US2469376A - Mixtures of alkyl aryl sulfonates - Google Patents

Description

Patented May 10, 1949 MIXTURES OF ALKYL ARYL SULFONATES Lawrence H. Flett, Scarsdale, N. Y., .assignor to Allied Chemical & Dye Corporation, New York, N. Y., a corporation of New York No Drawing. Application March 25, 1946, Serial No. 657,052. Canada July 28, 1941 This invention relates to a process for improving the storage properties of mixtures of substituted aryl sulfonates which contain as nuclear-substituents radicals corresponding to hydrocarbons of the type present in a petroleum distillate. More particularly it relates to a process for improving the storage properties of mixtures of alkyl benzene sulfonates which contain as nuclear substituents radicals derived from the hydrocarbons present in a kerosene fraction of petroleum or related olefins.

Compositions comprising mixtures of nuclearly substituted aryl sulfonates which contain as nuclear substituents radicals corresponding to hydrocarbons of the type present in petroleum distillates are valuable for use as detergents, wetting agents, emulsifying agents, soap substitutes, and the like. The substituted aryl sulfonates Present in such mixtures are conveniently referred to, as allrvl aryl sulfonates, the term alkyl being used in its broad sense to include generically: open-chain aliphatic hydrocarbon radicals (whether straight-chain or branched-chain) and radicals derived from cycloaliphatic and aromatic-aliphatic hydrocarbons which may be present in petroleum distillates. Depending upon the purpose for which they are to be used, the alkyl aryl sulfonate mixtures are derived from selected petroleum fractions, such as fractions within the upper gasoline range, the kerosene range, and higher ranges, or from selected fractions of related unsaturated hydrocarbon mixtures.

For example, where compositions are desired particularly adapted for use as wetting agents, petroleum distillates or related unsaturated hydrocarbon mixtures may be employed which boil as low as 100 C. In general, however, a petroleum distillate boiling substantially below the boiling point of any nonane is not employed. Thus, a petroleum distillate or olefin mixture useful for the manufacture of alkyl aryl sulfonate mixtures for use as wetting agents is one boiling within the range 140 to 180 C. Where it is desired to prepare a composition containing alkyl aryl sulfonates in which the substituent alkyl radicals contain an average of more than 20 carbon atoms, a petroleum distillate or olefin mixture having a boiling range which reaches a maximum temperature of 300 C. at 25 mm. abso-- lute pressure may be used.

For most purposes, particularly for use as a general detergent, products derived from petro-,

16 Claims. (Cl 260-505) is, those which boil 320 ,0. Those which boil for the most part (i. e., at least thereof) within the range 210 to 320 C. are preferred, especially when composed predominantly of aliphatic and/or alicyclic saturated or unsaturated hydrocarbons which boil within the range 210 to 290 C.

In general, the manufacture of the compositions in question involves forming the aromatic condensation product of a non-aromatic hydrocarbon mixture of mineral origin by condensing an romatic compound with a chlorinated petroleum fraction (e. g., chlorinated kerosene) or with an olefin (e. g., dehydrochlorinated kerosene chlorides, cracking products, dehydrogenation products, polymerized lower olefins, etc.) and sulfomating the mixture of alkyl aromatic compounds thus produced. The alkyl groups introduced into the aromatic nucleus are principallly hydrocarbon groups containing at least seven carbon atoms per molecule and the mixtures may comprise isomeric and homologous hydrocarbon groups. In addition to straight-chain and branchedchain alkyl groups, aralkyl and cycloalkyl groups may be present. The aromatic nucleus may be a benzene, naphthalene, or diphenyl nucleus which may contain one or two substituents of the group consisting of halogens and hydroxy, alkoxy, lower alkyl, and phenoxy radicals.

