CS199342B1 - Method of producing alkylbenzene from benzene and olefins or chloralkanes with 10 to 16 carbon atoms - Google Patents

Abstract

1488217 Alkylating benzene VEB DEUTCHES HYDRIERWERK RODLEBEN 16 April 1975 [6 Aug 1974] 15713/75 Heading C5E In a process for the alkylation of benzene, the residue fraction comprising polyalkyl benzenes and polyphenyl alkanes is added without preliminary treatment to an AlCl 3 complex and contact oil from the alkylation circuit during activation of the latter by the addition of further AlCl 3 , the resulting reaction mixture being restored to the alkylation circuit to effect an increase in the yield of alkylbenzene. In the examples, the invention is applied to the alkylation of benzene with C 10 -C 13 n-paraffins.

Description

The present invention relates to processes for the production of alkylbenzene from benzene and olefins or choralkanes and from 10 to 16 carbon atoms in a Friedel-Crafts reaction.

It is known that alkyl or smoked for later use as a laundry detergent raw material is obtained by Friedel-Crafts reaction with Lewis acids, and here preferably AlCl 3 or AlCl 3, originating from metallic aluminum in situ, and other necessary reagents from benzene and chlorinated paraffins having a chain length up to θ ^ Ο _С 1в, and optionally using HF as catalyst, when used instead of chlorinated paraffins corresponding olefins · the latter procedure has the advantage that the use of mono-olefins, such as olefins from a cracking process, the formation of by products not usable for detergent production small ·

Since chlorinated paraffins for the production of alkylbenzene can never be controlled by chlorination to form mono-compounds, polyphenylalkanes are always required to a large extent. At the same time, however, alkyl poles are also smoked during multiple reactions on the benzene nucleus.

Both groups of compounds form the residual fraction in the distillation of the crude alkylene after separation of the benzene used in excess and the paraffin of the alkylbenzene obtained.

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Necessarily falling off residual fraction ₉ which can, according ohloraÓQÍho degree up to 25% 'based on recovered alkylbenzene has a strong negative effect on the overall efficiency process ^for Whence ^e as strong pollution ^EVALUATION j ^.mu.l of optionally p ^{sing t just} like the TAP ^ nosnáho medi-ai, heating oil or after further processing in the field of timber · this shortcoming is amplified by the fact that the national economy is yet Velim products abridged form vedlejěíoh the world nedodatkové raw materials such as c ^hl or benzene a'para ^f ins ^ne aka & ^s at ^m ° l ^EKU l ^{s .gamma.CH network} ° h · ^ lacked ^beta Roto ^P series okus ^y of significant ^E ^ Zani necessarily ^eh of waste ⁱⁿ the ^fo rm ^of polyA ^lk y ^lbenzenů and polyfenylalkanů or to transfer these oily residual product Thus, it has been proposed in DOS 1,568,326 to carry out an alkylation reaction in the presence of diphenyl derivatives of higher alkanes. This is to be achieved by wauer residues of the diphenyl alkanes into the alkylation reaction mixture #, thereby avoiding the formation of further amounts of this component or increasing the yield of monophenylalkylates #

Furthermore, DOS 1,568,327 has been proposed to treat the entire AlCl3 residual fraction, but this requires an additional amount of benzene to force the dialkylbenzene dieproportionation, and between 5 and 25% AlCl3 based on the residual fraction must be used to achieve partial conversion of the residual MHC.

In another alternative embodiment of the same patent, it is proposed to further divide the residual fraction by distillation and isolate first the diphenyl alkanes and then treat them with the same amount of AlO 3 based on the residual fraction as in the first alternative.

A considerable drawback of both inventions is that in the case of DOS 1 568 326 and in the second alternative of DOS 1 568 527 an additional operation in the form of high-temperature and high-vacuum distillation is required to separate the oily residue. It is clear from this that only a portion of the by-product which is inevitably removed can be converted and that even further amounts of benzene and AlCl3 as catalyst are required for this conversion. According to the first alternative, even a considerable amount of benzene is used and AlCly ^{DOS 1} 5 ⁶⁸ 527 must be used.

Thus, attempts have been made to find other possibilities to reduce the amount of byproducts. According to the methods described in DOS 1 907 277, it is to be achieved by means of. more active catalysts and optimizations. chlorination of better alkylbenzene yield #

However, here too. It noted that in the catalyst during use of the lost activity by treatment with ^d e ^HTU and vedlejšíc ^h vypókomo ^L e ^k u ^l ARN ^Ch products MMN ^and Kaj ^í c ^Ch It runs ^h em reaction ^ea its aktLvita the meters ^already e maintain ^F ovata adding fresh ^j ^ o AJ.C ^or aluminum ovov ^é # also for ^loan Joint d ^e method can not completely. suppress the formation of by-products despite the use of increased amount of catalyst # Feely the invention will become p ^of EM n ^of less that ^it ^ ^{Excess amounts} of Otao verifies fraction ^{and d} is ^H noduc YM manner entirely valuable for the production of alkylbenzene detergents #

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It is an object of the invention to provide a simple method for converting the residual fraction.

