limiting the time during which the condensation-product is in heat exchange relationship with the heating medium to a period less than that required to effect substantial vaporization of the mixture of alkyl aryl compounds, separating the vapors of the aromatic hydrocarbon from the unvaporized mixture of alkyl aryl compounds, and forming al mixture of allqrl-aryl sulfonates from resulting alkyl aryl compounds.

-7. The process of producing a mixture of higher l alkylaryl sulfonates having good storage properties which comprises chlorinating a Ipetroleum distillate boiling for the most part above 100 C., condensing resulting chlorinated hydrocarbons with an aromatic compound selected from the group consisting of the aromatic compounds of 'the benzene, naphthalene, and diphenyl'seri'es capable oi condensing with an alkyl chloride, by a Friedel-Crafts condensation with the aid of an aluminum chloridek catalyst, the aromatic compound being employed in an amount in excess of that theoretically required for condensation with all of the chlorinated hydrocarbons,l

mechanically separating from the resulting condensation reaction mixture a condensation product comprising essentially a crude mixture of higher alkyl aryl compounds and the excess aromatic compound, said condensation product containing residual aluminum chloride catalyst, passing the condensation product, containing residual aluminum chloride catalyst, in heat exchange relationship with a heating medium, regulating the rate of ilow of the mixture, the temof the heat exchange relationship between the heating medium and the condensation product to heat the condensation product rapidly above the boiling point of the aromatic compound, vaporizing the aromatic'compound without substantially vaporizing the/mixture of higher alkyl 8. The process of producingv a mixture of higher alkyl aryl sulfonates of the benzene series in.

which the alkyl groups are derived from appetroleum distillate, which comprises introducing alkyl groups corresponding to the hydrocarbons of a petroleum distillate boiling for the most part within the range 210 to 320 C. into an aromatic compound of the benzene series by a Friedel- Crafts condensation with the aid of an aluminum chloride catalyst, in which condensation an ex'- cess of said aromatic compound is employed whereby a crude mixture of higher alkyl aryl compounds is formed whichcontains unreacted t perature of the heating medium, and the nature compounds from the condensation reaction mixture, rapidly heating the crude mixture of higher alkyl aryl compounds, containing-residual alu vaporizing the aromatic compound withoutsubstantially vaporizlng the mixture of higher alkyl aryl compounds, separating the vaporsv of the aromatic compound from the mixture, and forming a mixture of` higher alkyl aryl sulfonates from resulting higher alkyl. aryl compounds,`

whereby the mixture of alkyl aryl sulfonates is capable of being stored in the dry form for a considerable. period of time without developing an unpleasant odor to an undesirable degree.

9. The process of producing a mixture of alkyl aryl sulfonates in which the alkyl groups are derived from a petroleum distillate boiling for the most part above '100 C., which comprises halogenating the petroleumdistillate, condensing resulting halogenated hydrocarbons with an aromatic compound capable of condensing with an alkyl halide, by a Friedel-Crafts condensation with the aid of an aluminum chloride catalyst, the aromatic compound being employed in an amount in excess of'that theoretically required for reaction with al1 of the halogenated hydrocarbons, whereby a crude mixture of alkyl aryl compounds is obtained which contains the excess aromatic compound, rapidly vheating the crude mixture of alkyl aryl compounds, containing residual aluminum chloride catalyst distributed therein to a temperature above the boiling point of the aromatic compound but below the boiling point of the mixture of alkyl aryl compounds, vaporizing the aromatic. compound without substantially. vaporizing the mixture of alkyl aryl compounds, separating the vapors. of the aromatic compound-'from the mixture, land forming a mixture of alkyl aryl sulfonates from resulting alkyl aryl compounds, whereby Ythe mixture of alkyl aryl sulfonates is capable of being stored in the dry form for a considerable period of time Without developing an unpleasant odor to an undesirable degree.

