US2700052A - Preparation of detergent compositions - Google Patents

Description

Jan. 18, 1955 G. G. LAUER PREPARATION OF DETERGENT COMPOSITIONS Filed March- 25, 1952 uZOlrmv. L

R F. U RA.. OL T NG EE. WG J R.. Imi 0.5. 0C Vl B O Y N 20-03 ATTORNE S Unite PREPARATION OF DETERGENT CGMPOSITIONS Application March 25, 1952, Serial No. 278,400

16 Claims. (Cl. 260-504) This invention relates to a process for preparing detergent compositions. More particularly, the invention relates to a process for preparing sulfonates in the form of salts of sulfonation products, of high purity and elfectiveness, having detergent and wetting properties, which may be used for laundering and cleansing purposes in soft or hard water, and which do not leave undesirable deposits of unreacted materials on the surface of the object which is being cleansed.

This application is a continuation-in-part of my prior and co-pending application Serial No. 2,578, filed January 16, 1948, now abandoned.

The use of Water-soluble sulfonates as detergents and wetting agents is well known. Heretofore', it has been proposed to prepare these sulfonates by treating mineral and petroleum oils with varying concentrations of sulfuric acid, and subsequently neutralizing the resulting sulfonation products with an alkali to obtain watersoluble sulfonates, suitable for use as detergent and wet- -ting agents.

It has been found, however, that the reaction of unsaturated hydrocarbons, in the presence of saturated hydrocarbons, with sulfuric acid or other sulfonating agents for the production of sulfonates or sulfates and their salts, invariably leaves in the product of reaction certain quantities of unreacted saturated hydrocarbons and/or polymerized material which are not attacked, even by very highly concentrated acids. The presence of these unreacted compounds in the sulfonates thus produced, has resulted in obtaining detergent compositions of limited cleansing and wetting properties, and consequent low market value.

It is, therefore, a primary object of the present invention to provide a process for preparing improved sulfonates having detergent' and wetting properties.

Another object of the invention is to provide a process for preparing water-soluble sulfonates, having the aforementioned properties, which do not leave undesired deposits of unreacted materials when used as detergent or cleansing agents.

Still another object of the invention is to provide a process for preparing water-soluble sulfonates, having the aforementioned properties, from a hydrocarbon feedstock in which unsaturated hydrocarbons are converted to these sulfonates, substantially free of unreacted saturated hydrocarbons and other unreacted materials.

With the above and other objects and features in view, the invention broadly comprises the improved process of preparing water-soluble sulfonates, in the form of a salt of a sulfonation product possessing the aforementioned properties, by treating a feed-stock comprising unsaturated and saturated hydrocarbons having from 8 to 18 carbon atoms per molecule with selected sulfonating agents under controlled conditions, to form a reaction product comprising a sulfonated oil; next contacting this reaction product with an aqueous solution of a base and a ketone to form a sulfonation salt and unreacted hydrocarbons; and finally separating the unreacted hydrocarbons by extracting these unreacted hydrocarbons with a relatively light hydrocarbon treating agent. In another modiiication of the process of the invention, theaforementioned sulfonation reaction 'product may be contacted with an aqueous solution of a base to form the corresponding salt and unreacted hydrocarbons, followed by contacting the salt with a mixture of the lightv hydrocarbon treating agent and ketone, to effect separation of unreacted hydrocarbons from the sulfonation product, as more fully hereinafter described. Particular novelty rates Patent 2,700,052 Patented Jan. 18, 1955 ICC has been found to exist in the use of a ketone in the process of the invention, either in combination with an aqueous solution of the base in the aforementioned sulfonation step, or in combination with the relatively light hydrocarbon treating agent in the extraction step, wherein unreacted hydrocarbons are separated from the sulfonate. In this respect, I have found that alkali salts of the sulfonation product formed by contacting the aforementioned sulfonated hydrocarbons with an aqueous solution of a base exert a solutizing effect upon unreacted hydrocarbons, for the most part saturated hydrocarbons present in the formed sulfonation product, and hence subsequent extraction of these unreacted hydrocarbons by means of a light hydrocarbon material is extremely difficult. In adding a ketone, which is water-miscible in combination with either the aqueous solution of the base or the light hydrocarbon material, I have found that the solutizing power of the formed alkali salts of the sulfonation product upon the unreacted material is markedly lowered, and hence subsequent removal of the unreacted material from the resulting sulfonation saltis facilitated.

