DE2106507A1 - Mixture of synthetic detergents and processes for their manufacture - Google Patents

Description

Mixture of synthetic detergents and processes for their manufacture

The invention relates to mixtures of synthetic detergents which are biodegradable and their active ones Main ingredients the general formula

own. It relates in the same way to economical processes for the production of these mixtures.

Biodegradability is one of detergents particularly desirable property in order to avoid the pollution of wastewater with products produced by Bacteria cannot be broken down.

It is known that alkylbenzene sulfonates, which are prepared by alkylating benzene with a tetramer of propylene, followed by sulfonation and neutralization with an alkaline base, are good detergents. However, their biodegradability is only mediocre,

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because of the branching of the hydrocarbon chains.

The sulfonates of alkylbenzenes, the linear side chains can undergo more complete biodegradation.Therefore, there is a tendency to Replace alkylbenzene sulfonates with branched side chains. So the hydrocarbons that are assumed to obtain the linear alkylbenzene sulfonates, are made by catalytic ^ alkylation of benzene with a linear olefin or with a normal monochlorinated paraffin won. However, the cost of this method is very high, partly because of the cost of said suitable one Alkylation process and, on the other hand, because you have to prepare two starting materials accordingly, namely benzene and a linear olefin or a normal monochlorinated paraffin.

It is also known that sulfation of linear olefins followed by neutralization is also leads to good biodegradable detergents which are available in the form of an aqueous concentrated solution.

In another known process, alkylaryl sulfonates are preferably prepared, using straight, runs out of unbranched normal paraffins, which are subjected to catalytic dehydrocyclization. The severed ones After sulfonation and neutralization, alkylaryls lead to known detergents, such as. B. Orthodialkylbenzene sulfonates. It is also possible to sulfonate all of the product resulting from the dehydrocyclization. In this case the non-sulfonated hydrocarbons are separated and returned to the cyclization reactor

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All of the processes mentioned are aimed primarily at the production of the alkylbenzene sulfonates, which are known to be good detergents. For this, however, either two starting materials must be assumed, or it must be used in the course of the process multiple separations are performed. There is no known mix of detergents produced by a direct Sulphonation or sulphation of the products originating from a dehydrogenation reactor is produced and their The detergency and foam behavior has been proven to be the same as or better than that of the alkylbenzene sulfonates.

The invention is based on the object of creating mixtures of synthetic detergents which are biodegradable and , beginning with a single starting material, of developing an economical manufacturing process. According to the invention, the mixture of synthetic detergents, the main active ingredients of which has the general formula

[jQ _{n + 1} - JIq] _n - so, μ

have, in that ¹¹ M "represents an alkali metal or an ammonium ion," n "is 0 or 1," IL ^{M is} an orthodialkylbenzene radical with a linear alkyl group of carbon atoms from 1 to 18, a linear alkenyl "or a linear hydroxyalkyl radical the number of carbon atoms represents 14 to 24, and "Rg" represents a linear alkyl radical having a number of carbon atoms between 14 and 24.

According to the invention, these mixtures are obtained in that, starting from special hydrocarbons, these are subjected to a sulfonation followed by a neutralization, or a sulfation followed by a neutralization

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tion, then subjected to sulfonation with final neutralization.

The process according to the invention is characterized in that a catalytic dehydrogenation takes place in the presence of hydrogen from normal paraffin of carbon atom number 14- "to 24 is carried out, the resulting Kraekprodukte "said normal paraffin and the liberated hydrogen is removed and the aromatic and olefinic hydrocarbons obtained in this way are sulfonated with gaseous sulfur trioxide be subjected, and that the products obtained from the sulfonation are neutralized and with an alkaline Base to be hydrolyzed.

Another embodiment of the process according to the invention is that the aromatic and olefinic Hydrocarbons that are subjected to sulfonation consist at least in part of hydrocarbons which have been subjected to sulphation with concentrated sulfuric acid and partly from olefinic hydrocarbons, that result from the dehydration of normal paraffin and that the products coming from the sulphation neutralized and hydrolyzed with an alkaline base.

