US3843564A - Detergent compositions and methods of obtaining them - Google Patents

Abstract

1. A METHOD FOR PRODUCING ALKYL SULFATES AND MIXTURES OF OLEFINIC SULFONATES AND ALSO ORTHODIALKYL BENZENE SULFONATES HAVING DETERGENT AND DIODEGRADABLE PROPERTIES WITH SUPERIOR FOAM STABILITY, WHICH METHOD COMPRISES THE STEPS OF: (A) TREATING NORMAL PARAFFIN HYDROCARBONS HAVING BETWEEN 14 AND 24 CARBONATION CATALYST CHOSEN FROM ISOMERIZING DEHYDROGENATION CATALYST CHOSEN FROM THE GROUP CONSISTING OF: CHROMIUM OXIDE AND POTASSIUM OXIDE, DEPOSITED ON ALUMINA; PLATINUM, LITHIUM AND ARSENIC DEPOSITED ON ALUMINA; AND COPPER, POTASSIUM, AND CHROMIUM DEPOSITED ON ALUMINA; IN THE PRESENCE OF HYDROGEN TO YIELD A SUBSTANTIAL AMOUNT OF OLEFINS AND SATURATED STRAIGHT CHAIN ORTHODIALKYL BENZENE HYDROCARBONS; (B) SEPARATING HYDROGEN AND CRACKING PRODUCTS OF THE SAID NORMAL PARAFFIN HYDROCARBONS FROM THE EFFLUX; (C) SULFATING AT LEAST A PART OF THE OLEFIN HYDROCARBONS RESULTING FROM THE DEHYDROGENATION OF THE NORMAL PARAFFIN HYDROCARBONS BY CONTACT OF THE SAID OLEFIN WITH SULFURIC ACID OF A CONCENTRATION OF MORE THAN 90 PERCENT FOR A PERIOD OF TIME BETWEEN 1 AND 10 MINUTES, AT A TEMPERATURE BELOW 25*C.; (D) NEUTRALIZING THE EFFLUENT OF THE SULFATING STEP BY ADDITION OF AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METL HYDROXIDES AND AMMONIA (E) HYDROLYZING THE PRODUCTS THUS NEUTRALIZED WITH AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA TO CONVERT SULFURIC ESTERS PRESENT IN THE PRODUCTS FROM THE PRODUCTS FROM THE SULFATING STEP TO SULFATES WHEREIN AN ORGANIC PHASE AND AN AQUEOUS PHASE ARE PRODUCED; (F) SUBJECTING THE REMAINING EFFLUX FROM STEP (B) NOT UTILIZED IN STEP (C) AND THE ORGANIC PHASE FOR STEP (E) TO SULFONATION; (G) NEUTRALIZING OF SULFONATION PRODUCTS FROM STEP (F) BY ADDITION OF AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA; (H) HYDROLYZING THE PRODUCTS THUS NEUTRALIZED WITH AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA, TO CONVERYT SULTONES PRESENT IN THE PRODUCTS TO SULFONATES; (I) RECYCLING TO THE DEHYDROGENATION STEP THE ORGANIC PHASE WHICH CONSISTS OF NORMAL PARAFFINS, AND THE SMALL QUANTITIES OF NAPHTHENE, OLEFIN, AND AROMATIC HYDROCARBONS OBTAINED BY SETTLING AAFTER THE HYDROLYZIN STEP.

Description

Oct. 22, 1974 c, MARTY ETAL DETERGENT COMPOSITIONS AND METHODS OF OBTAINING THEM Filed Feb. 16, 1971 mm mm mm .om fi mm -N a 8 A t v. E 2 J x v m 9 Q United States Patent O "ice 3,843,564 DETERGENT COMPOSITIONS AND METHODS OF OBTAINING THEM Claude Marty, Le Havre, Jean Maurin, Montivilliers, and Joseph Edouard Weisang, Le Havre, France, assignors to Compagnie Francais de Rafiinage, Seine, France Filed Feb. 16, 1971, Ser. No. 115,488 Claims priority, application France, Feb. 16, 1970, 7005438 Int. Cl. C11d 1/14, 1/37, 11/04 US. Cl. 252-552 7 Claims ABSTRACT OF THE DISCLOSURE A detergent composition with linear side chains and consequent biodegradability being a mixture of orthodialkyl benzene sulfonates, alkenyl sulfonates, and hydroxy alkyl sulfonates with unexpectedly desirable foaming characteristics in aqueous solution. Also, alkyl sulfate biodegradable detergent compositions. Processes for manufacturing these compositions from normal paraffinic stock of a certain carbon range.