Ybeyond the` scope of the apparatus illustrated.

Referring to the drawing, a suitable acid reactive hydrocarbon feed-stock, such as mineral oil or a petroleum oil hydrocarbon fraction comprising unsaturated and saturated hydrocarbons having from 8 to 18 carbon atoms per molecule, is passed via line 10 into a sulfonation zone 11. Sulfonation zone 11, in the drawing, is representative of a reaction vessel or series of reaction vessels or similar conventional apparatus, into which a strong sulfonating agent is introduced through line 12.. This sulfonating agent may comprise a strong sulfonation reagent such as sulfuric acid having a concentration of at least 80%. Other sulfonating agents such as fuming sulfuric acid containing approximately 1% to 20% by weight of sulfur trioxide, aceto-sulfuric acid, or chlorosulfonic acid may be used. In all instances, it is preferred to use a strong sulfonating agent of suitable strength which is liquid at the desired. reaction temperature. It should be noted, that the aforementioned reagents such as sulfuric acid or chlorosulfonic acid, etc. are herein referred to in their commonly accepted form, as sulfonating agents regardless of whether they may form true sulfonates or sulfuric acid esters (.sulfates) or mixtures of both, according to the conditions of sulfonation.

ln sulfonation zone l1, the hydrocarbon-feed intro duced through line 10, and the sulfonating agent introduced through line 12, are brought into rapid and intimate contact by any conventional contacting means, at

a reaction temperature maintained in the range from about 20 C. to about 45 C. in the manner known to those skilled in the art. This sulfonating step is preferably carried out at atmospheric pressure but may be also carried out at super-atmospheric pressures if desired, within the above temperature range. The quantities of sulfonating agent admixed with quantities of Ca to C18 hydrocarbons undergoing sulfonation treatment, may vary from ratios of approximately 1:3 toapproximately 1:1, depending in each instance upon the quantities of unsaturated hydrocarbons present in the feed stock. Thus as the quantities of unsaturated hydrocarbons present in the feed are increased, the quantities of sulfonating agents employed are also proportionately increased. In some instances, it may be also desirable to add inert diluents to the sulfonating agent employed, such as ethyl ether or ethylene dichloride. In the latter event,v the ratios of diluent to the hydrocarbon feed may be relatively high such as 5:1 or even higher. i

From sulfonation zone 1l, the mixture of reactants is withdrawn through line 13. This mixture comprises sulfonated oils containing unreacted hydrocarbons which consist of either saturated hydrocarbons or both saturated and unsaturated hydrocarbons. To the sulfonated oil flowing through line 13, there is next added under suitable temperature control effective to diminish the violence of the reaction, an aqueous solution of a base and a water-miscible ketone, introduced through line 14 with which line 13 connects, in an amount suflicient to neutral- `ize the sulfonated oils (and any excess quantities of the have found that I may employ such aqueous solutions of inorganic bases as alkali or alkali earth oxides, hydroxides, or carbonates. I may also employ aqueous solutions of organic bases such as trimethylamine, diethanolamine, or triethanolamine and the like. It should be noted that the dilution of the aforementioned bases may be affected not only by the addition of suitable quantities of water, but may also be attained by admixture with proper quantities of ice. The use of ice may be desirable in some instances in order to reduce the violence of the reaction resulting from the aforementioned neutralization. As indicated above, the ketone introduced with an aqueous solution of the aforementioned base into line 13 through line 14, comprises a water-miscible ketone or a mixture of such ketones. While any water-miscible ketone may be successfully employed in the aforementioned step to lower the solutizing power of the formed alkali salts of the sulfonation product upon unreacted material, it is preferred, however, to employ ketones or mixtures of ketones such as acetone or methyl ethyl ketone. In addition,` while the quantities of the water-miscible ketone or mixture of such ketones, which is added to the aqueous solution of` the aforementioned base, may be varied in order to reduce the solutizing power of the formed alkali salts of the sulfonation product upon unreacted material to the degree desired, it is preferred, generally, to employ an aqueous solution of the base which contains from approximately to 60% of the ketone by volume. It will be understood, that in each instance the quantities of the base and ketone used, may necessarily be varied to obtain optimum neutralization conditions, accompanied by a sutlicient reduction of the solutizing power of the aforementioned salts upon unreacted material, as illustrated in the examples hereinafter shown. Ketones admixed with the base in line 14, are introduced via valved-line 15, with which line 14 connects.