A particular advantage of the mixtures according to the invention consists in addition to the economical production process in a surprising and unpredictable foam behavior. The foam formed in aqueous solution is only massive stable and is easily drawn into the solution in the course of a washing process without staying on the surface for too long to stay, whereby a rapid distribution of the detergent trapped in the foam is achieved. The alkyl

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aryl sulfonates have similar properties, on the other hand The alkenyl and hydroxyalkyl sulfonates foam much too much and the foam formed is very stable, so that in these cases, certain additives normally have to be added in order to "slow down" the foam showed that the foaming behavior of the mixtures according to the invention corresponded completely to that of the alkylaryl sulfonates; H. the foam formed was only moderately stable. This behavior is unpredictable and occurs even with mixtures according to Example III below, in which the proportion of alkenyl and hydroxyalkyl sulfonates is that of the alkylaryl sulfonates surpasses.

According to the process according to the invention, the normal paraffin used, which is subjected to dehydration, can be prepared in various ways. For example, a distillation cut enriched with normal paraffin can be subjected to an extractive crystallization with urea or a selective absorption with molecular sieves. These two processes are known and need not be described in detail. It is not necessary to use a normal paraffin that has a number of carbon atoms between 14 and 24. The invention can also be applied to a mixture of hydrocarbons like. Preferably, however, the process of extractive crystallization with urea and a distillation cut composed of normal paraffins with a carbon number between 15 and 21 are used.

The catalytic dehydrogenation of normal paraffin is carried out under pressure in a hydrogen atmosphere is added with the charge. The hydrogen can be recovered as waste and returned to the dehydration reactor.

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tion can be returned. The composition of the used Catalyst is not critical and is one of the advantages of the process. Such a catalyst is made of metals composed of "dehydrating properties" and deposited on a carrier such as aluminum are. However, it is necessary that the catalyst be of the non-isomeric type and, in order to obtain this property, be neutralized any acid groups present on the support · It is advantageous to use a catalyst that has a high turnover of the input material and which supplies the cracking reactions largely suppressed. For example, you can use a catalyst made up of chromium oxide and potassium oxide assembled and deposited on an aluminum support, or an equivalent catalyst composed of platinum, lithium and arsenic and also on an aluminum support is deposited. The conditions under which the dehydrogenation takes place depend on the catalyst used away. The temperature is generally between 250 ° C and 500 ° C. The degree of conversion of the normal paraffin can be important. The method according to the invention is not only based on obtaining olefinic hydrocarbons.

The product obtained from the dehydrogenation reagent consists of hydrogen, unconverted normal paraffins, aromatic and olefinic hydrocarbons and traces of naphtha together, as well as from cracked products. To If the hydrogen is to be separated off, it is advantageous to also remove the cracking products. This can be done simply by means of Distillation can be carried out.

An essential feature of the invention can be seen in the fact that the aromatic and olefinic hydrocarbons, caused by dehydration of the Toraalpar-

1 0 fi ■ "··.? 6/1 6 7 8

affins originate, are simultaneously subjected to a sulfonation or a sulfation followed by a sulfonation. These reactions can be carried out with a mixture of unconverted normal paraffins, olefinic and aromatic Hydrocarbons and naphthenes are carried out or even with a mixture that these olefinic and does not contain aromatic hydrocarbons.

