WO2004035530A2

WO2004035530A2 - Method for the production of alkylaryl sulfonates

Info

Publication number: WO2004035530A2
Application number: PCT/EP2003/011378
Authority: WO
Inventors: Ulrich Steinbrenner; Thomas Heidemann; Thomas Narbeshuber; Heiko Maas; Martina Prinz; Nils Bottke; Jürgen Tropsch; Regina Benfer; Frank Funke; Jürgen STEPHAN
Original assignee: Basf Aktiengesellschaft
Priority date: 2002-10-15
Filing date: 2003-10-14
Publication date: 2004-04-29
Also published as: AR041604A1; DE10248002A1; AU2003294692A8; AU2003294692A1; WO2004035530A3

Abstract

The invention relates to a method for producing alkylaryl sulfonates, the alkylaryl sulfonates obtained according to said method, alcohol mixtures and olefin mixtures obtained as intermediate products, alkylaromatic compounds obtained therefrom, the use of said alkylaryl sulfonates as surfactants, and detergents containing said surfactants.

Description

Process for the preparation of alkylarylsulfonates

description

The present invention relates to a process for the preparation of alkylarylsulfonates, the alkylarylsulfonates obtainable by this process and alcohol mixtures, olefin mixtures and alkylaromatic compounds obtainable as intermediates, the use of the alkylarylsulfonates as surfactants and detergents and cleaning agents containing them.

It is known to use alkylbenzenesulfonates (ABS) as surfactants in detergents and cleaning agents. After such surfactants based on tetrapropylene benzene sulfonate were initially used, but were poorly biodegradable, linear alkyl benzene sulfonates (LAS) were predominantly used in the subsequent period. Currently, surface-active compounds for use in detergents and cleaning agents face complex requirements with regard to their properties, which linear alkylbenzenesulfonates do not adequately meet. For example, in addition to good washing properties, which also include good cold washing properties, surfactants for this area of application should also have good water hardness stability and good biodegradability and should be easy to formulate into various end products. The performance properties of alkylarylsulfonates are largely determined by the chain length and the degree of branching of the alkyl chain. Too low a degree of branching can have a negative effect on the viscosity and solubility of the compounds and thus their formulability, whereas if the degree of branching is too high, the biodegradability of the products generally deteriorates. In addition to the degree of branching of the alkyl chain, the position of the aryl radical within the chain also plays a role in the product properties. Optimal results with regard to several properties (solubility, viscosity, washing properties, biodegradability) can usually be controlled by suitable selection of the proportions of different constitutional isomers (e.g. the 2-, 3-, etc. -phenylalkane fraction). Alkyl aryl sulfonates are usually prepared by alkylation of an aromatic, sulfonation and subsequent neutralization. The alkylation takes place, for example, according to the so-called Friedel-Crafts alkylation customary for the alkylation of aromatic rings, by reaction with an alkylating agent, generally at least one alcohol or olefin, in the presence of an alkylation catalyst. There is a great need for olefin or alcohol mixtures which are economically available in large quantities with a suitable degree of branching and a suitable position of the double bond or alcohol function as intermediates for further processing to alkylarylsulfonates with an advantageous profile of properties.

DE-A-100 39 995 (WO 02/14266) describes a process for the preparation of alkylarylsulfonates by metathesis of a C-01e-ene mixture for the preparation of an olefin mixture containing 2-pentene and / or 3-hexene, followed by di erization to give a Cιo -Cι ₂ -01efinemisch, implementation of this olefin mixture with an aromatic hydrocarbon in a Friedel-Crafts alkylation, sulfonation of the alkyl aromatic compounds obtained and neutralization to alkylarylsulfonates.

WO 02/44114 describes a process for the preparation of alkylarylsulfonates by alkylation of an aromatic hydrocarbon with a mixture of C 1 -C 1 olefins which are predominantly simply branched on a statistical average and subsequent sulfonation.

DE-A-101 48 577 (WO 03/29172) relates to a process comparable to DE-A-100 39 995, in which the production of the C-01eine mixture from liquid gases (liquified petroleum gas) available on an industrial scale, natural gas (liquified natural gas) or so-called MTO flows (methanol-to-olefins).

German patent application P 102 13 492.8 describes a process comparable to DE-A-101 48 577, it being possible to additionally add linear olefins to the C ₀ -C ₂ -olefin mixture before use for the alkylation.