In order to effect complete admixture of the aforementioned sulfonation product, and the aqueous solution 'I of the base and ketone, these components are preferably transferred through line 13 to a mixer 16. In mixer 16 the components are brought into intimate contact for a time sufficient to effect complete neutralization of the,

sulfonation product to form an aqueous solution containing the corresponding salts of the aforementioned reaction product, ketones and unreacted materials (these materials comprising saturated or both saturated and unsaturated hydrocarbons). This mixture is next withdrawn from mixer 16 through line 17. In order to facilitate subsequent separation of the unreacted material, the mixture is next treated with a relatively light hydrocarbon solvent treating agent which is introduced into line 17, via line 18, in an amount suicient to absorb therein substantially all of the unreacted material. This treating agent is preferably a low boiling hydrocarbon or hydrocarbon fraction having a boiling point lower than that of the unreacted hydrocarbons which are to be removed from the aforementioned formed sulfonation salts. Hence, I may preferably employ such hydrocarbons as liquid propane, butane, or pentane fractions, although higher boiling hydrocarbons or hydrocarbon fractions such as hexane or light naphthas, may also be successfully employed. While the proportions of the hydrocarbon treating agent and the solution comprising the formed sulfonation salts, excess ketones, and unreacted material may be varied, it is generally desirable to add the hydrocarbon treating agent to the solution in line 17 in a ratio of approximately 1:2. At this point, it should be noted that it is possible y as previously indicated to modify the process of the inf. 75 parts of n-pentane.

vention by introducing the aforementioned water-miscible ketone, or ketone mixtures, together with the hydrocarbon treating agent into line 17 via line 18, by closing off valvedline 15 and introducing the ketone component into line 18 via valved-line 19. In such event, the quantities per volume of the ketone introduced via line 19, may be present in a ratio of approximately 1:1 to 1:10 per volume of the aqueous solution of the neutralized sulfonation product in line 17.

In order to effect complete admixture of the hydrocarbon solvent treating agent and the constituents in line 17, these components are preferably transferred into a mixer 20. From mixer 20, this mixture is transferred through line 21 into a settling vessel, represented in the drawing by separator 22. In separator 22, the mixture is permitted to settle for a period of time sufficient to effect substantially complete separation, into an upper oil layer comprising a mixture of the hydrocarbon solvent treating agent and unreacted hydrocarbons, which is withdrawn through line 23 for further use or treatment outside the scope of the present process, and a lower layer comprising an aqueous solution of water-soluble salts of the sulfonation product and the ketone treating agent, which is withdrawn through line 24. The aqueous solution in line 24 is next transferred to a stripper 25 (or any conventional separation media) which is operated under conditions effective to distill overhead the ketone treating agent which is withdrawn through line 26. The puried aqueous solution of the aforementioned salts of the sulfonation product is withdrawn as bottoms through line 27 and may be transferred to any suitable storage facilities, or if so desired, can be dried by any suitable means, such as a spray dryer, to obtain the detergent composition in the solid form.

The aqueous solution of the salt of the sulfonation product in line 27 is free of unreacted hydrocarbons and has been found highly suitable as a detergent composition having outstanding detergent and wetting properties. This detergent is water-soluble, and has been found to have exceptional efficacy when used for laundering or cleansing purposes in either soft or hard water, without leaving undesirable deposits of unreacted materials or foreign matter on the surface or the object which is being cleansed. It will be understood, of course, that the detergent may also be used in highly dilute aqueous solutions, depending upon the degree of cleansing or wetting properties desired.