In a first standard of the method according to the invention the dehydrogenation product, freed from hydrogen and cracked products, becomes a sulfonation in a reactor at ambient temperature with gaseous sulfur anhydride | subjected. The sulfur anhydride is diluted with a gas, which does not react with the reaction products under the working conditions (this is the case with nitrogen and air). The sulfonation ion is achieved, for example, by covering a thin layer of hydrocarbons with sulfur anhydride or by blowing the sulfur anhydride into the liquid mass of the hydrocarbons. After sulfonation the products are subjected to neutralization with soda at normal temperature. Then be through an alkaline Hydrolysis in an autoclave and by abundant soda at temperatures between 150 ° C and 260 ° C die Sulphones converted into sulphonates. By decanting an aqueous phase that contains the sodium sulfonates | contains and an organic phase, which mainly unconverted normal paraffins from dehydration, weak Contains traces of naphthenes and traces of olefinic and aromatic hydrocarbons. This organic phase is returned to the dehydrogenation reactor

A second embodiment of the process according to the invention consists in the sulfation of the product that

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comes from the dehydrogenation reactor and has been "freed from hydrogen and cracked products" by contact with sulfuric acid a concentration above 90%, at ambient temperature or below and short contact times. Afterward this is followed by neutralization with soda at ambient temperature and alkaline hydrolysis with soda at one temperature of 80 ° C, preferably in an organic phase, which is obtained after separating off the aqueous phase. The aqueous Phase now contains the sodium alkyl sulfates.The organic phase undergoes a sulfonation according to the previously described type subjected. An advantage of the two working methods described is the ease of recovery of the hydrocarbons, to be returned. After the alkaline hydrolysis, they are separated off by decanting.

The third and fourth embodiment of the method according to the invention correspond to the first and second embodiment with the exception that the feed intended for sulfonation or sulfation is pretreated to remove the normal paraffins and traces of naphtha that are returned to the dehydrogenation reactor. This separation can be carried out by selective adsorption on molecular sieves. The amount of after hydrolysis of the Organic phase recovered sulfonates is less than those that are obtained according to the first and second embodiment of the method according to the invention. This organic Phase is returned to the sulfonation reactor.

The sulfate-containing aqueous phase, like the sulfonate-containing aqueous phase, traces of Contain hydrocarbons. These traces can be removed with a suitable solvent, e.g. B. a mixture of ether

1 0 ^f ■ ■ / I (5 7 8

and nbrmalpentane or a mixture of ither / nbrmalpentane and isopropyl alcohol are extracted · The sodium alkyl sulfates obtained are colorless liquids, The number of Carbon atoms of these sulfates is larger than that of the Sulphates Actually Available on the Market · It is, in the case of the sulphates according to the invention, depending on the one used Distillation cut between 14 and 24 atoms for an unbranched chain.

The mixture of the sodium sulfonates obtained consists from orthodiacylbenzene sulfonates, alkenyl sulfonates, and hydroxyalkyl sulfonates. After the water has evaporated, the sulfonates are obtained in the form of a powder Step can be carried out by means of a pulverization process, wherein the sulfonate solution with a Hot air countercurrent is brought into contact. This process also has the advantage of complete de-oiling Since you want to obtain a completely colorless powder, you can advantageously decolorize the sulfonates with the help a dilute sodium hypochlorite solution. These However, treatment is not necessary and, moreover, has no influence whatsoever on the detergency of these mixtures.

The method according to the invention is to be explained in more detail using the attached scheme:

One introduces with normal paraffins of carbon number 15 to 21 enriched diesel oil along the line 1 in a unit of selective extraction with urea 2, taken along line 3A to oil 6 pulls the deparaffinierte diesel from · In a reactor for a non-isomeric Dehy drierung be Konaal paraffins introduced along line 3 , recycled hydrocarbons (which are mainly

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- ίο -

borrowed from normal paraffins and traces of naphthenes) along line 4 and hydrogen along line 5. The dehydrogenation catalyst is composed of platinum, Lithium and arsenic, applied to an aluminum support in amounts of 0.75 »0.5 and 0.36 percent by weight, based on the catalyst. The hourly rate of the liquid feed to the rate of the catalyst is equal to 1, the molar ratio of hydrogen to hydrocarbons is equal to 5 · The work is carried out at one temperature of 450 ° G. The pressure is slightly above 1 bar.

After the hydrogen has been separated off in 7, part of it is returned along the line 5, while the cracked products, which consist mainly of hydrocarbons with carbon atoms between 6 and 15, separated at the top of the column 8 and sucked off along the line 9 will.