The present invention is based on the object of providing a process for the preparation of alkylarylsulfonates which are advantageously suitable for use as surfactants in detergents and cleaning agents. In particular, they should have a suitable property profile consisting of good washing properties, in particular good cold-washing properties, good biodegradability, insensitivity to water hardness and good ability to be formulated into various end products. The process should be based on large-scale, inexpensive and easily accessible building blocks.

Surprisingly, it has now been found that this object is achieved by a process for the preparation of alkylarylsulfonates, in which is then subjected to a C ^ -C _ß monoolefins containing hydrocarbon mixture of a hydroformylation and aldehyde mixture obtained to an aldol condensation and subsequent hydrogenation. Alcohol mixtures with an advantageous degree of branching of the alkyl chain and position of the alcohol function are obtained as intermediates, which can be further converted to alkylarylsulfonates, if appropriate after dehydration to give a C 1 -C ₄ -monoolefin mixture intermediate with comparable advantageous properties. The invention therefore relates to a process for the preparation of alkylarylsulfonates, in which

a) provides an olefin-containing hydrocarbon mixture which essentially contains monoolefins having 4 to 6 carbon atoms,

b) hydroformylating the monoolefin mixture by reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to give an aldehyde mixture,

c) the aldehyde mixture is subjected to an aldol condensation to obtain a mixture of condensed α, β-unsaturated aldehydes,

d) the mixture obtained in step c) is hydrogenated in the presence of a hydrogenation catalyst to give a mixture of saturated alcohols having 10 to 14 carbon atoms,

e) optionally dehydrating the alcohol mixture obtained in step d) to give an olefin mixture which essentially contains olefins having 10 to 14 carbon atoms,

f) reacting the alcohol mixture obtained in step d) or the olefin mixture obtained in step e) with an aromatic hydrocarbon in the presence of an alkylation catalyst to obtain a mixture of alkyl aromatic compounds, and

g) the mixture of alkyl aromatic compounds obtained in step f) is sulfonated and neutralized. Provision of an olefin-containing C ₄ -C ₆ hydrocarbon mixture

In step a) of the process according to the invention, an olefin-containing hydrocarbon mixture is preferably provided which is derived from one or more technically available olefin mixtures. Preferred olefin mixtures available on an industrial scale result from the hydrocarbon splitting in petroleum processing, for example by cat cracking, such as fluid catalytic cracking (FCC), thermal cracking or hydrocracking with subsequent dehydrogenation. A suitable technical olefin mixture is the C _{4 cut} . C ₄ cuts are available, for example, by fluid catalytic cracking or steam cracking of gas oil or by steam cracking from naphtha. Depending on the composition of the C _{4 cut, a} distinction is made between the total C _{4 cut} (raw C _{4 cut} ), which after separation from

1,3-butadiene so-called raffinate I and the raffinate II obtained after the isobutene separation. Another suitable technical olefin mixture is the C _{5 cut} available from naphtha cleavage. Olefin-containing hydrocarbon mixtures with 4 to 6 carbon atoms which are suitable for use in step a) can furthermore be obtained by catalytic dehydrogenation of suitable paraffin mixtures which are available on an industrial scale. For example, the production of C ₄ -01efin mixtures from liquefied gases (liquefied petroleum gas, LPG) and liquefiable natural gases (liquified natural gas, LNG). In addition to the LPG fraction, the latter also comprise larger amounts of higher molecular weight hydrocarbons (light naphtha) and are therefore also suitable for the production of C ₅ - and Cg-olefin mixtures. The production of olefin-containing hydrocarbon mixtures, which contain monoolefins having 4 to 6 carbon atoms, from LPG or LNG streams can be carried out by customary processes known to the person skilled in the art, which generally comprise one or more workup steps in addition to the dehydrogenation. A suitable production process includes, for example, the dehydrogenation, subsequent separation or partial hydrogenation of the dienes and alkynes obtained in the dehydrogenation, and the isolation of the C ₄ -Cg-01-fine. Alternatively, the dehydrogenation can be followed by the isolation of the C ₄ -C ₆ -01efins, followed by the removal or partial hydrogenation of the dienes and / or alkynes and, if appropriate, further by-products. Furthermore, it is also possible to first isolate a suitable C ₄ -C ₆ paraffin cut and then to subject it to dehydrogenation and further workup. Suitable processes and catalysts for the dehydrogenation of saturated hydrocarbons are described, for example, in DE-A-100 47 642, US 4,788,371, WO 94/29021, US 5,733,518, EP-A-0 838 534, WO 96/33151 and WO 96/33150, to which full reference is made here.