One process for preparing the alkyl aryl sulfonates involves chlorinating the selected petroleum distillate, condensing resulting chlorhydrocarbons with an aromatic compound, usually in the presence of a condensation catalyst (such as, aluminum chloride or zinc chloride), sulfonating the resulting substituted aromatic compounds, converting the resulting sulfonic acids in the sulfonation mass to salts 'by treatment with a suitable alkaline compound, usually aqueous caustic soda, and drying the mixture of salts thus produced. Thus, one method for the manufacture of wetting, dispersing, emulsifying, and cleansing agents from kerosene and similar distillate fractions involves chlorinating a selected distillate fraction, for example a fraction of Pennsylvania, Michigan (Mt. Pleasant), or similar petroleum kerosene, so selected that the hydrocarbons therein contain for the most part between 7 and 19, and preferably 10 to 16, carbon atoms to the molecule, to obtain a mixture which comprises chlorinated hydrocarbons, and which for convenience may be called a keryl chloride. The keryl chloride is then condensed with an aromatic compound (for example, benzene, toluene, naphthalene, diphenyl, chlorobenzene, phewithin the range 180 to nol, cresol, anisole, phenetole, hydroxydiphenyl, alpha-naphthol, or betanaphthol) to form a corresponding keryl aryl compound (e. g., keryl benzene, keryl phenol, etc), and the keryl aryl compoundis then sulfonated with or without intermediate purification treatments.

These mixtures of alkyl aryl sulfonates ofier 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 a mixture of compounds having properties varying among themselves, 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 alkyl aryl sulfonate mixtures, particularly the keryl benzene sulfonates, in the form of the free acids or their sodium, potassium,

ammonium, alkyl-ammonium, or hydroxy-alkylammonium salts, area class of products which are most satisfactory for general household uses.

However, the alkyl aryl sulfonates, which in the pure form are substantially white, colorless and tasteless products, are ordinarily obtained in the form of impure mixtures containing impurities of various types and in varying amounts when prepared from hydrocarbon mixtures of mineral origin by processes such as those described above. Thus, they have an unpleasant odor and a disagreeable taste, and are frequently discolored.

I have developed a number of improvements in the preparation and treatment of alkyl aryl sulfonates derived from hydrocarbons of mineral origin, and especially from kerosene fractions of petroleum distillates, which lead to products of improved properties, particularly with respect to color and odor. Processes for making keryl benzene sulfonates of improved properties are disclosed, for example, in my United States Patents 2,233,408, 2,223,364, 2,247,365, 2,267,725, 2,317,986, and 2,387,572..

While in some cases, as when freshly prepared, the alkyl aryl sulfonate mixtures may accordingly be obtained as substantially odorless products, they have the undesirable property of developing a rancid odor on standing. Thus, a synthetic detergent comprising a mixture of alkyl benzene sulfonates derived from'a kerosene of the above type obtained from Pennsylvania petroleum, which has been produced in an odor-.

free form by a process of the type referred to above, develops an objectionable odor uponstanding, even in closed containers in the dark at room temperature.

The present invention has for an object improvement in storage properties of alkyl aryl sulfonate mixtures of the type discussed above, whereby said mixtures may be stored for a relatively-long period of time without developing rancid odors to an objectionable degree.

A more specific object of the invention is to provide a process for the treatment of alkyl benzene sulfonate mixtures, the alkyl groups of which have been derived from a kerosene fraction of petroleum by a process including chlorination of the kerosene, condensation of resulting chlorhydrocarbons with benzene, and sulfonation of the resulting alkyl benzenes, whereby the properties of the alkyl benzene sulfonate mixtures are improved with respect to development of odor during storage.

Other objects in part will be obvious and in part will appear hereinafter.

It has been discovered, in accordance with the present invention, that the stability to storage of alkyl aryl 'sulfonate mixtures of the above class, and particularly alkyl benzene sulfonate mixtures in which the substituent alkyl groups correspond to aliphatic and alicyclic hydrocarbons of a kerosene fractionof petroleum, which have the property of developing undesirable odors upon being stored, can be improved by incorporating with the alkyl aryl sulfonate mixtures a very small amount of one or more oxidation inhibitors which are amino-aromatic compounds having not more than H) nuclear carbon atoms per aromatic nucleus. Said compounds comprise derivatives of benzene and its homologs (having 6 carbon atoms per aromatic nucleus), and of naphthalene and its homologs, having at least one amino-nitrogen atom linked to a carbon atom of the aromatic nucleus. They include mono-amines and poly-amines of the benzene, naphthalene, and biphenyl classes (biphenyl being a phenyl-substituted benzene). The aminonitrogen atoms may be further substituted, for example, by alkyl, aryl, acyl, carbamyl, thiocarbamyl, and guanyl radicals, which radicals in turn may carry further substituents. Further-' more, the aromatic nuclei may be further substituted, for example, by one or more halogen atoms, or by one or more alkyl, aryl, carboxyl, acyl, alkoxy, hydroxy, or sulfo groups.