According to the invention, this is accomplished by adding 2 to 3% by weight in the circulating phase of the contact oil of the residual fraction of the crude alkylate distillation, containing polyphenylalkanes and polyalkylbenzenes, to the reaction mixture introduced in the alkylation cycle. activated 0.6 to 0.9 wt. % aluminum chloride ·

By the process according to the invention, by-products are converted to benzene, paraffin and predominantly alkylbenzene during the activation of the contact oil · Technologically conventional dosing of the contact oil · all the former components of the oily residue are then alkylated · Alkylation is thereby not adversely affected and distillation is carried out ·

In the present invention, the effect of the maximum attainable catalyst concentration on the residual fraction is utilized to convert the residual fraction to alkylbenzene.

^{PU are} processes by ^l e VYN & Cutting amortized gills ^and thread formation nežtóouc ^ secondary-CB PRODUKTIE without installing additional ^¹H ancillary ^ PoC ^h ODU · a straight ^{essentially Enhancing} yield off ^z to reaction Furthermore it is now possible to modify poohod chlorination by way that conventional chlorination degree of 0.3 to 0.4, yet limiting the generation of byproducts can exit and reach the degree of chlorination of 0.5 · ^{d p solutions} ccording VYN ^s climb is ^{d, and} Le ^closer explained e ^ ЗДЗлЛу executed! ·

Example 1

In Bank ^Y · ¹ with an attached reflux cWad ^ em perfectly am ⁱ and ^{i 0,} 5 1 benzene-free thiophene with 750 ml of the contact oil · Contact oil was removed from álkylačnibn apparatus operable continuously, revitalized 15 g AlCj so that it contains 35 up to 40 weights. % catalytically foil containing AlCl 3. Son ^and the p ^r i ^to the AP ^and V ^{and at} 55 and ⁶⁰ ° C ^h em ^b of from ^{1 h i} n ^{y 1} of ^one nrpáráf ^{bl l} nu ^produced by chlorination of a mixture of n-paraffins with a chain C, to C ^ j of medium molecular weight 166 and containing 7,5% chlorine, with stirring ·

After completion of the reaction, the mixture is allowed to react for a further 30 minutes and then the contact oil phase is separated. After washing with hydrochloric acid and drying over sodium sulfate, 192 g of alkylbenzene and 43 g of residual fraction are obtained from 1000 g of reaction mixture.

Example 2

The procedure is' similarly as in Example 1 except that, - nblorpáráfinu 75 ml residues ^é fr ^and Functions of ice ^^ 1 ^T his was přikapáH. · In a flask ^p nrnvh ^ck with BC fallow ^Cart 1 permits to increase the yield by 1.65% alkylbenzene ·

Example 3

In ^B and ^{n are} 1 CE 4 with attached reflux condenser and d ^ em ^ ⁱ The intense mixing. 750 ml TONT tního ol ^ ^e as in posptao přttladu 1, and 75 m ^l of fraction zbytlcové treasure 1 one ^hour at 55 s

19В 342 to 60 ° 0 · Now a mixture of 0.5 l of thiophene-free benzene and 1 l of chloro paraffin, as in Example 1, is added dropwise to the contents of the flask over 1 hour · Further processing is carried out as in Example 1 ·

Compared to Example 1, alkylbenzene yield increased by 15.1% ·

Example 4

1.77 weights per hour are fed to the continuous alkylation apparatus. parts of benzene, 3.29 wt. parts of chloroparaffin, similar to that described in Example 1, and 4.17 parts by weight. parts of contact oil animated with 0.07 parts by weight of AlO1 ^. After separation of the contact oil phase and washing of the hydrochloric acid, 1.00 parts by weight of alkylbenzene and 0.184 parts by weight of the residual fraction are obtained after distillation of the reaction mixture.

Example 5

In the alkylation plant operating continuously as described in Example 4, 0.244 parts by weight of the residual fraction remaining in the AlCl3 contact oil recovery operation are added in a stationary state and partially converged therein. 1.11 parts by weight of alkylbenzene and 0.03 parts by weight. díl /

residual fraction The increase in alkylbenzene yield compared to Example 1 is 11%.

Example 6

In a continuously operating alkylation plant as described in Example 4, a similar procedure is followed, but the residual fraction remaining in the distillation of the reaction mixture is added completely in the recovery operation to the AlCl3 contact oil and is completely converted there. In a stationary state, 1.13 parts by weight of alkylbenzene per hour. Compared to Example 4, the increase in alkylbenzene yield is 13%.

Claims (1)

A process for the production of alkylbenzene from benzene and olefins or chloroalkanes having from 10 to 16 carbon atoms by a Friedel-Crafts reaction, characterized in that the residual fraction leaving during the distillation of the crude alkylate containing polyalkylbenzenes and polyphenylalkanes is added to the reaction mixture in the alkylation cycle. in an amount of 2 to 3 wt.% in the circulating phase of a contact oil activated with 0.6 to 0.9 wt. % aluminum chloride ·