A suitable process for converting LNG streams into 5 C ₄ -01efin mixtures is the so-called methanol-to-olefin process (MTO process) or also known as the methanol-to-gasoline (MTG) process the methanol is dehydrated on a suitable catalyst. In this regard, reference is made to the disclosure in Weissermel, Arpe, Industrial Organic Chemistry, 10 4th edition 1994, VCH-Verlagsgesellschaft, Weinheim, p. 36 ff.

Another method for producing olefin-containing hydrocarbon mixtures suitable for use in step a)

15 is the chlorination-dehydrochlorination of suitable paraffins. This process is particularly suitable for the production of linear olefin mixtures from linear paraffins. Suitable olefin-containing hydrocarbon mixtures, in particular Cβ-olefin mixtures, are also obtained by oligomerization and optionally fractionation

20 lower olefins obtained. These include, for example, the dimersol process for the production of isomeric hexenes by oligomerizing propenes and butenes on transition metal catalysts.

In addition to monoolefins with 4 to 6 carbon atoms, the hydrocarbon mixtures used in step a) can additionally contain saturated hydrocarbons with the same, lower or higher number of carbon atoms, such as propane, butane, pentane, hexane, heptane etc. The proportion of these components which behave inertly to the process measures 30 according to the invention, can be in a range from about 1 to 99 mol%, preferably 1 to 60 mol% and is preferably less than 40 mol% (based on the total hydrocarbon mixture).

In addition to monoolefins having 4 to 6 carbon atoms, the hydrocarbon mixtures used according to the invention can also contain mono-olefinically unsaturated hydrocarbons with a lower or higher number of carbon atoms, such as propene, heptenes, octenes, etc. The proportion of such monoolefins is preferably at most 10 mol%, particularly preferably at most 5 mol% and 40 in particular at most 3 mol% (based on the total olefin content).

If the olefin-containing hydrocarbon mixture for use in step a) contains diolefins and / or alkynes, these are preferably removed to less than 45-10 ppm, in particular to less than 5 ppm, before the hydroformylation. The distance tion is preferably carried out by selective hydrogenation by known methods, for. B. according to EP-A-81 041 and DE-A-1 568 542.

Alternatively, diolefins or alkynes 5 are removed by extraction, in particular by extractive distillation. The volatility of the components to be separated of a mixture, such as. B. butadiene, reduced by the addition of suitable organic solvents. Suitable solvents for extractive distillation are, for example, acetone, furfural, acetoni-

10 tril, dimethylacetamide, dimethylformamide and N-methylpyrrolidone. Extractive distillation is particularly suitable for working up C ₄ crack cuts which, in addition to butadiene, also contain relatively high proportions of alkynes, such as methyl, ethyl and vinyl acetylene and methyl alleles.

15

Preferably, oxygen-containing compounds such as alcohols, aldehydes, ketones or ethers are also largely removed from the hydrocarbon mixture provided in step a). If desired, other hydrocarbon

20 mixed impurities such as water, organic chlorides, sulfur compounds etc. are removed. For this purpose, the olefin-containing hydrocarbon mixture with suitable adsorbents, such as. B. a molecular sieve, especially a molecular sieve with a pore diameter of 3 to 5 Å, in contact

25 are brought. Suitable adsorbent materials are, for example, Selexsorb® CD and CDO.

Preferably, in step a) a hydrocarbon mixture is provided comprising from 0 to 80 wt .-% C ₄ -01efine, 20 to 100 wt .-%

30 C ₅ -01efine, 0 to 60 wt .-% C ₆ -01efine and 0 to 10 wt .-% of olefins different from the aforementioned olefins, each based on the total olefin content. The hydrocarbon mixture provided in step a) particularly preferably contains 0 to 50% by weight of C ₄ -0efins, 50 to 100% by weight of C ₅ -01efins, 0 to