Thus it has been found, in accordance with the present invention, that the tendency of mixtures of alkyl aryl sulfonates of the above type to develop rancid odors can be inbitied by incorporating therewith very small amounts of compounds of the following types, so that the mixtures of alkyl aryl sulfonates containing the said aminoaromatic compounds may be stored over a relatively long period of time without developing undesirable odors to an unpleasant degree:

Amino-benzenes Amino-naphthalenes Amino-biphenyls Amino-phenols Amino-naphthols Amino-hydroxybiphenyls Amino-phenyl sulfones Amino-benzoates Phenyl-ureas (including thioureas) Phenyl-guanidines Phenyl-glycines It has further been found, in accordance with the present invention, that the presence of any of the said amino-aromatic compounds in small but sufficient amount to inhibit the development of objectionable odor has no appreciable harmful eflect upon the wetting, detergent and emulsifying properties of the alkyl aromatic sulfonate compositions to which the amino-aromatic compounds are added. I

The amino-aromatic compounds can be incorporated with the mixtures of alkyl aromatic sulfonates in any suitable manner and in the presence or absence of a solvent or diluent. Inasmuch as the-amount of amino-aromatic compound employed, relative to the mixture of alkyl aryl sulfonates, is very small (i. e., a fraction of aexample, in the preparation of alkyl aryl sulionate products by a procedure involving, as the final operation, evaporation 01' an aqueous solution of an alkyl aryl sulfonate mixture to dryness, a dry product can be produced having increased stability against the development of undesirable odor upon being stored, by adding to the solution, prior to evaporation of the latter, an amino-aromatic compound of the class herein defined in very small amount.

The present invention accordingly makes possible the production of a mixture of alkyl benzene sulfonates, in which the substituent alkyl groups are derived from kerosene or related olefins which can be marketed for many purposes for which the untreated material is not suitable.

The particular type of amino-aromatic compound employed in a particular case will depend upon the extent to which the particular mixture of alkyl aromatic sulfonates tends to develop rancid odors, the length of time the product is to be stored, and the use to which the product is to be put.

Thus, for the preparation of detergent compositions which are to be used extensively in the household arts and frequently in solutions making contact with the skins of animals and human beings, it is important that the amino-aromatic compound used and the amounts thereof incorporated with such compositions should be nontoxic and non-irritating to animal and human skins. Further, for the production of compositions which, in solid form, or when used in solution, would be objectionable if they tended to become colored or to impart color to their solutions, amino-aromatic compounds are preferably employed which, upon oxidation, do not develop objectionable color. Preferred odor inhibitors which are free from objectionable toxic eflects and which, upon oxidation, do not. form highly colored compounds are di-aryl-thioureas, and of these di-phenyl-thiourea and di-tolyl-thiourea are especially preferred because of their effective odor-inhibiting properties, even when used in very small amounts.

On the other hand, when the mixtures of alkyl aryl sulfonates are intended for uses in which the physical appearance and/or toxicity of the composition and/or its solution are of little importance and are not objectionable to the users thereof, such amino-aromatic compounds as phenyl-alpha-naphthylamine and phenylene-dlamine can be used.

Because of the state of the development of the present art, it is believed to be unnecessary to enumerate all of the various types of hydrocarbon mixtures whose alkyl aryl s'ulfonate derivatives may be treated in accordance with the present process to improve their odor characteristics. It is sufiicient to point out that treatment by the present process may be applied advantageously to alkyl aromatic sulfonates which have the undesirable property of developing odors upon being stored and are derivatives of hydrocarbon mixtures which boil for the most part within ranges whose lower limits are above 100 0. As previously indicated, the most important compositions for general detergent use are those which are obtained from kerosenes that are composed predominantly of aliphatic and alicyclic hydrocarbons, by a process involving chlorination of the kerosene condensation of resulting chlorhydrocarbons with an aromatic compound, and sulfonation of resulting condensation products.