Part of the distillation residue is introduced into the sulfation reactor 11 along the line 10. The sulfuric acid at a concentration of 98 % is introduced into the reactor along line 12. The contact time between the sulfuric acid and the insert is 5 minutes. The temperature of the reactor is fixed at 5 ° C. The product then comes into a neutralization reactor 13, into which soda solution with the concentration 4 normal is introduced along the line 14. The neutralization is carried out at ambient temperatures. The product is then subjected to an alkaline hydrolysis in the reactor 15 for a period of three hours at a temperature of 80 ° C,

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After decanting in container 16, the sodium alkyl sulfates are recovered along line 17. You can still be subjected to a de-oiling, which is not shown on the scheme. The organic phase that is sucked out of the decanting vessel along line 18, as is part of the distillation residue that originating from the column 8, are in the sulfonation reactor 20 introduced. A nitrogen stream of 1 percent by weight containing gaseous sulfuric anhydride is introduced into the bulk of the liquid hydrocarbons along line 21. The gas stream is sucked off along the line 22. The product of the sulfonation reactor is introduced into a f Neutralization reactor 23, into which a 4-normal soda solution is fed along line 24. The neutralization is carried out at ambient temperatures. Afterward an alkaline hydrolysis of the product occurs in the reactor 25 carried out at 250 ° C for one hour under a pressure of 41 bar. After decanting in container 26, the organic phase, which mainly consists of normal paraffins and traces of naphthenes that have not been converted in reactor 6 consists, returned along the line 4. The aqueous phase is along the line 27 in a device for de-oiling 28 introduced. The solvent consists of a mixture of ethyl ether and normal pentane and is along the | Line 26 introduced into the de-oiling tank. After decanting In the container 30 an organic phase is obtained along the line 31, the traces of oil dissolved in the solvent contains and along the line 32 a solution of SuI-fonaten. These are fed to an evaporator device 33, from which the pulverulent sulfonates are passed along line 34 wins. The water vapor is along the line 35 deducted.

1 0 ^r . / 1 β 7 8

A variation of the method according to the invention described in the scheme consists in adding a decantation vessel between the steaming reactor 13 ¹ UHd to the hydrolysis reactor 15. Place · An aqueous phase composed of sulphates and an organic phase which is subjected to hydrolysis in the reactor 15 are then also obtained · After the hydrolysis of the sulfur diesters, an aqueous phase 17 * composed of sulphates and an organic phase 18 which is subjected to sulphonation

Further details and advantages of the invention emerge from the following examples:

Example I.

A stream of normal octadecane and hydrogen is passed into a reactor over a period of 4 hours one containing a catalyst for non-isomeric dehydrogenation. The catalyst is made of platinum, Lithium, and arsenic together, which are applied to an aluminum support, in amounts of 0.75 $ 0.5 and 0.16 percent by weight, based on the catalyst. The reaction conditions are as follows:

! Temperature: 440 ° C $

Speed of normal liquid octadecane to the speed of the catalyst: 1 molar ratio of hydrogen to Mbrmal-Octadecane: 5 ·

In Table 1 below, the yields obtained after a reaction of the normal octadecane are obtained

1 OC 'V / 1 B7 8

Product components and the degree of isomerization for 100 g of converted input quantity, as well as the composition of aromatic hydrocarbons in parts by weight of 100 g of aromatic hydrocarbons applied

Table I.

Turnover % Crack ^r gaseous hydrocarbons 31 i 2.1 Yield (in grams for 100 g of converted product) Products Number of carbon atoms <5) hydrogen liquid hydrocarbons 1.7 , Number of carbon atoms> 5) olefinic hydrocarbons 5.9 aromatic hydrocarbons 4-1.0 naphthenic hydrocarbons 44.3 carbon 4.0 Degree of isomerization 1.0 2.0

A mass spectrometric analysis of the aromatic hydrocarbons showed that they consist mainly of dialkyl benzenes. By means of a nuclear magnetic resonance measurement, it was found that these are rhodialkylbenzenes, the alkyl radicals of which are linear.