35 50% by weight of Cβ-olefins and 0 to 5% by weight of different olefins. In particular, the hydrocarbon mixture provided in step a) contains 0 to 40% by weight of C ₄ -01efins, 60 to 100% by weight of C ₅ -01efins, 0 to 30% by weight of Cβ-olefins and 0 to 3% by weight % of which are different olefins. A very particularly preferred

40 th hydrocarbon mixture contains 0 to 10 wt .-% C ₄ -01efine, 80 to 100 wt .-% C ₅ -01efine, 0 to 20 wt .-% C ₆ -01efine and 0 to 3 wt .-% of different olefins ,

In step a), a hydrocarbon mixture is preferably provided which has a linear monoolefin content of at least 80% by weight, particularly preferably at least 90% by weight and in particular at least 95% by weight, based on the total olefin content. content, has. The monoolefins are selected from 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene and mixtures thereof.

The provision of the olefin-containing hydrocarbons in step a) can include a separation of branched olefins. Customary separation processes known from the prior art are suitable, which are based on different physical properties of linear and branched olefins or on different reactivities which enable selective reactions. For example, isobutene can be separated from C4-01efin mixtures, such as raffinate I, by one of the following methods:

- Molecular sieve fractional distillation reversible hydration to tert-butanol acid-catalyzed alcohol addition to a tertiary ether, for. B. methanol addition to methyl tert. -butyl ether (MTBE) - irreversible catalyzed oligomerization to di- and tri-

Isobutene - irreversible polymerization to polyisobutene

Such methods are described in K. Weissermel, H.-J. Arpe, Industrial Organic Chemistry, 4th edition, pp. 76 - 81, VCH-Verlaggesellschaft Weinheim, 1994, to which reference is made in full here.

In step a), an olefin-containing hydrocarbon mixture is preferably provided, the linear pentenes and / or hexenes content of which is at least 80% by weight, particularly preferably at least 90% by weight, in particular at least 95% by weight, based on the total olefin content , is.

The hydrocarbon mixture provided in step a) preferably has a linear pentene content (1-pentene and / or 2-pentene) of at least 80% by weight, preferably at least 90% by weight, in particular at least 95% by weight on the total olefin content, on.

According to a preferred embodiment of the process according to the invention, to provide the olefin-containing hydrocarbon mixture in step a), a C ₄ -hydrocarbon mixture containing 1-butene and 2-butene is subjected to metathesis on a metathesis catalyst and the reaction mixture obtained is separated, a 2-pentene being separated containing electricity and possibly little at least one further stream containing monoolefin is obtained for use in step b).

C ₄ -hydrocarbon mixtures suitable for metathesis, which contain 1-butene and 2-butene and optionally isobutene, are the aforementioned C ₄ cuts, as are obtained, for example, by fluid catalytic cracking of gas oil and steam cracking of gas oil or naphtha. The butene mixtures described above are also suitable, such as those obtained in the dehydrogenation of butane-containing hydrocarbon mixtures or in the dimerization of ethene. Diolefins or alkynes are preferably removed from the C ₄ -hydrocarbon mixture before the metathesis. The proportion of these components in the hydrocarbon mixture used for the metathesis is preferably less than 10 ppm, in particular less than 5 ppm. In addition, oxygen-containing compounds, such as alcohols, aldehydes, ketones or ethers, as well as sulfur compounds and other impurities, are preferably removed by the conventional methods described above, such as extraction or adsorption.

The butene content, based on 1-butene, 2-butene and isobutene, of the C ₄ -hydrocarbon mixture used for the metathesis is preferably 1 to 100% by weight, particularly preferably 40 to 99% by weight, and in particular 50 to 90% by weight. -%. The ratio of 1-butene to 2-butene is preferably in a range from 20: 1 to 1: 2, in particular approximately 10: 1 to 1: 1. The C ₄ hydrocarbon mixture used for the metathesis preferably contains less than 5% by weight, in particular less than 3% by weight, of isobutene. A so-called raffinate II, which is a C _{4 cut} depleted in butadiene and isobutene from an FCC system or a steam cracker, is particularly preferably used as the starting material. Raffinate II has the following typical composition:

i-, n-butane 15 to 26 mol%, preferably 15 to 20 mol% i-butene 1 to 3 mol%

1-butene 26 to 40 mol%, preferably 35 to 40 mol% trans-2-butene 27 to 32 mol% cis-2-butene 14 to 16 mol%