The invention will be illustrated by the follow- Exnrru 1 Pennsylvania kerosene boiling from 185 to 275 was chlorinated between 60 and 70 in the presence of 3.8 parts iodine per 1,000 parts kerosene, until the specific gravity of the latter had increased from 0.788 at 24 to 0.918 at 24. 10 parts of the resulting chlorinated hydrocarbon mixture, 20 parts of benzene and 0.5 part of anhydrous aluminum chloride were mixed at 35; the mixture was held for about 1 /2 hours at 45, then allowed to stratify; the upper layer of oil was removed from the tarry lower layer and distilled; and the fraction boiling between 150 at '75 to 100 mm. of mercury absolute pressure and 250 at 14 mm. of mercury absolute pressure was collected separately as the part which was chiefly alkyl aromatic compounds. The collected fraction was refined by agitating it with 18.4% of its weight of 100% sulfuric acid at 25 to 30 for 45 minutes, allowing the mass to settle 30 minutes and discarding the lower acid layer. The refined oil was mixed with 1.32 times its weight of 100% sulfuric acid at 30 to 35. The mixture was warmed to 55 to 60, agitated at that temperature for 1 hour, allowed to stratify for about 1 hour, and the middle stratum which was separated from an upper layer of oil and from a lower layer of spent acid, was drowned in 4 parts of a mixture of ice and water. The resulting aqueous solution was neutralized with 50% aqueous caustic soda, and anhydrous sodium sulfate was added in such amount that the solute in the solution contained about 62% of inorganic salts (chiefly sodium sulfate) and 38% of sodium alkyl benzene suli'onates. Thesolution was then di luted to such an extent that it contained 20 parts by weight of solute per 100 cc. of solution.

This solution was divided into equal portions, each containing about 100 parts of solute, which were treated as follows and subjected to accelerated aging at The development of odor under conditions of accelerated aging was determined for each product by placing a oneounce sample of the product in a two-ounce glass bottle, loosely stoppering it with a cork stopper, and heating the bottle (each containing a sample of one of the products undergoing tests) at a controlled temperature in an oven for a specified period of time. At stated intervals, the bottles were removed and unstoppered, the odors were determined by smelling the contents of the bottles, the stoppers were replaced, and the bottles were returned to the oven. The condition of the resulting products after 16 hours was as shown in the following Table 1:

EXAMPLE 2 A solution containing about 30% by weight of a detergent composition containing about 40 parts of 'a mixture of sodium alkyl benzene sulfonates and about 60 parts of sodium sulfateper 100 parts of detergent composition and prepared in the manner described in Example 1, was divided into equal portions. Para-amino-phenol was incorporated with one portion and para-hydroxy-benzylaniline (para-benzylamino-phenol) was incorporated with another portion, each in an amount equal to 1 part per 1,000 parts of the detergent composition present in the portion of the solution. Nothing was added to a third portion. The three solutions were then drum-dried, and the dry products were subjected to accelerated aging in the manner described above at about 85. The product which contained no added oxidation inhibitor developed a strongly rancid odor in 16 hours. The other two products had practically no odor after 230 hours.

EXAMPLE 3 10,620 lbs. of Pennsylvania kerosene (specific gravity 0.788.at 24 and boiling range 179 to 265) were charged into a lead-lined kettle fitted with a lead-covered agitator, thermometer well and other accessories. 4.4 lbs. of iodine were dissolved in the agitated kerosene charge. The resulting charge was warmed to about 63 and maintained at that temperature while chlorine gas was passed into it at an average rate of about 500 lbs. per hour for hours and then at an average rate of 300 lbs. per hour until the specific gravity of the chlorinated kerosene had become 0.918 at 24.

A mixture of 14,805 lbs. of benzene (part of which was recovered from a previous batch) and 321 lbs. of anhydrous aluminum chloride was agitated, and 6,417 lbs. of the chlorinated kerosene mixture were added thereto, over a period of three hours, during which the temperature of the mass rose to about 40. The mixture was then heated to 45, and held there for about 1 hours with agitation. Agitation was then stopped, the mixture was allowed to stand for about 2 hours, and the lower tarry layer was then withdrawn. The upper layer was conveyed to a stripping kettle in which the liquid was stripped of low-boiling hydrocarbons, chiefly benzene, by boiling the liquid first under atmospheric pressure and finally at 150 under reduced pressure of 3 to 4 inches of mercury absolute pressure. The material left after this stripping was distilled in vacuo until about 22% of the charge in the still had been removed as distillate. The distillation was then continued further and distillate therefrom was collected separately until the boiling point of the distillate was 230 at 5 mm. mercury pressure. This last distillate weighed 7,915 lbs. and was chiefly a mixture of alkylated benzenes, in which the alkyl groups were derived from the chlorinated kerosene.