The following specific examples will serve to illustrate, but are not intended in any way to limit unduly the broad scope of the invention in the preparation of the aforementioned detergent compositions.

Example I parts of a blend containing chiefly unsaturated Cs-Cis hydrocarbons having an average molecular weight of 200 and an iodine number of 93 obtained from the product produced in the catalytic hydrogenation of carbon monoxide, are slowly added to 50 parts of commercially water-free sulfuric acid with constant stirring for several minutes at a temperature of about 0-20 C. and then poured over ice. The cooled mixture is next neutralized at a temperature below 45 C. with a 40% solution of sodium hydroxide containing approximately 30% acetone by volume. These constituents are thoroughly mixed and next contacted with approximately 75 parts of npentane to remove unreacted saturated hydrocarbons. The treated mixture is then subjected to phase separation to obtain an upper oil layer containing unreacted material dissolved in pentane, and a lower aqueous phase containing the formed sulfonation salt in admixture with acetone. The aqueous phase is next distilled at a temperature sufficiently high to take the ketone overhead. Thus a slightly hygroscopic material is obtained as bottoms having a yellowish appearance and which is found to possess excellent detergent and wetting properties.

Example II Example I. The mixture is next poured over ice and neutralized with a 40% solution of sodium hydroxide. These constituents are thoroughly mixed and contacted with a mixture consisting of 60 parts of methyl ethyl ketone and The treated mixture is next subjected to phase separation .to obtain an upper phase containing unreacted saturated hydrocarbons dissolved in pentane, and a lower Vaqueous phase containing methyl ethyl ketone and a sulfonate in the form of the salt of the reaction product. This `aqueous phase is next distilled at a temperature suciently high to take the ketone overhead, leaving Athe salt as `bottoms possessing properties similar to that of the salt obtained in Example I.

Having thus described my invention, what I claim .and desire to secure by Letters Patent is:

1. A process for preparing a salt of a sulfonation product wherein said salt possesses detergent and wetting properties which comprises the steps of: contacting a feedstock comprising unsaturated and saturated hydrocarbons having from 8 to 18 carbon atoms per molecule with a sulfonating agent containing a free acid group, whereby unsaturated hydrocarbons are reacted without reacting saturated hydrocarbons, to form a reaction product cornprising a sulfonated oil; contacting said sulfonated oil with a treating agent comprising an aqueous solution of a base to form a mixture comprising a salt of said sulfonated oil and unreacted saturated hydrocarbons; subjecting said mixture to extraction treatment with a treating agent comprising a light hydrocarbon to obtain an extract phase comprising unreacted saturated hydrocarbons and hydrocarbon treating agent and a raiiinate phase comprising said salt of the sulfonated cil; introducing a water-miscible ketone in combination with one of said treating agents in said aforementioned treating steps; separating said extract and rafiiniate phases; and separating said salt of the sulfonated oil fr-om said rainate phase.

`2. A process for preparing a salt of a sulfonation product wherein said salt possesses detergent and wetting properties which comprises the steps of: lcontacting a feedstock produced in the catalytic hydrogenation of carbon monoxide comprising unsaturated and saturated hydrocarbons having from 8 to 18 carbon atoms per molecule with a sulfonating agent containing a free acid group at a temperature between about 20 C. and about 45 C., whereby unsaturated hydrocarbons are reacted without reacting saturated hydrocarbons, .to form a reaction product comprising a sulfonated oil; contacting said sulfonated oil with a treating agent comprising an aqueous solution of a base to form a mixture comprising a salt of said sulfonated oil and unreacted saturated hydrocarbons; subjecting said mixture to extraction treatment with a treating agent comprising a light hydrocarbon to obtain an extract phase comprising unreacted saturated hydrocarbons and hydrocarbon treating agent and a raiiinate phase comprising said salt of the sulfonated oil; introducing -a water-miscible ketone in combination with one of said treating agents in said aforementioned treating steps; separating said extract and raiinate phases; and separating said salt of the sulfonated oil from said rainate phase.