Suitable metathesis processes for the production of streams containing 2-pentene and optionally further streams containing monoolefin are described, for example, in DE-A-100 13 253, EP-A-1 069 101, WO 00/39058 and DE-A-100 39 995, where - Reference is made here in full. The term "metathesis" formally designates the exchange of the alkylidene groups between two alkenes in the presence of homogeneous or heterogeneous transition metal catalysts according to the following equation:

The following primary reactions of the starting materials occur in principle in the metathesis of hydrocarbon mixtures containing 1-butene and 2-butene:

Cross metathesis of 1-butene with 2-butene

[Kat.j

1-butene 2-butene propene 2-pentene

Self-metathesis of 1-butene

[Kat.j

1-butene ethene + 3-witch

In addition, there may be secondary reactions between the products formed in the primary reactions or between products and starting materials still present. A reaction which is important for the composition of the product mixture obtained in the metathesis is the ethenolysis of 2-butene by ethene formed or added in the metathesis according to the following scheme:

Ethenolysis of 2-butene

2-butene ethene propene If small amounts of isobutene or other branched olefins are still contained in the C ₄ -hydrocarbon mixture used for the metathesis, small amounts of branched products can also be formed in the metathesis. The amount of branched C ₅ - and C _β -olefins formed in the metathesis is preferably kept as small as possible and in particular less than 3% by weight.

Depending on the products aimed for, such as 2-pentene, 3-hexene, possibly their isomers and optionally propene, the external mass balance of the process can be influenced in a targeted manner by shifting the equilibrium by recycling certain partial flows. For example, the 3-hexene yield can be increased by recycling the 2-pentene to the reaction zone used for metathesis

Balance of the cross metathesis of 1-butene with 2-butene is shifted towards the educts. In the self-metathesis of 1-butene to 3-hexene, which then preferably takes place in the reaction zone, ethene is additionally formed, which reacts in a subsequent reaction with 2-butene to give the valuable product propene.

The reaction conditions in the metathesis and the procedural measures in the separation of the reaction mixture obtained are preferably selected such that a monoolefin-containing stream with a high 2-pentene content is obtained. In step a), an olefin-containing hydrocarbon mixture having a 2-pentene content of at least 50% by weight, preferably at least 80% by weight and in particular at least 90% by weight, based on the total olefin content of the hydrocarbon mixture, is preferably obtained. The 2-pentene content is preferably at least 1% by weight, particularly preferably at least 10% by weight and in particular at least 50% by weight, based on the total hydrocarbon mixture.

The reaction conditions of the metathesis and the procedural measures for the separation of the reaction mixture obtained are preferably selected so that a further 3-hexene-containing stream is obtained. This stream preferably has a 3-hexene content of at least 50% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, based on the total olefin content of the stream. The 3-hexene content of the stream is preferably at least 1% by weight, preferably at least 10% by weight and in particular at least 50% by weight, based on the total hydrocarbon content of the stream.

For the separation, the reaction mixture of the metathesis can be subjected to one or more separation steps. Suitable separation devices are the usual apparatuses known to the person skilled in the art. These include e.g. B. distillation columns, e.g. B. tray columns, which can optionally be equipped with bells, sieve plates, sieve plates, valves, side draws, etc., evaporators, such as thin-film evaporators, falling film evaporators, wiper blade evaporators, Sambay evaporators, etc. and combinations thereof. The olefin fraction is preferably isolated by single- or multi-stage fractional distillation.

In general, the reaction mixture of the metathesis is separated into

1) a purge stream,

2) a stream enriched in unreacted starting materials which is returned to the metathesis reactor, and 3) a product stream.

For the metathesis in step a), the methods described in EP-A-1 069 101 and DE-A-100 13 253 can preferably be used, to which reference is made in full here. In the first process, any ethene formed in the metathesis is returned to the reaction zone, while in the second process ethene is additionally metered into the reaction zone.

