DE1066579B - - Google Patents

Description

GERMAN

kl. 12 ο 23/02

INTERNAT. KL. C 07 C

PATENT OFFICE

N12420IVb / 12o

REGISTRATION DATE: JUNE 28, 1956

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EXPLORATION PAPER. 8 OCTOBER 1959

According to a known process for the preparation of higher alkenes by cracking paraffin-containing hydrocarbon mixtures in the vapor phase, mixtures give way to the aromatics present in them beforehand removed entirely or for the most part by extraction with selective solvents as a paraffin-containing starting material a heavy oil, which in the fractional distillation of a cracked product is obtained from the catalytic cracking of hydrocarbon oils, optionally in a mixture with the residue oil, which is withdrawn as a bottom product in such a distillation will.

The alkenes with at least 8 carbon atoms formed in the process mentioned were found to be particularly suitable for the preparation of arylalkanes, of which alkylarylsulfonates with excellent surface-active properties can be produced by sulfurization.

It has now been shown that the cracked distillate obtained in the above manner, which alkenes with 8 or more carbon atoms, can work up into surfactants, advantageously in the way that the production of secondary sulfuric acid alkyl ester salts in characteristic Way is associated with that of alkylarylsulfonates.

The invention therefore consists in a process for the production of surface-active, secondary Sulfuric acid alkyl ester salts and alkyl aryl sulfonates from one by thermal vapor phase cracking distillate represented by paraffinic hydrocarbons with a high alkene content, which contains at least 8 carbon atoms per molecule, which according to the invention is characterized in that the vapor-cracked distillate from which one starts, either from one by fractionation cyclic heavy oil separated from the product of catalytic cracking of hydrocarbon oils originates or a mixture of this product with the process withdrawn as the bottom product during fractionation for the production

of surface-active secondary sulfuric acid alkyl ester salts

and alkyl aryl sulfonates

Applicant:

N. V. De Bataafsche Petroleum Maatschappij, The Hague

Representative: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man, Patent Attorneys, Munich 9, Schweigerstr. 2

Claimed priority: The Netherlands, June 30, 1955

Pieter Leendert Kooijman, Amsterdam (Netherlands), has been named as the inventor

NEN residual oil, the aromatics wholly or largely from the heavy oil or the mixture beforehand were extracted with selective solvents, and that one after having the cracked distillate first has processed in a known manner on secondary sulfuric acid alkyl ester salts, which here are not converted organic components freed from polymers in whole or in part for the purpose of producing Reacts alkylarylsulfonates with benzene or toluene under alkylation conditions in a known manner, the resulting arylalkanes sulfonated, and finally the sulfonic acids obtained in the usual manner in transferred to the corresponding alkylarylsulfonic acid salts.

The method according to the invention can be represented schematically by the following flow chart:

Paraffin from heavy cracking oil
(possibly mixed with residual oil)

Cracking

Mixture of olefins

Fr action

909 63T / 417

+ Unimplemented, ■■ ". benzene Y still olefinic or organic material toluene 1,066,579 Alkylation
• mixture from Alkylbenzenes mixture 3 4 from ι.: - ■■ ■; . j Sulfonation Alkylarylsulfonic acids Olefin fraction each with the desired molecular weight Sulfation mixture from Monoalkyl sulfuric acids

A more complete conversion of the alkenes can can be achieved if part of the cracked distillate obtained in this way for the production of Ester salts and another part is used for the production of alkylarylsulfonates. It results This results in a higher overall yield of surface-active substances than if only ester salts or alkylarylsulfonates were used would be made from it. It has also been shown, surprisingly, that after this Process prepared alkylarylsulfonates, in which from: unreacted organic material for the Representation of the ester salts was assumed even slightly better surface-active properties, e.g. B. a not inconsiderably improved foam effect compared to the alkylarylsulfonates obtained directly from the cracked distillate in question and which in themselves already have excellent properties.

■. The raffinate used as starting material for thermal vapor phase cracking is obtained by removing the aromatics from the oil coming from the "catalytic cracker" and at about 300 ° C, the so-called heavy oil or a mixture of it with the oil residue, the at the same time during cracking .: is obtained, the so-called oil sludge. This distance is through Extraction with selective solvents such as furfural, mixtures of phenol and water or with liquid sulfur dioxide, carried out, the extraction usually in three or more stages im Countercurrent process is going on. When using furfural or mixtures of phenol with water you can make an almost aromatic-free raffinate with a medium solvent ratio, for example 2.0 to 3.5.

The thermal cracking of the raffinate is achieved by heating the vapors of the raffinate along with Steam or other inert diluent for a short period, such as a few Seconds at a high temperature such as 500 to 560 ° C. After separating the usual gaseous constituents, the cracked product is distilled into the desired cracked distillate and a higher-boiling bottom body separated, which can be fed to a cracking again.