The present invention relates to biodegradable detergent compositions and also to economic methods of manufacturing said compositions.

Biodegradability of detergents are becoming a necessity in order to avoid the pollution of waters with by-products which bacteria cannot destroy.

It is known that the alkyl benzene sulfonates obtained by alkylation of benzene by propylene tetramer, followed by sulfonation and neutralization with the use of an alkaline base, constitute good detergents. However, their biodegradability properties are poor due to branching in the hydrocarbon chains.

The alkyl benzene sulfonates having linear side chains undergo much more complete biological degradation. Consequently, they are tending to replace the alkyl benzene sulfonates with branched side chains. The hydrocarbons used in the preparation of the linear alkyl benzene sulfonates are obtained by catalytic alkylation of benzene by a linear olefin or by a normal monochloroparaffin. However, the cost of these processes is very high, on the one hand, because the cost of the alkylation process proper and, on the other hand, due to the fact that two raw materials must be prepared, namely, the benzene and the linear olefin or normal monochloroparaffin.

Furthermore, it is known that the sulfation of linear olefins, followed by neutralization, also leads to good biodegradable detergents which are available in the form of concentrated aqueous solutions.

An object of the present invention is to produce high quality detergent compositions having good ecological properties, including biodegradability, starting from a single raw material.

The applicants have found that such compositions can be obtained from specific hydrocarbons, namely, by sulfonation and then neutralization, or by sulfation and then neutralization, followed by a sulfonation and a neutralization.

A preferred embodiment of the present invention is a method of obtaining biodegradable sulfonate detergent compositions by carrying out in a stream of hydrogen a nonisomerizing catalytic dehydrogenation of normal parafiins having between 14 and 24 carbon atoms, eliminating the hydrogen and the cracking products of the said normal parafiins from the effiux, subjecting the olefin and aromatic hydrocarbons, resulting from the dehydrogenation, to a sulfonation by sulfuric anhydride in gaseous state, and neutralizing and hydrolyzing with an alkaline base the products resulting from the sulfonation.

3,843,564 Patented Oct. 22, 1974 Another embodiment of the present invention is a similar method for obtaining biodegradable detergent sulfonate and sulfate compositions wherein the olefin and aromatic hydrocarbons subjected to the sulfonation are at least in part composed of the hydrocarbons remaining after a sulfation by concentrated sulfuric acid of at least a part of the olefin hydrocarbons resulting from the dehydrogenation of the normal paraffins and by the fact that the products resulting from the sulfation are neutralized and hydrolyzed by an alkaline base.

Still another preferred embodiment of the present invention is a biodegradable detergent composition containing, as active products, primarily orthodialkyl benzene sulfonates, alkenyl sulfonates and hydroxy alkyl sulfonates of an alkali metal or ammonium ion. The alkyl and alkenyl radicals are linear and contain between 1 and 18 carbon atoms in the case of the ortho-dialkyl benzene sulfonates and between 14 and 24 carbon atoms in the case of the alkenyl sulfonates and the hydroxy alkyl sulfonates.

A surprising advantage of the foregoing composition has been discovered by the applicants; namely, the foam generated by this composition in aqueous solution has unexpectedly a desirable degree of stability. This property is not one which would be deduced from the corresponding properties of the individual components of the composition. It is known that the foam produced by detergent compositions must have a certain degree of stability. However, ecologically it is important that the detergent composition foam not be too stable. Such foam discharged with waste water into the public waterways must not remain floating on the surface of the water for long dis tances, or it will result in a disagreeable accumulation of scum. Instead, it should rapidly disperse the detergent of the foam into the waste water.

The alkyl aryl sulfonates have satisfactory foam stability. However, because alkenyl sulfonates and hydroxyalkyl sulfonates produce foams of such quantity and stability, it is usual to include with them additives adapted to break the foam.

One would suppose, therefore, that the mixture of the particular ingredients of the foregoing compositions would give rise to a much too stable foam, especially when (as in the case in Example 11, below) the quantities of alkenyl sulfonates and of hydroxyalkyl sulfonates present in the composition are clearly in excess of the quantity of the alkyl aryl sulfonates. However, tests by the applicants have proven quite the contrary. Even in this unfavorable case, the detergent composition of the present invention, contrary to all expectations, gives rise to a foam having perfectly satisfactory stability, comparable to that of alkyl aryl sulfonates alone.

Still another embodiment of the present invention 1ncludes biodegradable detergent compositions containing active products which are primarily alkyl sulfates of an alkali metal or ammonium ion, the alkyl radicals being linear and containing between 14 and 24 carbon atoms.