The metathesis method used in step a) preferably comprises the following steps:

al) reaction of a C- ₄ hydrocarbon mixture containing 1-butene, 2-butene, optionally containing isobutene and saturated hydrocarbons, in a reaction zone in the presence of a metathesis catalyst to give a hydrocarbon mixture containing C ₂ -C ₆ -01efins,

a2) separation of the discharge from the reaction zone by distillation into a first low boiler fraction enriched in C ₂ -C ₄ olefins and containing butanes, which is removed, and in a high boiler fraction enriched with Cs-Cg olefins and containing butenes and butanes,

a3) separation by distillation of the first high boiler fraction obtained in step a2) into a second low boiler fraction enriched in butenes and butanes, a middle boiler fraction enriched in pentenes and a second high boiler fraction enriched in hexenes, the second low boiler fraction and optionally at least part of the middle boiler fraction or the second high boiler fraction are returned to the reaction zone and the led parts of the middle boiler fraction and the second high boiler fraction are discharged as a product, or

a4) separation of the first high boiler fraction obtained in step a2) by distillation into a second high boiler fraction enriched with butene, pentenes and butanes and a second high boiler fraction enriched with hexenes, the second low boiler fraction being returned to the reaction zone and the second high boiler fraction being discharged as product.

The variants described above are explained below for the purpose of illustration in FIGS. 1 and 2 using simplified process diagrams. For a better overview, the reactions are shown in the C ₄ feed without any significant amounts of isobutene. Mean:

c ₂ = = ethene c ₃ = = propene C = = 1- and 2-butene c ₄ ^~ = n- and i-butane c ₅ = = 2-pentene c ₆ = = 3 -hexene

C -Re = C ₄ -Recycle n-Bu = n-butenes

C / ₅ -Re = _C4 / ₅ -Recycle

C ₅ -Re = C ₅ -Recycle

Alternatively, the metathesis process comprises steps a) to d), where

a) a stream containing C ₄ -alkenes C ₄ ⁼ with a metathesis catalyst which contains at least one compound of a metal from VI.b, VII. or VIII. Subgroup of the Periodic Table of the. Contains elements in contact, at least some of the C ₄ -alkenes being converted to C- to Cβ-alkenes, and the resulting stream of C- to C _β -alkenes containing stream (stream C ₂ _ ₆ ⁼ ) from the metathesis catalyst separates,

b) removed in a step b) from stream C ₂ _ ₆ ⁼ ethylene by distillation and thus produces a stream containing C ₃ - to Cβ-alkenes (stream C ₃ _ ₆ ⁼ ) and a stream consisting essentially of ethylene (stream C ₂ ⁼ ) produces,

c) in a step c) the stream C ₃ _ ₆ ^{= by} distillation into an im

Material flow consisting essentially of propylene (flow C ₃ ⁼ ), a material flow consisting essentially of C ₆ -alkenes (Stream Cg ⁼ ) and one or more material streams selected from the following group: a material stream consisting essentially of C ₄ -alkenes (stream C ₄ ⁼ ), a material stream consisting essentially of C ₅ -alkenes (stream Cs ⁼ ) and one essentially separates material stream consisting of C ₄ - and Cs-alkenes (stream C ₄ _ ₅ ⁼ ),

d) in a step d) one or more material streams or parts thereof, selected from the group stream C ₄ ⁼ , stream Cs ⁼ and stream C ₄ _ ₅ ⁼ , used in whole or in part to produce output stream C ₄ = (recycling stream) , and optionally the stream or streams or parts thereof which are not recycled stream are discharged.

This process is described in the German patent application

102 14 442.7, to which reference is made in full here.

Metathesis with two-stage distillation and partial C ₄ recycling Obtaining 2-pentene and 3-hexene (Fig. 1):

The discharge stream of the metathesis reactor R consisting of C ₂ -C ₆ -01efins and butanes is separated in the distillation Dl into a fraction of ethene, propene and 0 to 50% of the unreacted butenes and butanes, which are optionally fed into the processing sequence of a cracker , as well as a high boiler fraction consisting of residual C ₄ and 2-pentene and 3-hexene formed. The latter is distilled in a column D2 to obtain 2-pentene as a side draw and 3-hexene. Both flows occur with a purity of> 99%. The C ₄ fraction is withdrawn overhead and returned to the metathesis reactor R. Column D2 can also be designed as a dividing wall column. The reactor R and the column D1 can be coupled to form a reactive distillation unit.

The top discharge from the distillation column Dl can be recycled to the metathesis reactor R to increase the yield of Cs / Cg olefins if required.