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This table shows that one can achieve a relatively violent degree of conversion · Furthermore, one can determine that the degree of isomerization, as well as the amounts of the resulting cracking products, are very low.

The resulting olefinic hydrocarbons consist of more than 95 % monoolefins.

After the hydrogen and the cracked products have been separated off, the one coming from the dehydrogenation is subjected Product of sulfation at a temperature of 5 ° C with 98% sulfuric acid. The contact time is short (5 minutes), to avoid the formation of polymers. The molar ratio of sulfuric acid to olefins used is

The conversion rate of the olefinic hydrocarbons (the only ones that react with sulfuric acid) is 52%, of which less than 5 % are in the form of polymers. The total yield of sodium alkyl sulfates from 100 g of converted olefins is 75 % (after neutralization of the sulfur monoesters with 4 normal soda solution at ambient temperature and hydrolysis of the sulfur diesters with a 4 normal sodium carbonate solution in excess for 3 hours) The aqueous phase obtained consists mainly of a sodium alkyl sulfate solution whose alkyl radicals are linear and whose number of carbon atoms is 18.

The organic phase is subjected to sulfonation by blowing a stream of nitrogen containing 1.2 % sulfur anhydride into said organic phase at a temperature of 22 ° C. The duration of the reaction is 1 hour and 30 minutes. The sulfonic acids obtained are

1 o s;> ι;.; / 1 6 7 8

then with 4-normal soda solution at ambient temperature neutralized.

The subsequent alkaline hydrolysis is carried out in an autoclave with the help of a soda solution at one temperature from 250 ° O carried out for a period of one hour. After decanting, the organic phase can not converted normal octadecane, as well as traces of naphthenes ^, are returned to the dehydrogenation reactor. The aqueous phase consists mainly of sodium alkenyl sulfonates, Sodium hydroxyalkyl sulfonates and sodium orthodialkylbenzene sulfonates. The total conversion of the olefinic and aromatic hydrocarbons according to the SuIf onation, neutralization and hydrolysis is 96% · Die The aqueous phase can be subjected to de-oiling in order to remove traces of dissolved hydrocarbons. These Extraction can be done with the help of a mixture of ethyl ether and normal pentane can be carried out. After dehydration, a powder with detergent properties is produced, which is biological is degradable. This powder contains sodium sulfate, which was formed during neutralization with soda and which can possibly be removed »This separation is not necessary, however, since the sodium sulfate is a substance that is also normally found in washing powder mixes.

Example II

A stream of normal octadecane oxd hydrogen is passed over a dehydrogenation catalyst for two hours, which consists of chromium, copper and potassium on aluminum as a carrier substance. These three metals are in shape their nitrates deposited after a calcination

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800 ° C arise. Its components in percent by weight based on aluminum are: 4-, 97% chromium, 3.03 % copper and 1.00 % potassium. The rate of normal octadecane measured in the liquid state to the rate of the catalyst is 1, the temperature of the catalyst is 440 ⁰ O. The molar ratio of hydrogen to normal octadecane is 5 non-isomeric dehydrogenation is introduced is 19%. For every 100 g of the normal octadecane used, 12.8 g of olefinic hydrocarbons and 5.9 g of aromatic hydrocarbons are obtained. The olefinic hydrocarbons obtained, as well as the aromatic hydrocarbons, are simultaneously subjected to sulfonation by blowing in a gas stream mixed with sulfur anhydride and nitrogen, the molar concentration of the sulfur anhydride in nitrogen being 1%. After neutralization of the sulfonic acids with 4-normal soda solution at normal temperature and subsequent alkaline hydrolysis at a temperature of 250 ° C. under a pressure of 4-1 bar for one hour, the excess of soda is neutralized by sulfuric acid. It is then evaporated until a dry product is obtained.

The detergent properties of the product obtained have been compared with those of a commercially available soap by the following experiment.