In the method of the invention, the charge of normal paraffin which is subjected to the dehydrogenation can be prepared by various methods. Thus a fraction rich in normal parafiins can be subjected to an extractive crystallization in urea or to a selective absorption on molecular sieves. These two methods are known and will, therefore, not be described in detail. It is not nemssary to prepare a normal paraffin having a specific number of carbon atoms between 14 and 24; the invention may, as a matter of fact, be carried out on a mixture of hydrocarbons. Extractive crystallization with urea is, however, the method preferred by the applicants. The preferred fraction is that which consists of normal paraffins having between 15 and 21 carbon'atoms.

The catalytic dehydrogenation of normal paraifins is carried out in the presence of hydrogen under pressure. This gas is introduced with the charge. The hydrogen can be recovered in the elflux and be recycled to the dehydrogenation reactor. The composition of the catalyst used is not critical, and this constitutes one of the advantages of the process. One such catalyst consists of metals having dehydrogenating properties deposited on a support, such as alumina. However, it is necessary that the catalyst is not isomerizing, and in order to obtain this property, the acid sites of the support, should the latter contain any, are neutralized for this purpose. It is advantageous to employ a catalyst consisting of chromium oxide and potassium oxide deposited on alumina. Mention may also be made of the catalyst consisting of platinum, lithium, and arsenic deposited on alumina. The conditions under which the dehydrogenation is effected depend on the catalyst used. The temperature is generally between 250 C. and 500 C. The rate of conversion of the normal parafiins can be substantial. As a matter of fact, the method of the invention does not make it necessary to obtain solely olefin hydro carbons.

The efilux of the dehydrogenation reactor is formed of hydrogen, unreacted normal paraffins and aromatic and olefin hydrocarbons, as well as traces of naphthenes and cracking products. After separation of the hydrogen, it is advantageous to eliminate the cracking products from this effiux. This can be effected in simple fashion by distillation.

A distinctive characteristic of the invention resides in the fact that the aromatic and olefin hydrocarbons coming from the dehydrogenation of the normal paraflins are subjected simultaneously to a sulfonation reaction or to a sulfation reaction followed by a sulfouation reaction. These reactions may be effected either on the mixture of unreacted normal paraffins, ole-fin and aromatic hydrocarbons and naphthenes, or on a mixture containing only olefin and aromatic hydrocarbons.

In a first embodiment of the process of the invention, the dehydrogenation efilux after removal of the hydrogen and the cracking products is subjected to a sulfonation in a reactor at room temperature by gaseous sulfuric anhydride, diluted in a gas, which latter does not react with the products of the reaction under the operating conditions (this is true of nitrogen and air). The sulfonation is effected, for instance, by causing the sulfuric anhydride to sweep over a thin film of hydrocarbons or by bubbling sulfuric anhydride into the liquid mass of hydrocarbons.

After sulfonation, the resultant products 'are subjected to neutralization by soda at ordinary temperature. Thereupon, by an alkaline hydrolysis in an autoclave by means of excess soda, at a temperature between 150 C. and 260 C., the sultones are transformed into sulfonates. By settling, there is obtained an aqueous phase containing the sodium sulfonates and an organic phase which contains primarily the normal paraffins which did not react upon the dehydrogenation and small quantities of naphthenes and olefin and aromatic hydrocarbons. This organic phase is recycled to the dehydrogenation reactor.

A second embodiment of the method of the invention consists in sulfating the efllux of the dehydrogenation reactor, which has been freed of the hydrogen and cracking products, by contact with sulfuric acid of a concentration 1 of more than 90 percent at room temperature or lower for short periods of contact, and then neutralizing the resultant products with soda at room temperature and effecting an alkaline hydrolysis with soda at the temperature of 80 C., preferably on the organic phase obtained 4 of recovering the hydrocarbons to be recycled; they simply separate out after the alkaline hydrolysis.

The third and fourth embodiments of the invention are similar to the first and second embodiments, respectively; however, the charge subjected to the sulfonation or sulfation is previously treated so as to remove the normal paraffins and the traces of naphthenes which are recycled to the dehydrogenation reactor. This separation can be effected by selective absorption on molecular sieves. The volume of the organic phase collected after hydrolysis of the sulfonates is much less than that obtained with the first and second embodiments of the invention. This volume is recycled to the sulfonation reactor.

The aqueous phase which contains the sulfates, as well as the aqueous phase which contains the sulfonates, may contain traces of hydrocarbons. These traces are extracted by means of a suitable solvent, for instance, a mixture of ether and normal pentane or a mixture of ether, normal pentane and isopropyl alcohol The sodium alkyl sulfates obtained are colorless liquids. The number of carbon atoms in these sulfates is larger than the number of carbon atoms in the sulfate at present available on the market since the sulfates comprise, in accordance with the invention and depending on the fraction from which one starts, between 14 and 24 carbon atoms which form a nonbranched chain.