600 parts of said mixture of alkylated benzenes were refined by mixing it with about 18% of its weight of 100% sulfuric acid and agitating the mixture for about 45 minutes at about 20 to 25. The mixture was allowed to stand for about a half hour to permit Stratification, and the lower layer of spent acid was withdrawn and discarded. To the upper layer of refined oil (alkyl benzene mixthe list of compounds in Table 2.

The mixture was then warmed to 55 and agitated at 55 to for 1 hour. It was then allowed to stand for 1 hour, during which time three layers formed. The upper layer was chiefly unsulfonated material, the middle portion was chiefly sulfonated alkyl benzenes, and the lower layer was spent acid. The middle layer was separated from the others, drowned in cracked ice, and neutralized with an aqueous solution of caustic soda. To the neutralized solution, sumcient sodium sulfate was added to bring the inorganic salt content.of the solute up to 58.4% The resulting solution was then drum-dried. The solid detergent thus obtained was used in the following tests:

A stock solution was prepared which contained 28.4 parts of the solid detergent per 100 volume parts of solution. To 176 volume parts of this solution containing 50 parts of solid detergent) there were added 0.05 part of one of the aminoaromatic compounds listed in the following Table 2. Thus, there were about 24 parts of oxidation inhibitor for each 10,000 parts of sodium alkyl benzene sulfonate in the solution. After agitating the aqueous mixture to insure dispersion of the odor inhibitor, the solution was drum-dried. A number of samples were thus prepared from A control sample, to which nothing was added, was similarly dried. Each sample so prepared was tested for development of offensive odor by the accelerated aging procedure described above, at 85. Odor which developed at the end of periods of 16, 40, 112, and 160 hours was noted and recorded. The effect of the amino-aromatic compounds as inhibitors of development of odor in the detergent mixture of sodium alkyl benzene sulfonates is shown in the following Table 2 in which odor is rated according to the following scale:

I=slight II=moderate III=bad IV=extremely bad Table 2 Degree of Odor Developed Amino-Aromatic Compound Added 16 40 112 160 Hrs. Hrs. Hrs. Hrs.

Di-p-tolyl-thiourea I- I- I- I- ture) there were added during 10 minutes about EXAMPLE 4 A detergent composition of which was a mixture of sodium alkyl benzene sulfonates derived from a kerosene containing mostly hydrocarbons having 10 to 16 carbon atoms in the molecule and 10% was sodium sulfate, and which had been prepared by a process of the type described above, was made into an aqueous solution of about 25% concentration. The solution was divided into portions containing equal weights of thedetergent composition on a dry basis. One portion was dried on a double drumdrier without further treatment as a control. Diphenyl-urea and phenyl-urea (carbamyl-anilide) were added, respectively, to other portions,

each in an amount equal to 0.1% of the weight A=no rancidity B=slight trace of rancidity C=mi1dly rancid D=distinctly rancid E=very strongly rancid Table 3 Developed Odor EXAMPLE 5 A plurality of aqueous solutions of about 20% strength was prepared, each containing 50 parts of detergent composition of the type employed in Example 4. One solution was drum-dried without further treatment for use as a control. To one of each of the other solutions, 0.05 part (0.1%)of one of each of the amino-aromatic compounds set out in the following Table 4 was added. The solutions were heated at 60 to 70 with agitation until the amino-aromatic compound was thoroughly dispersed, and then were dried on a double drum drier. A sample of each of the resulting dried products was tested for development of offensive odor by the accelerated aging procedure described above, at 85. Odor which developed at the end of periods 40 and 64 hours was noted and recorded. The results are shown in the following Table 4, in which odor is rated according to the scale employed in Example 4:

Table 4 D veloped Odor Amino-Aromutic Compound Added EXAMPLE 6 A plurality of aqueous solutions of about 20% strength was prepared, each containing 50 parts of detergent composition of the type employed in Example 3. One solution was drum-dried without further treatment for use as a control. To one of each of the other solutions, 0.05 part (0.1%) of one of each of the amino-aromatic compounds set out in the following Table 5 was added. The solutions were heated at 60 to 70 with agitation until the amino-aromatic compound was thoroughly dispersed, and then were dried on a double drum drier. A sample of each of the resulting dried products was tested for development of offensive odor by the accelerated aging procedure described above, at Odor which developed at the end of periods of 24, '72, and 120 hours was noted and recorded. The effect of the amino-aromatic compounds as inhibitors of development of odor is shown in the following Table 5, in which odor is rated according to the scale employed in Example 4:

Table 5 I I Developed Odor Amino-Aromatic Compound Added 24 Hrs. 72 Hrs. 120 Hrs.

None (control) B D E Acetanilido A O E o-Amino-diphenyl A O O Benzidine A A A Isopropoxy-diphenylamine. A A A p-p' Diemlno-dlphenyl-sullone A A A p-Amino-dimethyl-aniline A A A Ethyl p-aminobenzoatc A A A It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that changes can be made without departing from the scope of the invention.

Thus, instead of the amino-aromatic compounds employed as odor inhibitors in the examples, other amino-aromatic compounds of the type referred to above can be used. The following are additional illustrations of suitable com-- pounds: 1,8-naphthalene-diamine, diamino-phenol, N-methylaminophenol and di-isobutyl N- para-hydroxyphenyl-asparate (diisobutyl ester of N-para-hydroxyphenylamino-succinic acid).

The amount of amino-aromatic compound which is effective for this invention has been found to be very small in comparison with the mixture of alkyl aryl sulfonates with which it is incorporated. Because of the variance among diiTerent alkyl aryl sulfonate mixtures, depending upon the hydrocarbon mixtures used in their preparation, the details of the process employed, the purpose for which they are to be used, and other variable factors, it is not possible to state definitely the amount of amino-aromatic compound to be used in all cases. In general, incorporation of the amino-aromatic compound in amounts greater than 3 parts per 10,000 parts by weight of mixture of alkyl benzene sulfonates (exclusive of inorganic salts, when present) is sufficient to repress the development of odor in the treated, dry compositions to the extent that the compositions can be stored for long periods of time before development of odors in them takes place to an unpleasant degree. Thus, amounts which range from 3 parts "to parts per 10,000 parts by weight of alkyl benzene sulfonate mixtures may be employed. In general, amounts ranging from 3 parts to 40 parts per 10,000 parts are preferred. Amounts which are less than the above minimum amount may be desirable when the alkyl aryl sulfonate mixtures are to be stored only for relatively short periods; while amounts greater than the above maximum amount may be used whenever the oxidation inhibitor does not itself impart detrimental effects, such as an undesired odor an-d/or color, toxicity, etc., or where one or more of such effects are less objectionable than the rancid odors which in time develop in the untreated compositions.

While in the above examples the mixtures of alkyl aryl sulfonates treated are derivatives of benzene, other alky1 aryl sulfonate mixtures which are derived from homologs of benzene and from other aromatic compounds may be simip or more of said compounds.

C. The treatment is particularly adapted to the compounds derived from aryl hydrocarbons.

Compounds derived from phenol have less tendency to develop odor, because of the presence of the phenolic group. Further, the alkyl aryl sulfonate mixtures may be in the form of neutral salts other than the sodium salt, and especially in the form of other water-soluble salts; as for example, the potassium, magnesium, lithium, nickel, ammonium and tri(hydroxylethyl)ammonium salts.

Instead of the mixtures of alkyl benzene sulfonates employed in the above examples, equal amounts of mixtures of sodium alkyl benzene sulfonates obtained by condensing benzene with higher olefins, especially olefins containing to 16 carbon atoms and more particularly those obtained by polymerizing lower olefins (for example, tributylene, tetrapropylene, etc.), followed by sulfonation and' neutralization with sodium hydroxide, can be employed. The resulting dried products have similar improved stability against the development of unpleasant odor. I In general, the amino-aromatic compounds used in accordance with the present invention may be employed individually but sometimes they are advantageously employed as mixtures of two Moreover, they may be employed in addition to a treatment ,of the alkyl aryl sulfonate mixtures with chemical agents adapted to react with the constituents of said alkyl aryl sulfonates which tend to form substances having an objectionable odor, or in addition to other treatments, such as a treatment with decolorizing carbon.