10. The process of producing a mixture of alkyl benzene sulfonates in which the alkyl groups are derived from a petroleum distillate, which comprises preparing a crude mixture of alkyl benzenes from said distillate and benzene by a Friedel-Crafts condensation with the aid of an aluminum chloride catalyst, in which condensation an excess o1 benzene is employed whereby the crude mixture of alkyl benzene compounds contains unreacted benzene, rapidly heating the crude mixture of alkyl benzenes, containing residual aluminum chloride catalyst vdistributed therein, to a temperature above the boiling point of benzene but Ibelow the boiling point of the mixture of alkyl benzenes, vaporizing benzene without substantially vaporizing the mixture of alkyl benzenes, separating the vapors of benzene from the mixture, and forming a mixture of alkyl .benzene sulfonates from resulting alkyl benzenes, whereby the mixture of alkyl benzene sulfonates is capable of being stored in the dry form for 15 which comprises preparing a crude mixture of alkyl -aryl compounds from said distillate and an aromatic compound by aV procedure including a Friedel-Crafts condensation with the aid of an aluminum chloride catalyst, inwhich condensa.-

tion an excess ot the aromatic compound is em pioyed whereby the crude mixture of alkyl aryl compounds contains unreacted aromatic compound, rapidly heating the crude mixture of higher alkyl aryl compounds, containing residual aluminum chloride catalyst distributed therein, to a temperature above the boiling point of the aromatic compound, vaporizing' the aromatic compound without substantially vaporizing the mixture of higher alkyl aryl compounds by limiting the heating o! the crude mixture to a period of time insuillcient to eiiect substantial vaporization of the mixture of higher alkyl aryl compounds, separating the vapors of the aromatic compolmd from the mixture, and forming a mixture of higher alkyl aryl sulfonates from resulting higher alkyl aryl compounds, whereby the mixture oi' higher alkyl aryl sulfonates is capable of being stored in the dry form for a considerable period of time without developing an unpleasant odor to an undesirable degree.

12. The process oi' producing a mixture of higheralkyl aryl sulfonatesv in which lthe alkyl groups are derived from a petroleum distillate, which comprises preparing a lcrude mixture of alkyl aryl'compolmds from said distillate and an aromatic compound by a procedure including` a Friedel-Crans condensationwith the aid of an aluminum chloride catalystfin which condensation' an excam of the aromatic compound is employed whereby the crude mixture of alkyl aryl compounds contains unreacted aromatic compoimd, contacting the'crude mixture of higher alkyl aryl'v compounds, containing residual aluminum chloride catalyst distributed therein, with a heated surface which is ata temperature above aluminum chloride catalyst distributed therein aromatic compo' Friedel-Crafts "c vdensation with the aid of an tion an excess o aluminum chlor atalyst, in 'which condensa'- earomaticcompound is employed whereby-the crude mixture of alkyl aryl compoundsl contains unreacted aromatic `compound', rapidly heating-V the crude mixture of higher alkyl aryl compounds, containing residual to a temperature 'above the boiling point of the aromatic compoundbut belowjthe boiling point of the -mixture oi higher alkyl aryl-compounds, vaporizing the aromatic compound without substantially vaporizing the mixture of higher alkyl aryl compounds, separating the-vapors of the aromatic compound from the mixture, and forming a mixture of higher allwl aryl sulfonates from the resulting higher alkyl aryl compounds, whereby the mixture of higher alkyl aryl suly fonates is capable of being stored in the dry\form the boiling point of the aromatic compound,

vaporlxing the aromatic compound, limiting the contact of the crude mixture with Athe heated surface to a period of time less than that required to eil'ect substantial vaporization ofthe mixture of higher alkyl aryl-compounds, .separating the vapors of the aromatic compound from the mix- .for a considerable period of time without developing `an unpleasant odor to an undesirable degree.

LAWRENCE il. FLE'IT.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS g Date Number Name 1,835,063 Langmeier Dec, 8, 1931 1,900,694 Coupeau et al. Mar. 7, -1933 1,996,852 Bergell a Apr. 9, 1935 2,220,099

Gunther et al Nov. 5, 1940

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