The sodium sul-fonate composition obtained consists of a mixture of ortho-dialkyl benzene sulfonates, alkenyl sulfonates and hydroxy alkyl sulfonates.

After effecting the evaporation of the water, the sulfonates are obtained in the form of a powder. This phase may be carried out in a spray tower into which the solution of sulfonates are introduced against a counter-current of hot air. Furthermore, this apparatus has the advantage of effecting the removal of oil.

When it is desired to obtain a completely colorless powder, it may be advantageous to effect the decoloration of the sulfonates with the use of a dilute solution of sodium hypochlorite; however, this treatment is not necessary and, furthermore, has no effect on the detergent properties of the composition.

Reference is made to the applicants earlier copending application, Ser. No. 22,337, filed Mar. 24, 1970, now Pat. No. 3,761,532 for priority of any common subject matter claimed herein and otherwise for generalized background of the improvement.

The sole figure attached to the specification is a diagram of a preferred process of the invention. It is not intended to be limitative. Referring to said figure:

A gas oil rich in normal paratfins and having between 15 and 21 carbon atoms is introduced through the line 1 into a urea selective extraction unit 2. This unit 2 has not been shown in detail in the figure. The dewaxed gas oil is collected via the line 3a. The normal parafiins are in-. troduced into a nonisomerizing dehydrogenation reactor 6 via the line 3, the recycled hydrocarbons (which are composed primarily of normal parafiins and traces of naphthenes) via the line 4, and the hydrogen via the line 5. The dehydrogenation catalyst consists of platinum, lithium, and arsenic deposited on an alumina support in quantities, expressed in percent of the weight of the catalyst, of 0.75,.0.50, and 0.36, respectivelyfThe hourly space speed of the liquid charge is equal to l. The molar ratio of hydrogen to hydrocarbons is equal to 5. The operation is carried out at a temperature of 450 C., the pressure being slightly more than 1 bar. V After separation of the hydrogen at 7, a part thereof is recycled via the line 5, while the cracking products composed primarily of hydrocarbons having a number of carbon atoms of between 6 and 15 are removed at the top of a column 8 and evacuated through the line 9. I

A part of the distillation residue is introduced through the line 10 into a sulfation reactor 11. The sulfuric acid of a concentration of 98 percent is introduced into the reactor through the line 12. The time of contact between the sulfuric acid and the charge is 5 minutes. The temperature of the reactor is fixed at 5 C. .The effiux is then introduced into a neutralization reactor 13 into which soda of a concentration of 4 N is introduced through the line 14. The neutralization is effected at room temperature. The efllux is then subjected to alkaline hydrolysis in the reactor 15 for a period of three hours at a temperature of 80 C.

After decantation in the container 16, the sodium alkyl sulfates are recovered via the line 17. They can be subjected to a de-oiling, which has not been shown in the diagram. The organic phase discharged through the line 18 from the decantation vessel, as well as the distillation residue coming from the column 8 which circulates in the line 19, are introduced into a sulfonation reactor 20. A stream of nitrogen,'containing 1 percent by weight sulfuric anhydride in gaseous form, is introduced into the liquid mass of the hydrocarbons via the line 21. The efilux from the sulfonation reactor is introduced into a neutralization reactor 23 into which soda of a concentration of 4 N is introduced through the line 24. The neutralization is effected at room temperature. An alkaline hydrolysis of the efflux is then effected in the reactor 25 at 250 C. for 1 hour under a pressure of 41 bars. After decantation in the vessel 26, the organic phase, composed primarily of normal paraffins which have not been reacted in the reactor 6, together with traces of naphthenes, is recycled via the line 4. The aqueous phase is introduced via the line 27 into a de-oiling' device 28. The solvent, composed of a mixture of ethyl ether and normal pentane, is introduced through the line 29. After decantation in the vessel 30, the organic phase, consisting of the traces of oil dissolved in the solvent, is recovered via the line 31 and a solution of the sulfonates via the line 32. The latter are introduced into an evaporation device 33 from where the powder of the sulfonates is collected by the line 34, the water being eliminated through the line 35.

A variant of the embodiment of the method described in the diagram consists in placing a settling vessel between the neutralization reactor 13 and the hydrolysis reactor 15. There is thus recovered an aqueous phase which is is composed of sulfates and an organic phase which is subjected to hydrolysis in the reactor 15. After hydrolysis of the sulfuric diesters, an aqueous phase 17, consisting of sulfates, and an organic phase 18 are collected in the settling vessel 16, the organic phase being subjected to sulfonation. v i

The invention is further illustrated by the following examples which are not of a .limitative character.