It will thus be seen that the present invention provides a simple and economical means for improving the storage properties of mixtures of a1ky1 aryl sulfonates derived from petroleum distillates, so that the mixtures of alkyl aryl sulfonates may be kept for a considerable period of time without developing rancid odors to an undesirable degree.

This application isa continuation-in-part of my application Serial No. 350,143, filed August 2, 1940, issued March 26, 1946, Patent No. 2,-

Iclaim:

1. A composition comprising a solid mixture of alkyl aryl sulfonates in which the alkyl groups are derived from a hydrocarbon mixture which boils for the most part above 100 C., which solid mixture develops a rancid odor onbeing stored, and in admixture therewith a fraction of a percent of its weight of an amino-aromatic compound having not more than 10 nuclear carbon atoms per aromatic nucleus, as an odor inhibitor.

2. A composition comprising a solid mixture of watersoluble alkyl benzene sulfonates in which the alkyl groups are derived from a petroleum distillate which boils for the most part above 100 C., which solid mixture develops arancid odor on being stored, and in admixture therewith a fraction of a percent of its weight of an amino-aromatic compound having not more than 10 nuclear carbon atoms per aromatic nucleus and containing no element other than car- 12 bon, hydrogen, nitrogen, oxygen and sulfur, as an odor inhibitor.

3. A composition comprising a solid mixture of water-soluble alkyl mononuclear aryl sulfonates in which the alkyl groups are derived from a kerosene fraction of petroleum which boils for the most part within the range of 180 to 320 C., which solid mixture develops a rancid odor on being stored, and in admixture therewith a fraction of a percent of its weight of an aminoaromatic compound having not more than 10 carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen, oxygen and sulfur, as an odor inhibitor.

4. A composition comprising a solid mixture of alkyl benzene sulfonates in which the alkyl petroleum which boils for the most part within therange 210 to 320 C., which solid mixture develops a rancid odor on being stored, and in admixture therewith a fraction of a percent of its weight of an aromatic compound having. at least one amino radical, said compound having not more than 10 nuclear carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen, oxygen and sulfur, as an odor inhibitor;

6. A composition comprising a solid mixture of sodium alkyl benzene sulfonates in which the alkyl groups are derived from a hydrocarbon mixture which boils for the most part within the range 180 to 320 C., which solid mixture develops a rancid odor on being stored, and in admixture therewith a fraction of a percent of its weight of an amino-hydroxy-aromatic compound having not more than 10 carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen and oxygen, as an odor inhibitor.

7. A composition comprising a solid mixture of sodium'alkyl benzene sulfonates in which the alkyl groups are derived from a mixture of olefins containing 10 to 16 carbon atoms, which solid mixture develops a rancid odor on being stored, and in admixture therewitha fraction of a percent of its weight of an amino-aromatic compound having not more than 10.carbon atoms per aromatic nucleus; and containing no element other than carbon, hydrogen, nitrogen, oxygen and sulfur, as an odor inhibitor.

8. A composition comprising a solid mixture of sodium alkyl benzene sulfonates in which the alkyl groups are derived from polymerized olefins containing 10 to 16 carbon atoms, which solid mixture develops a rancid odor on being stored,

and in admixture therewith a fraction of a percent of its weight of an amino-aromatic compound having not more than 10 carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen, oxygen and sulfur, as an odor inhibitor.

9. A composition comprising a solid mixture of water-soluble alkyl benzene sulfonates in which l3 the alkyl groups are derived from a petroleum distillate which boils for the most part within the range 180 to 320 C., which solid mixture develops a rancid odor on being stored, and in admixture therewith a fraction of a percent of its weight of a diaryl-urea having not more than carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen, oxygen and sulfur, as an odor inhibitor.

10. A composition comprising a solid mixture of Water-soluble alkyl benzene sulfonates in which the alkyl groups are derived from a petroleum distillate which boils for the most part within the range 180 to 320 C., which solid mixture develops a rancid odor on being stored, andin admixture therewith a fraction of a percent of its weight of a diaryl-thiourea having 6 carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen and sulfur, as an odor inhibitor.