The preparation of sulfuric acid alkyl ester salts in the first stage of the process is usually carried out by sulphation of the desired cracked distillate, usually the C ₈ -C ₁₈ fraction, and then the sulphation product is converted into secondary sulfuric acid alkyl ester salts by treatment with an alkaline substance. When the resulting pure ester salt solution is purified by extraction with gasoline or similar low-boiling hydrocarbons, the so-called unreacted organic material from the ester salt production is found in the extract. This unreacted organic material, the amount of which z. B. 50 or more percent by weight, consists of a complex mixture which, in addition to the saturated hydrocarbons, polymers and higher alcohols, has a fairly high content of alkenes that were not converted during the sulfation.

Before the unreacted organic material in the second stage of the process to form alkylarylsulfonates is worked up, it is freed from the polymers. For this purpose it is, optionally under reduced Pressure, distilled at a temperature which is by no means more than about 50 ° C above the the highest boiling point of the original crack distillate. The polymers are in the residue.

_{The C 10} -C ₁₄ fraction boiling within the boiling range of the cracked distillate is preferably used for the ester salt production.

The work-up in alkylarylsulfonates is done by first adding the unreacted organic Material or fraction thereof with benzene or

Toluene, usually reacted in large excess and in the presence of an alkylation catalyst is .. The alkylation product is then sulfonated and the resulting. Alkylarylsulfonic acids in the corresponding sulfonic acid salts converted.

The alkylation of the aromatic hydrocarbons is preferably carried out using hydrogen fluoride Catalyst at ordinary or slightly elevated temperature, e.g. B. at 20 to 50 ° C executed. To The end of the alkylation, which is usually carried out continuously, is separated. the acid phase and forwards it to the process again. The hydrocarbon phase is fractionally distilled. Included the excess aromatic hydrocarbon goes first and then the desired alkylation product over, while the higher-boiling components remain as a residue.

The alkylation product can in the usual way with about 20% oleum at a temperature of 10 to 50 ° C are sulfonated. After the sulfonation, any acid that may still be present can be used entirely or partially remove. The sulfonation product is then treated with sodium hydroxide, sodium carbonate or another inorganic or organic substance with an alkaline reaction. the Alkylarylsulfonates are obtained in the form of an aqueous slurry or paste.

The secondary sulfuric acid alkyl ester salts, which in the first step of the process as aqueous solutions can be converted into solid end products in the same way. You have excellent surface-active properties, in particular a good cleaning effect and good foaming effect. The ester salts, like the alkylarylsulfonates obtained in the second step, are consequently special valuable as cleaning and washing agents for household and industry, or as active components for such.

The alkylarylsulfonates obtained by the process are excellent, along with the ester salts Quality. Their surface-active properties, especially their foaming effects, are even something better than the similar alkyl aryl sulfonates taken directly from that used in this process Special crack distillate can be produced without this beforehand in a separate step for the production the ester salts would have been used.

The invention is explained in more detail by the following example.

example

The starting material was a Cg-Cjg-cracking fraction (b.p. 145-300 ⁰ C), which had been separated from the raffinate of the product to a thermal Dampfphasencrackung. This raffinate was obtained by extracting from a mixture of cyclic heavy oil (boiling point between about 300 and 500 ° C.) which came from the fractionation of a liquid cracking product obtained by catalytic cracking of a mineral oil distillate (boiling point between about 300 and 500 ° C.) , and a residual oil withdrawn as a bottom product during this fractionation, extracted the aromatics with furfural.

This C ₈ -C ₁₈ cracked fraction, which contains approximately 90% by weight of alkenes, was treated at 15 ° C. for 5 minutes with 98% strength sulfuric acid with a molar ratio of sulfuric acid to cracked fraction of 0.8. The sulfated product was then worked up in the usual way with caustic solution at 95 to 100 ° C .; after extraction with gasoline, the pure sodium alkyl sulfates were obtained in this way. Based on the cracked fraction, the yield of sodium alkyl sulfates was 71 percent by weight. . ,. .

The unreacted organic substances that occur as a by-product in the preparation of ester salts from the extract phase in the cleansing treatment

ίο were obtained are freed from the polymers and used for the alkylation of benzene. The alkylbenzenes obtained are sulfonated and neutralized to alkylbenzenesulfonates.

The following examples explain the preparation of C ₁₀ -C ₁₄ , C ₈ -C ₁₃ and C ₁₄ -C ₁₈ -alkylbenzenesulfonates from the unreacted organic material:

C ₁₀ -C ₁₄ alkyl benzene sulfonates

A C ₁₀ -C ₁₄ fraction (boiling range 170 to 260 ° C) was separated from the unreacted organic substances by fractional distillation and used for the alkylation of benzene by.

the isolated fraction was reacted continuously with benzene in a reaction vessel equipped with a powerful stirrer at about 30.degree. C., liquid hydrogen fluoride serving as the catalyst. The molar ratio of benzene to those in the C ₁₀ -C ₁₄ fraction

The alkanes present was approximately 10: 1, the weight ratio of the acid phase to the hydrocarbon phase about 1: 1. The residence time in the reaction vessel was about 30 minutes.