l3. A process for preparing a salt of a sulfonation product wherein said salt possesses detergent and wetting properties which comprises the steps of: cont-acting a feedstock comprising'unsatura-ted and saturated hydrocarbons having from 8 to 18 carbon atoms per molecule with a sulfonating agent containing a free acid group, whereby unsaturated hydrocarbons are reacted without reacting saturated hydrocarbons, to form a reaction product comprising a sulfonated oil; contacting said sulfonated oil with an aqueous solution of a base and w-ater-miscible ketone to form a mixture comprising a salt of said sulfonated oil and unreacted saturated hydrocarbons; subjecting said mixture to extraction treatment with a light hydrocarbon treating agent to obtain an extract phase comprising unreacted saturated hydrocarbons and hydrocarbon treating agent and a rafnate phase comprising said salt of the sulfonated oil; separating said extract and raffinate phases; and separating said salt of the sulfonated oil from said raiiinate phase.

4. A process for preparing a salt of a sulfonation product wherein said salt possesses detergent and wetting properties which comprises the steps of: contacting a feedstock produced in the catalytic hydrogenation of carbon monoxide comprising unsaturated and saturated hydrocarbons having from 8 to 18 carbon atoms per molecule with a sulfonating agent containing a free acid group at a temperature between about 20 C. and about 45 C., whereby unsaturated hydrocarbons are reacted without reacting saturated hydrocarbons, to form a reaction product comprising a sulfonated oil; contacting said sulfonated oil with an aqueous solution of a base and a water-miscible ketone to form a mixture comprising a salt of said sulfonated oil and unreacted saturated hydrocarbons; subjecting said mixture to 4extraction treatment with a light hydrocarbon treating agent to obtain an -extractphase comprising unreacted saturated hydrocarbons and hydrocarbon treating agent and a raffinate phase comprising said salt of the sulfonated oil; separating said extract and raffinate phases; and separating said salt of the sulfonated oil from said raffinate phase.

5. A process in accordance with claim 4 wherein said base is an alkali metal hydroxide.

6. A process in accordance with claim 4 wherein said base is trimethylamine.

7. A process in accordance with claim 4 wherein said ibase is diethanolam'ine.

8. A process in accordance with claim 4 wherein said ketone is acetone.

9. A process in accordance with claim 4 wherein said ketone is methyl ethyl ketone.

10. A process in accordance with claim 4 wherein said sulfonating agent is sulfuric acid having a concentration of at least 11. A process in accordance with claim 4 wherein said sulfonating agent comprises fuming sulfuric acid containing from 1 .to 20% by weight of sulfur trioxide.

12. A process in accordance with claim 4 wherein said sulfonating agent is chlorosulfonic acid.

13. A process in accordance with claim 4 wherein said sulfonating agent is aceto-sulfuric acid.

1'4. A process for preparing a salt of a sulfonation product wherein said salt possesses detergent and wetting properties which comprises the steps of: contacting a feedstock comprising unsaturated and saturated hydrocarbons having from 8 to 18 carbon atoms per molecule with a sulfonating agent containing a free acid group, whereby unsaturated hydrocarbons are reacted without reacting saturated hydrocarbons, to form a reaction product comprising a sulfonated oil; contacting said sulfonated oil with an aqueous solution of a base to form a mixture comprising a salt of said sulfonated oil and unreacted saturated hydrocarbons; subjecting said mixture to extraction treatment with a mixture comprising a light hydrocarbon treating agent and a water-miscible ketone to obtain an extract phase comprising unreacted saturated hydrocarbons and hydrocarbon treating lagent and a raffinate phase comprising said salt of the sulfonated oil; separating said extract and raffinate phases; and separating said salt of the sulfonated oil from said rainate phase.