11. In the manufacture of a solid mixture of sodium alkyl aryl sulionates by a process involving chlorinating a petroleum distillate which boils for the most part within the range 180 to 320 0., condensing the resulting chlorhydrocarbone with an aromatic compound in the presence of aluminum chloride, sulfonating resulting condensation products, and neutralizing resulting sulfonation products, the method of inhibiting the development of rancid odors in the resulting mixture of allryl aryl sodium sulfonates which comprises adding to an aqueous solution of the mixture of sulfonates from 3 to 95 parts of an amino-aromatic compound per 10,000 parts by weight of said mixture of sulfonates, said aminoaromatic compound having not more than 10 nuclear carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen, oxygen and sulfur, and drying the resulting solution,

12. In the manufacture of a solid mixture of sodium alkyl benzene sulfonates by a process involving chiorinating a kerosene fraction of petroleum composed predominantly of hydrocarbons selected from the group consisting of aliphatic and alicyclic hydrocarbons which boils for the most part within the range 180 to 290 (7., condensing the resulting chlorhydrocarbons with benzene in the presence of aluminum chloride,

sulfonating the resulting condensation products,

and neutralizing resulting sulfonation products, the method of inhibiting the development of rancid odors in the resulting mixture of alkyl benzene sodium sulionates which comprises adding to an aqueous solution or the mixture of sulfonates from 3 to 95 parts of an amino-hydroxyaromatic compound per 10,000 parts by weight of said mixture of sulfonates, said amino-hydroxyaromatic compound having 6 carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen and oxygen, and drying the resulting solution.

13. In the manufacture of a solid mixture of sodium alkyl benzene siflfonates by-a process involving chlorinating a kerosene fraction of petr0-' leum composed predominantly of hydrocarbons selected from the group consisting of aliphatic and alicyclic hydrocarbons which boils for the from 3 to parts of a diaryl-thiourea per 10,000

parts by weight of said mixture of sulfonates, said diaryl-thiourea having 6 carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen and sulfur, and drying the resulting solution.

14. In the manufacture of a solid mixture of sodium alkyl aryl sulfonates by a process involving condensing a mixture of olefins containing 10 to 16 carbon atoms with an aromatic compound, sulfonating resulting condensation products, and neutralising resulting sulfonation products, the method of inhibiting the development oi rancid odors in the resulting mixture of alkyl aryl sodium sulfonates which comprises adding to an aqueous solution of the mixture of sulfonates a fraction of a percent of its weight of an aminoaromatic compound having not more than 10 nuclear carbon atoms per aromatic nucleus and containing no element other than carbon, hydrogen, nitrogen, oxygen and sulfur, and drying the resulting solution.

15. A composition comprising a solid mixture of sodium alkyl benzene sulfonates in which the alkyl groups are derived from a hydrocarbon mixture whichboils for the most part within the range to 320 C., which solid mixture develops a rancid odor on being stored, and in admixture therewith a fraction of a percent of its weight of para-benzylamino-phenol, as an odor inhibitor.

16. A composition comprising a solid mixture of sodium alkyl benzene sulfonates in which the alkyl groups are derived from a hydrocarbon mixture which boils for the most part Within the range 180 to 320 C., which solid mixture develops a rancid odor on being stored, and in admixture therewith a fraction. of a percent of its weight of a di-para=-tolyl-thiourea, as an odor inhibitor.

LAWRENCE H. FLETT.

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

UNITED STATES PATENTS Number Name Date 2,130,321 Kharasch Sept. 13, 1938 2,154,341 Martin Apr. 11, 1939 Certificate of Correction Patent No. 2,469,376. May 10, 1949.

LAWRENCE H. FLETT It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 36, for inbitied read inhibited; column 6, line 54, for the word bottlehrgad bottles; column 9, line 26, Table 3, under the heading 160 Hrs, for B rea and that the said Letters Patent should be read with these corrections therein that. the same may conform to the record of the case in the Patent Oflice. l

Signed and sealed this 11th day of October, A. D. 1949.

THOMAS F. MURPHY,

Assistant Oonum'm'mr of Patents.