EXAMPLEI Temperature: 440 C. Hourly space velocity of the liquid moctadecane: 1 Molar ratio .of hydrogen to normal octadecane: 5.

In Table I below there is found the conversion of the normal octadecane, the yields of ,the .components ofthe efllux and the isomeri zationrate for ,100 g. of converted charge, as well as the composition of the aromatic hydrocarbons expressed in weight for 100 g. of aromatic hydrocarbons.

6 TABLE I Conversion, percent 31 Yield (in grams per 100 g. of converted product):

Hydrogen 2.1 Cracked products:

Gaseous hydrocarbons+(number of carbon atoms 5) 1.7 Liquid hydrocarbons (number of carbon atoms )5) 5.9 Olefin hydrocarbons 41.0 Aromatic hydrocarbons 44.3 Naphthene hydrocarbons 40 Carbon 1.0 Isomerization rate 2.0

Analysis by mass spectrometry of the aromatic hydrocarbons obtained reveals that they are composed primarily of dialkyl benzenes. By nuclear magnetic resonance the applicants have found that they are orthodialkyl benzenes having linear alkyl radicals.

This table shows that one can expect relatively high conversion rates. Furthermore, it is noted that the isomerization rate, as well as the quantities of cracked products, are very low. The olefin hydrocarbons obtained consist of more than percent monoolefins.

After removal of the hydrogen and the cracked products, the effiux from the dehydrogenation reactor is subjected to sulfation at a temperature of 5 C. by means of 98 percent sulfuric acid. The contact time is short (5 minutes) so as to avoid the formation of polymers. The molar ratio of sulfuric acid to olefins to be sulfated is equal to 1.5.

The conversion rate of the olefin hydrocarbons (which are the only ones ones to react with the sulfuric acid) is equal to 52 percent, including less than 5 percent polymers. The total yield of sodium alkyl sulfates per 100 g. of olefins converted is equal to 75 percent (after neutralization of the sulfuric monoester with 4 N soda at room temperature and hydrolysis of the sulfuric diester by a 4 N soda solution in excess for 3 hours). The aqueous phase obtained is composed primarily of a solution of sodium alkyl surfates, the alkyl radical being linear and having 18 carbon atoms.

The organic phase is subjected to a sulfonation reaction. A gaseous stream containing 1.2 percent sulfuric anhydride in nitrogen is bubbled into the said organic phase at a temperature of 22 C. The time of reaction is 1 /2 hours. The sulfonic acids obtained are then neutralized with 4 N soda at room temperature.

An akaline hydrolysis is then effected in an autoclave by means of soda solution at a temperature of 250 C. for 1 hour. After settling, the organic phase, which contains the normal octadecane which has not been converted as well as the naphthenes, can be recycled into the dehydrogenation reactor. The aqueous phase is composed primarily of sodium alkenyl sulfonates, sodium hydroxy alkyl sulfonates and sodium ortho-dialkyl benzene sulfonates. The total conversion of the olefin and aromatic hydrocarbons after sulfonation, neutralization and hydrolysis is equal to 96 percent; The aqueous phase can be subjected to a de-oiling in order to extract therefrom the traces of dissolved hydrocarbons. This extraction can be effected by means of a mixture of ethyl ether and normal pentane. The dehydration yields a biodegradable detergent powder. This powder contains dissodium sulfate formed upon the neutralization with the soda. The latter may be separated. However, it is not necessary to do so, since sodium sulfate is a substance which is contained in the composition of wash powders.

EXAMPLE II mina. These three metals have been deposited in the form of nitrates in such a manner that after calcination at 800 0., they have the following weight percent composition, referred to the alumina: 4.97% chromium, 3.03% copper, and 1.00% potassium. The hourly space velocity of the normal octadecane measured in liquid state is equal to l; the temperature of the catalyst is 440 C. The molar ratio of hydrogen to normal octadecane is equal to 5. The conversion of the normal octadecane introduced into the nonisomerizing dehydrogenation reactor is equal to 19 percent. For 100 g. of normal octadecane charged, there are collected 12.8 g. of olefin hydrocarbons and 5.9 g. of aromatic hydrocarbons. The olefin hydrocarbons, as well as the aromatic hydrocarbons collected, are subjected simultaneously to sulfonation by bubbling a gaseous stream of sulfuric anyhdride in nitrogen, the molar concentration of sulfuric anhydride in nitrogen being equal to 1 percent. After neutralization of the sulfonic acids by 4 N soda at ordinary temperature and then alkaline hydrolysis at a temperature of 250 C. and under a pressure of 41 bars for a period of 1 hour, the excess soda is neutralized by sulfuric acid. Evaporation is effected until a dry product is obtained.