15. A process for preparing a salt of a sulfonation product wherein said salt possesses detergent and wetting properties which comprises the steps of: contacting a feedstock produced in the catalytic hydrogenation of carbon monoxide comprising unsaturated and saturated hydrocarfbons having from 8 to 18 carbon atoms per molecule with a sulfonating agent containing a free acid group at a temperature between about 20 C. and about 45 C., whereby unsaturated hydrocarbons are reacted without reacting saturated hydrocarbons, to form a reaction product comprising a sulfonated oil; contacting said sulfonated oil with `an aqueous solution of a base to form a mixture comprising a salt of said sulfonated oil and unreacted saturated hydrocarbons; subjecting said mixture 4to extraction treatment with a mixture compri-sing a light hydrocarbon treating agent and a water-miscible ketone to obtain an extract phase comprising unreacted saturated hydrocarbons and hydrocarbon treating agent and a ranate phase comprising said salt of the sulfonated oil; separating said extract and raffinate phases; and separating said salt of the sulfonated oil from said raffinate phase,

16. A process for preparing a salt of a sulfonation product wherein said salt possesses detergent and wetting properties which comprises the steps of: contacting a feedstock comprising unsaturated and saturated hydrocarbons having from 8 to 18 carbon atoms per molecule with sulfuric a-cid having a concentration of at least 80% at a temperature between about 20 C. and about 45 C., whereby unsaturated hydrocarbons are reacted without reacting saturated hydrocarbon-s, to form a reaction product comprising a sulfonated oil; contacting said sulfonated oil with an aqueous solution of an alkali metal hydroxide and Iacetone to form a mixture comprising a salt of said sulfonated oil and unrea-cted saturated hydrocarbons; subjecting said mixture to extraction treatment with a light hydrocarbon treating agent to obtain an extract phase comprising unreacted saturated hydrocarbons and hydrocar- 'bon treating agent and a raiinate phase comprising said salt of the sulfonatcd oil; separating said extract and rafnatc phases; and separating said salt of the sulfonated oil from said raffinate phase.

References Cited in the file of this patent UNITED STATES PATENTS Humphreys Nov. 26, 1918 Ramayya Oct. 17, 1933 Retaillian May 16, 1939 Beckham Mar. 7, 1944 Beckham July 25, 1944 Beckham Apr. 17, 1945 Fessler Aug. 21, 1945 Showalter Dec. 17, 1946

Claims (1)

1. A PROCESS FOR PREPARING A SALT OF A SULFONATION PRODUCT WHEREIN SAID SALT POSSESSES DETERGENT AND WETTING PROPERTIES WHICH COMPRISES THE STEPS OF: CONTACTING A FEEDSTOCK COMPRISING UNSATURATED AND SATURATED HYDROCARBONS HAVING FROM 8 TO 18 CARBON ATOMS PER MOLECULE WITH A SULFONATING AGENT CONTAINING A FREE ACID GROUP, WHEREBY UNSATURATED HYDROCARBONS, ARE REACTED WITHOUT REACTING SATURATED HYDROCARBONS, TO FORM A REACTION PRODUCT COMPRISING A SULFONATED OIL; CONTACTING SAID SULFONATED OIL WITH A TREATING AGENT COMPRISING AN AQUEOUS SOLUTION OF A BASE TO FORM A MIXTURE COMPRISING A SALT OF SAID SULFONATED OIL AND UNREACTED SATURATED HYDROCARBONS; SUBJECTING SAID MIXTURE TO EXTRACTION TREATMENT WITH A TREATING AGENT COMPRISING A LIGHT HYDROCARBON TO OBTAIN AN EXTRACT PHASE COMPRISING UNREACTED SATURATED HYDROCARBONS AND HYDROCARBON TREATING AGENT AND A RAFFINATE PHASE COMPRISING SAID SALT OF THE SULFONATED OIL; INTRODUCING A WATER-MISCIBLE KETONE IN COMBINATION WITH ONE OF SAID TREATING AGENTS IN SAID AFOREMENTIONED TREATING STEPS; SEPARATING SAID EXTRACT AND RAFFINATE PHASES; AND SEPARATING SAID SALT OF THE SULFONATED OIL FROM SAID RAFFINATE PHASE.

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