The product according to the invention is used to prepare a washing powder with the following composition:

- 20% by weight of pure detergent to be tested

- 18% sodium pyrophosphate

5 % sodium perborate

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- 4 % colloidal magnesium silicate 9% sodium carbonate (anhydride)

- 4-3 % sodium sulfate (anhydride)

1 % carboxymethyl cellulose (Blanose R 130).

With this powder "one prepares two aqueous solutions to, one with 5 g / l »the other with 2 g / l.

A piece of fabric impregnated with a standard soiling is washed with each solution (the fabric is commercially available under the name "Cotton Soil Test Cloth 51 S 4-7 ^w ") in a gate direction known as the "Laun" aerometer " is known, under the following conditions: 5 g of the tissue sample are washed in 2 liters of solution for 30 minutes at 90 ° C by moving ten stainless steel balls with a diameter of 6 mm.

An EeflexLons measurement is carried out to estimate the washing power using a device known commercially as the Photovolt, made by the company PHOTOVOLT COEPORATION is produced.

The following luminosity values are determined using a green filter

- Te: luminosity of the fabric after washing

- Ys ι luminosity of the fabric impregnated with a standard soiling

- Xt: luminosity of the fabric without impregnation

with a standard pollution.

The detergency PD, as a percentage, is calculated using the following formula »

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PD

Ye - Ts

Yt - Ys

χ 100

In a par all el attempt was made among the same Conditions the tissue pieces with two solutions, one • 5 g / l and one 2 g / l of a commercial soap with 1 g / l Containing sodium carbonate (anhydride) washed. The results are summarized in the following table II,

Table II

pure
laundry detergent
in g / l Ys Yt Ye PD
(in %) invention
appropriate 5 28.0 93.3 5 ^, 2 40.1 mixture 2 27.9 92.1 50.5 35.2 trade
usual 5 28.0 93.3 41.1 20.1 soap 2 27.9 92.1 39.3 17.7

These tests provide evidence of the exceptional quality of the detergents according to the invention, which comparable to those of the dodecylbenzene sulfonates with branched chains that are normally on the market are available.

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Example III

The sulfonates prepared by the method described in Example II are used in the following experiment for biological Subject to degradability:

A culture of microorganisms is grown for a period of 7 days with constant aeration, at a temperature of 25 ° C in a semi-synthetic medium containing 20 mg o / oo of the test product, then after At the end of this time, add the same amount of detergent again and continue the experiment until the second day On the seventh and tenth days, analyzes are carried out to measure the disappearance of the product and can be used on this Way to determine the biodegradability of the product. The broth contains the microbial culture used in this experiment between 2 and 4- χ 1Cr microorganisms per mm. It is prepared through an aerobic fermentation in a more nutritious way Environment, the microorganisms are the Seine water taken from the feed line of the great collector von Olichy in Paris.

The detergent content of the microbial cultures is determined using a method from LONGWELL and MANISOE according to the following Principle analyzed. A colored complex is formed with methylene blue, extracted with chloroform and a colorimetric method is carried out Measurement by comparison with a calibration substance.

The degree of biodegradation, T ", after expiration of 7 days, is given by the following formula »

T, ² Q - ^ ^C E7 - ^C t7> * ¹⁰ °

1 0 G:.; / 1 G 7 8

where C-gr, the content of detergent in the test solution on the seventh day in mg o / oo and G. “represents the detergent content in a comparison solution on the seventh day in mg o / oo represents.

In an analogous way, the following applies to the degree of biological degradation after ten days have elapsed, ^ ₁ Qi formula:

⁴⁰ - (Oe ₁₀ - 0 _t i0) χ 100

where Cjjio ^ ^en keep ³ ^ ⁰ - represents detergent in the test _{solution on the tenth day in mg o / oo and CL 10 expresses} the content of detergent in a comparison solution on the tenth day in mg o / oo.

Finally, the actual degree of biodegradation T is given by the following formula:

1.5

The results are shown in Table III below registered.