The detergent properties of the product obtained have been compared with those of an ordinary commercial soap by carrying out the following test.

A wash powder of the following composition was prepar-ed with the product of the invention:

Two aqueous solutions were prepared with this powder, one of 5 g./l. of pure detergent and the other of 2 g./l.

With each solution a cloth, impregnated with a standard soilage (cloth marketed under the name Cotton Soil ClothSl S 47), was washed in the apparatus known by the name of Launderometer under the following conditions: washing of a sample of 5 g. of cloth in 2 liters of solution for 30 minutes at 90 C. with agitation by balls of stainless steel of about 6 mm. in diameter.

In order to establish the detergent power, reflection measurements were carried out with the use of the apparatus sold under the name Photovolt by the Photovolt Corporation.

Ye: luminance of the cloth after washing.

Ys: luminance of the cloth impregnated with the standard soilage.

Yt: luminance of the support cloth not impregnated with the standard soilage.

The detergent power DP in percent was calculated by means of the following formula:

Under the same conditions, washings of the same cloth were also etfected with solutions of 5 g. per liter and 2 g./l. of a current commercial soap also containing 1 g./l. of anhydrous sodium carbonate. The results are set forth in Table II.

Sulfonates prepared in accordance with the method described in Example 11 are subjected to the following biodegradability test:

For 7 days a microorganism culture is maintained with constant aeration at a temperature of 25 C. in a semisynthetic medium containing 20 mg. per mil of the product to be tested and then, at the end of this time, the same quantity of detergent is again introduced, and the test is continued until the second day. On. the 7th and 10th days determinations are made to note the elimination of the products and establish their biodegradability.

The culture broth used in the tests comprises between 2 and 4x10 microorganisms per mm. It was prepared by aerobic fermentation, in a rich nutrient medium, of microorganisms taken from the water of the Seine River at the point of discharge of the large Clic'hy sewer in Paris.

The detergent content of the microorganism cultures is determined in accordance with the method of Longwell and Manisoe, the principle of which is as follows: a colored complex is formed with methylene blue; it is extracted with chloroform and a calorimetric measure is effected by comparison with a standard'product.

The biodegradation rate T at the end of 7 days is given by the formula:

2o- (Cm-0.7) X 100 20 in which C is the content of detergent in the test medium on the 7th day, expressed in mg. per mil, and Ct is the content of detergent in a control medium on the 7th day, expressed in mg. per mil.

In similar fashion, the biodegradation at the end of 10 days, T is given by the formula:

The results obtained appear in Table HI below- TABLE III Composition of the invention Test Test Control No. 1 No. 2

Concentration of detergent 7th day (parts i 7 per million 0.80 3. 00 '2. 30 Biodegradation percent, 7th day 89. 00 92. 50 Concentration of detergent, 10th day- 0. 65 p 2. 2. 65 Biodegradation percent, 10th day 94. 5 95. 00

Biodegradabilitmln ni 92.6 94.1

Average 93.35

Hydroxyalkyl sulfonates 47 Other 1 2 Total 10 In the commercial production the percentage composition for each will range from to 60% for alkyl aryl sulfonates, 8% to 45% for alkenyl sulfonates, and 20% to 72% for hydroxyalkyl sulfonates.

We claim:

1. A method for producing alkyl sulfates and mixtures of olefinic snlfonates and also orthodialkyl benzene sulfonates having detergent and biodegradable properties with superior foam stability, which method comprises the steps of:

(a) Treating normal paraffin hydrocarbons having between 14 and 24 carbon atoms with a cyclicizing nonisomerizing dehydrogenation catalyst chosen from the group consisting of: chromium oxide and potassium oxide, deposited on alumina; platinum, lithium and arsenic deposited on alumina; and copper, potassium, and chromium deposited on alumina; in the presence of hydrogen to yield a substantial amount of olefins and saturated straight chain orthodialkyl benzene hydrocarbons;

(b) Separating hydrogen and cracking products of the said normal'parafiin hydrocarbons from the efllux;

(c) Sulfating at least a part of the olefin hydrocarbons resulting from the dehydrogenation of the normal parafiin hydrocarbons by contact of the said olefins with sulfuric acid of a concentration of more than 90 percent for a period of time between 1 and 10 minutes, at a temperature below 25 C.;