Thereafter, the acid phase was separated off and fed back into the reaction. The reaction mixture withdrawn from the reaction vessel was initially at atmospheric pressure to about 200 ° C and, then even further at reduced pressure. (20 mm Hg) fractionated distilled. The excess benzene initially goes together with the unconverted components.

the C ₁₀ -C ₁₄ fraction and then the alkylated fraction, which consists of C ₁₀ -C ₁₄ -alkylbenzenes

(Boiling range about 270 to 340 ° C at 760 mm Hg).

The alkylbenzene fraction was then at 50 ° C and a reaction time of 30 minutes with 20% Sulfonated oleum (molar ratio of total sulfur trioxide to alkylbenzene fraction is 3: 1). The sulfonation product obtained was diluted with 30% water from the excess Separated sulfuric acid and neutralized with sodium hydroxide solution, whereby a slurry was obtained which consisted of about 20% sodium alkylbenzenesulfonates.

The yield was 30 percent by weight based on the cracked C ₈ -C ₁₈ fraction.

When used as cleaning agents in the form of a mixture with a high content of so-called "builders", these alkylbenzenesulfonates have even better properties than the C ₁₀ -C ₁₄ -alkylbenzenesulfonates, which were obtained directly from a cracked distillate prepared as above. In a standardized dishwashing test, 22 plates could be washed with this product, but only 20 plates were washed with the one obtained directly from the cracked distillate.

Cg-Cjj alkyl benzene sulfonates

_{A C 8} -C ₁₃ separated from the unreacted organic substances by fractional distillation

Fraction (boiling range 125 to 240 ° C) was at 0 ° C with benzene in the presence of liquid hydrogen fluoride reacted, the other circumstances being as described above.

The C ₈ -C ₁₃ -alkylbenzenes obtained (boiling range about 240 to 330 ° C. at 760 mm Hg) were worked up as above to give Cg-C ^ -alkylbenzenesulfonates.

The yield was about 36 percent by weight based on the cracked C ₈ -C ₁₈ fraction.

10

C ₁₄ -C ₁₈ alkyl benzene sulfonates

One of the unreacted organic matter separated by fractional distillation C ₁₄ -C ₁₈ fraction (boiling range 250-315 ⁰ C) ₁₃ to fraction C ₁₄ -C was analogous to the C ₈ -C ₁₈ alkylbenzenes (boiling range 325-395 ° C at 760 mm Hg) and further converted to alkylbenzenesulfonates. The yield was about 30 percent by weight based on the cracked fraction.

From the following comparative examples it is clear that in the method according to the invention a significant increase in yield is achieved:

1 part by weight of C ₈ -C ₁₈ alkene gives 0.71 part by weight of C ₈ -C ₁₈ ester salt on direct work-up.

1 part by weight of C ₈ -C ₁₈ alkene gives 1.13 parts by weight of C 8 -C 18 -alkylbenzenesulfonates on direct work-up.

1 part by weight of C ₈ -C ₁₈ alkene, when worked up according to the invention, gives 0.71 part by weight of C ₈ -C ₁₈ ester salt and 0.66 part by weight of C 8 -C 18 -alkylbenzenesulfonates.

From the above it can be seen that 2 parts by weight of C ₈ -C ₁₈ alkene with direct work-up give 1.84 parts by weight of surface-active mixture and 2 _{parts by weight of C 8} -C ₁₈ -alkene with work-up according to the invention give 2.74 parts by weight of surface-active mixture, ie an increase in yield of about 50%, based on the yield with direct work-up.

Claims (3)

Patent claims: 1. Process for the preparation of surface-active, secondary sulfuric acid alkyl ester salts and alkylarylsulfonates from a paraffin-containing thermal vapor phase cracking Hydrocarbons with a high alkene content represented distillate, which per molecule at least Contains 8 carbon atoms, characterized in that the distillate cracked in the vapor phase, from which one starts, either from one by fractionation from the product of the catalytic cracking of hydrocarbon oils separated cyclic heavy oil originates or a mixture of this product with the as Bottom product withdrawn during fractionation is residual oil, from the heavy oil or the Mixture previously extracted the aromatics wholly or largely with selective solvents were, and that after you have the cracked distillate first in a known manner on secondary Has processed sulfuric acid alkyl ester salts, which here unreacted, freed from polymers organic components wholly or partially for the purpose of producing alkylarylsulfonates with Reacts benzene or toluene under alkylation conditions in a known manner, the resulting Arylalkanes sulfonated, and finally the sulfonic acids obtained in the usual way in the corresponding Converted alkylarylsulfonic acid salts. 2. The method according to claim 1, characterized in that a C ₁₀ -C ₁₄ fraction is separated from unreacted organic material and used for the alkylation of the aromatic hydrocarbons. 3. The method according to claim 1 or 2, characterized in that the alkylation is carried out in the presence of liquid hydrogen fluoride as an alkylation catalyst at a temperature of 20 to 50 ° C. (MlQ (ΛΊΟΛΊ O KO