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Table III

Focus on
laundry detergent
on the 7th day (ppm) 0.80 According to the invention
mixture attempt
No. 2 96.45 Comparative , "., _,.,"., _ "".,.
Biolog · degradation%,
7 day attempt
number 1 2.3 ι solution Focus on
laundry detergent
on the 10th iDag (ppm) 0.65 3.0 92.5 Biolog · degradation%,
10th day 89.0 2.65 Biolog · degradation 2.85 95 Average 9 ^, 5 94.1 92.6

1 0 9 f ::; B / 1 6 7 8

Claims (1)

- 22 claims 1 · Mixture of synthetic detergents that are biodegradable and their main active ingredients are the general formula _{a + 1} possess, characterized in that M represents an alkali metal or an ammonium ion, η is 0 or 1, R * represents an orthodialkylbenzene radical with a linear alkyl group with an atomic number of 1 to 18, a linear alkenyl or a linear hydroxyalkyl radical with an atomic number of 14 to 24, Ep is a linear alkyl radical with a number of carbon atoms represents between 14 and 24. Terfahren for the production of the substances according to claim 1, M characterized in that in the presence of hydrogen a catalytic dehydrogenation of normal paraffins of the Carbon atom number 14 to 24 is carried out, the resulting cracking products said normal paraffines and the liberated hydrogen are removed, and the aromatic and olefinic hydrocarbons thus obtained be subjected to sulfonation with gaseous sulfur trioside, and that those obtained from the sulfonation Products neutralized and hydrolyzed with an alkaline base will· 3 · The method according to claim 2, characterized in that the aromatic and olefinic hydrocarbons that 1 0 9 G , H / 1 6 7 8 are subjected to sulfonation, at least partially from hydrocarbons "consist of sulfation with concentrated sulfuric acid and partly from olefinic hydrocarbons produced by derive from the dehydration of normal paraffin, and that the products coming from the sulfation are neutralized and hydrolyzed with an alkaline base 4 ·. Process according to Claims 2 and 3, characterized in that that the unconverted normal paraffins of the catalytic, non-isomeric dehydrogenation, as well Traces of naphthenic hydrocarbons after the new ( tralization and hydrolysis of the obtained by the sulfonation Products are recovered and returned to the dehydrogenation reactor. 5. The method according to claims 2 and 3 »characterized in that that the unconverted normal paraffins of the catalytic non-isomeric dehydrogenation, as well as Traces of naphthenic hydrocarbons can be recovered by removing that originating from the dehydrogenation reactor Waste gas is passed over molecular sieves and is returned to the dehydrogenation reactor. 6. The method according to any one of claims 2 to 5 »characterized by the following featuresί a) The hydrocarbons that are the catalytic non-isomeric Are subjected to dehydration, have a carbon number between 15 and 21. b) The catalytic ^ non-isomeric dehydrogenation is in Presence of a catalyst consisting of platinum, 109:, K / 167 8 Lithium and arsenic carried on an aluminum support, c) The sulfonation of aromatic and olefinic hydrocarbons is in a single beactor at temperatures between 20 ° G and 25 ° 0, by blowing in gaseous sulfur anhydride, diluted with an inert gas carried out under reaction conditions. d) The products of sulfonation are neutralized by adding
carried out by adding soda at a temperature close to 22 ° 0 e) The hydrolysis of the products of sulfonation is carried out after neutralization by means of a soda solution under pressure carried out at temperatures between 150 ° G and 300 ° G. 7. Method according to one of Claims 3 to 6, characterized by the following features: a) The sulfation of the olefinic hydrocarbons is brought about by the contact of said hydrocarbons with sulfuric acid at a concentration above 90%, for a time of 1 to 10 minutes, and one Temperature equal to or below 25 ° C. b) The sulfation products are neutralized by adding soda at a temperature close to 22 ° 0. c) The hydrolysis of the sulfation products is after Neutralization by adding a soda solution at a temperature between 50 ° C and 150 ° 0 advertises.