(d) Neutralizing the efiluent of the sulfating step by addition of an alkaline base selected from the group consisting of alkali metal hydroxides and ammonia;

(e) Hydrolyzing the products thus neutralized with an alkaline base selected from the group consisting of alkali metal hydroxides and ammonia to convert sulfuric esters present in the products from the products from the sulfating step to sulfates wherein an organic phase and an aqueous phase are produced;

(f) Subjecting the remaining efilux from step (b) not utilized in step (c) and the organic phase from step (e) to sulfonation;

(g) Neutralizing the sulfonation products from step (f) by addition of an alkaline base selected from the group consisting of alkali metal hydroxides and ammonia;

(h) Hydrolyzing the products thus neutralized with an alkaline base selected from the group consisting of alkali metal hydroxides and ammonia, to convert sultones present in the products to sulfonates;

(i) Recycling to the dehydrogenation step the organic phase which consists of normal parafiins, and the small quantities of naphthene, olefin, and aromatic hydrocarbons obtained by settling after the hydrolyzing step.

2. A method for producing alkyl sulfates and mixtures of olefinic sulfonates and also orthodialkyl benzene sulfonates having detergent and biodegradable properties With superior foam stability, which method comprises the steps of:

(a) Treating normal parafiin hydrocarbons having between 14 and 24 carbon atoms with a cyclizing nonisomerizing dehydrogenation catalyst chosen from the group consisting of: chromium oxide and potassium oxide, deposited on alumina; platinum, lithium and arsenic deposited on alumina; and copper, potassium, and chromium deposited on alumina; in the presence of hydrogen to yield a substantial amount of olefins and saturated straight chain orthodialkyl benzene hydrocarbons;

(b) Separating out hydrogen and cracking products of said normal paraflin hydrocarbons from the efllux and additionally separating naphthene and unreact d parafiin hydrocarbons from said efilux and recycling the nephthene and unreacted parafiin hydrocarbons to said dehydrogenation step (a);

(c) Sulfating at least a part of the olefin hydrocarbons resulting from the dehydrogenation of the normal paraffin hydrocarbons by contact of the said olefins with sulfuric acid of a concentration of more than percent for a period of time of between 1 and 10 minutes, at a temperature below 25 C.;

(d) Neutralizing the eflluent of sulfating step by addition of an alkaline base selected from the group consisting of alkali metal hydroxides and ammonia;

(e) Hydrolyzing the products thus neutralized with an alkaline base selected from the group consisting of alkali metal hydroxide and ammonia to convert sulfuric esters present in the products from the sulfating step to sulfates, wherein an organic phase and an aqueous phase are produced;

(f) Subjecting the remaining efllux from step (b) not utilized in step (c) and the organic phase from step (e) to sulfonation;

(g) Neutralizing the sulfonation products from step (if) by addition of an alkaline base selected from the group consisting of alkali metal hydroxides and ammonia;

(h) Hydrolyzing the products thus neutralized with an alkaline base selected from the group consisting of alkali metal hydroxides and ammonia, at a sufficient temperature above room temperature to convert sultones present in the products to sulfonates;

(i) Recycling the organic phase resulting from the products of the hydrolysis step (h) to the sulfonation step (f):

3. A method as claimed in Claim 2 wherein the separation of the naphthenes and 14 to 24 carbon normal paraffin hydrocarbons is by selective absorption on molecular sieves.

4. A method as claimed in Claim 1 wherein said neutralizing step (g) is around room temperature and said hydrolyzing step (h) is at a temperature between C. and 300 C.

5. A method as claimed in Claim 1 wherein said normal paraflins contain from 15 to 21 carbon atoms.

6. The method of Claim 1 wherein said catalyst consists essentially of chromium, copper and potassium deposited on alumina in the form of nitrates and thereafter calcinated to give approximate weight percentages of 4.99% chromium, 3.03% copper, and 1.00% potas- .sium; the hourly space velocity of the hydrocarbon reactants in said catalytic reaction in step (a) is about one; the temperature of the catalytic reaction in step (a) is about 440 C.; hydrogen is supplied to the reaction in step (a) in a molar ratio relative to said hydrocarbon reactants of about five; and the pressure is about one bar.

7. The method of Claim 1 wherein said catalyst consists essentially of platinum, lithium, and arsenic deposited on alumina in amounts approximately equal to 0.75%, 0.50%, and 0.36%, respectively, of the weight of the catalyst; the hourly space velocity of the hydrocarbon reac tants in said catalytic reaction in step (a) is about one; the temperature of the catalytic reaction in step (a) is about 440 C.; hydrogen is supplied to the reaction in step (a) in a molar ratio relative to said hydrocarbon reactants of about five; and the pressure is about one bar.

References Cited UNITED STATES PATENTS 3,506,580 4/1970 Rubinfeld et al. 252-550 (XR) 3,458,447 7/1969 Shultz 260-505 A (XR) 3,480,556 11/1969 DeWitt et al. 260-458 (XR) 3,437,585 4/ 1969 Kuchar 208-96 3,409,637 11/1968 Eccles et al. 260-327 3,346,505 10/1967 'Blakeway et a1. 252558 2,210,316 8/1940 Dreisbach 260460 2,871,254 1/1959 Hoog et al. 260460 3,531,544 9/1970 Berg 260-6833 (Other references on following page) UNITED STATES PATENTS Taylor et a1. 260-668 Bloch 260-683.3 Keblys 260683.3 Kuchar 260--683.3 Kirschenbaum 260-683.3 Eccles et a1. 252558 Bloch 260505 A Bloch et a1 260460 FOREIGN PATENTS 8/ 1961 Great Britain.

Great Britain.

I 12 OTHER REFERENCES Liddicoet, Alpha-Olefins in the Surfactant Industry, IAOCS, vol. 40, November 196-3, pp. 631-633.

5 LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner [1.8. CI. X.R.

Claims (1)

1. A METHOD FOR PRODUCING ALKYL SULFATES AND MIXTURES OF OLEFINIC SULFONATES AND ALSO ORTHODIALKYL BENZENE SULFONATES HAVING DETERGENT AND DIODEGRADABLE PROPERTIES WITH SUPERIOR FOAM STABILITY, WHICH METHOD COMPRISES THE STEPS OF: (A) TREATING NORMAL PARAFFIN HYDROCARBONS HAVING BETWEEN 14 AND 24 CARBONATION CATALYST CHOSEN FROM ISOMERIZING DEHYDROGENATION CATALYST CHOSEN FROM THE GROUP CONSISTING OF: CHROMIUM OXIDE AND POTASSIUM OXIDE, DEPOSITED ON ALUMINA; PLATINUM, LITHIUM AND ARSENIC DEPOSITED ON ALUMINA; AND COPPER, POTASSIUM, AND CHROMIUM DEPOSITED ON ALUMINA; IN THE PRESENCE OF HYDROGEN TO YIELD A SUBSTANTIAL AMOUNT OF OLEFINS AND SATURATED STRAIGHT CHAIN ORTHODIALKYL BENZENE HYDROCARBONS; (B) SEPARATING HYDROGEN AND CRACKING PRODUCTS OF THE SAID NORMAL PARAFFIN HYDROCARBONS FROM THE EFFLUX; (C) SULFATING AT LEAST A PART OF THE OLEFIN HYDROCARBONS RESULTING FROM THE DEHYDROGENATION OF THE NORMAL PARAFFIN HYDROCARBONS BY CONTACT OF THE SAID OLEFIN WITH SULFURIC ACID OF A CONCENTRATION OF MORE THAN 90 PERCENT FOR A PERIOD OF TIME BETWEEN 1 AND 10 MINUTES, AT A TEMPERATURE BELOW 25*C.; (D) NEUTRALIZING THE EFFLUENT OF THE SULFATING STEP BY ADDITION OF AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METL HYDROXIDES AND AMMONIA (E) HYDROLYZING THE PRODUCTS THUS NEUTRALIZED WITH AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA TO CONVERT SULFURIC ESTERS PRESENT IN THE PRODUCTS FROM THE PRODUCTS FROM THE SULFATING STEP TO SULFATES WHEREIN AN ORGANIC PHASE AND AN AQUEOUS PHASE ARE PRODUCED; (F) SUBJECTING THE REMAINING EFFLUX FROM STEP (B) NOT UTILIZED IN STEP (C) AND THE ORGANIC PHASE FOR STEP (E) TO SULFONATION; (G) NEUTRALIZING OF SULFONATION PRODUCTS FROM STEP (F) BY ADDITION OF AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA; (H) HYDROLYZING THE PRODUCTS THUS NEUTRALIZED WITH AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA, TO CONVERYT SULTONES PRESENT IN THE PRODUCTS TO SULFONATES; (I) RECYCLING TO THE DEHYDROGENATION STEP THE ORGANIC PHASE WHICH CONSISTS OF NORMAL PARAFFINS, AND THE SMALL QUANTITIES OF NAPHTHENE, OLEFIN, AND AROMATIC HYDROCARBONS OBTAINED BY SETTLING AAFTER THE HYDROLYZIN STEP.

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