Metathesis step with two-stage distillation and partial C ₄ and Cs recycling, maximizing the hexene yield (FIG. 2):

The discharge stream of the metathesis reactor R consisting of C ₂ -C ₆ -olefins and butanes is separated in the distillation Dl into a fraction of ethene, propene and 0 to 50% of the unreacted butenes and butanes, which are optionally fed into the processing sequence of a cracker , as well as a high boiler fraction, which consists of residual C ₄ and formed 2-pentene and 3-hexene. The latter is distilled in a column D2 to obtain 3-hexene, which is isolated with a purity of> 99%. The C ₄ fraction is taken together with pentene overhead and returned to the metathesis reactor R. The reactor R and the columns D1 and D2 can be coupled to form a reactive distillation unit.

A metathesis process is preferred, comprising the steps a1 to a3) described above in accordance with FIG. 1. This process makes it possible to increase the yield of the non-recycled olefin by recycling 3-hexene or 2-pentene into the reaction zone. In the process according to the invention, the 3-hexene-containing stream is preferably partially or completely recycled into the reaction zone, a monoolefin-containing stream having a high 2-pentene content being obtained as a medium-boiler fraction for use in reaction step b).

A further possibility for controlling the product ratio in the reaction mixture obtained in the metathesis consists in a corresponding adjustment of the 1-butene / 2-butene ratio in the olefin-containing hydrocarbon mixture used for the metathesis. For this purpose, the feed hydrocarbon mixture can, if desired, be subjected to isomerization before the metathesis reaction. Suitable catalysts for the isomerization are described in DE-A-100 13 253, to which reference is made in full here.

Suitable catalysts for metathesis are known and comprise heterogeneous and homogeneous, preferably heterogeneous catalyst systems. In general, catalysts based on a transition metal of VI., VII. Or VIII. Subgroup of the Periodic Table of the Elements are suitable for the process according to the invention, catalysts based on Mo, W, Re and Ru preferably being used.

A particularly preferred heterogeneous catalyst is Re ₂ 0 ₇ on a support material. Suitable carrier materials are A10 ₃ , such as γ-Al ₂ 0 ₃ , and mixed oxides, such as. B. Si0 ₂ / Al ₂ 0 ₃ , B ₂ 0 ₃ / Si0 ₂ / Al ₂ 0 ₃ or Fe ₂ 0 ₃ / Al ₂ 0 ₃ . The rhenium oxide content is independent of the carrier in a range from 1 to 20% by weight, preferably from 3 to 10% by weight, based on the total weight of the catalyst.

Suitable homogeneous catalysts are those that a) at least one transition metal alkylidene complex (transition metal carbene complex) or

b) a combination of a transition metal compound and at least one further suitable for forming a complex a)

Agent, preferably an alkylating agent, or

c) a transition metal compound suitable for forming a complex a) with the olefins contained in the hydrocarbon mixture provided

include.

These include homogeneous catalysts, which are selected from ruthenium alkylidene complexes of the formula RuCl ₂ (= CHR) (PR ' ₃ ), preferably

RuCl ₂ (= CHC ₆ H ₅ ) (P (C ₆ H _U ) ₃ ) ₂ ,

(η6-p-cymene) RuCl ₂ (P (C ₆ Hιι) ₃ ) / (CH ₃ ) ₃ SiCHN ₂ ,

(η ⁶ -p-cymene) RuCl ₂ (P (C ₆ Hn) ₃ ) / C ₆ H ₅ CHN ₂ , molybdenum alkylidene complexes, preferably ((CH ₃ ) ₃ CO) ₂ Mo (= N- [2,6- ( iC ₃ H ₇ ) ₂ -C ₆ H ₃ ]) (= CH-C (CH ₃ ) ₂ C ₆ H ₅ ), [(CF ₃ ) ₂ C (CH ₃ ) O] ₂ Mθ (= N- [2 , 5- (iC ₃ H ₇ ) ₂ -C ₆ H ₃ ]) (= CH-C (CH ₃ ) ₂ C ₆ H ₅ ) and

CH ₃ Re0 ₃ / C ₂ H ₅ AlCl ₂ , WOCl ₂ (0- [2, 6-Br ₂ -C ₆ H ₃ ]) / Sn (CH ₃ ) ₄ ,

WCl ₆ / C ₂ H ₅ AlCl ₂ (Sn (CH ₃ ) ₄ ) / EtOH, W0Cl ₄ / Sn (CH ₃ ) ₄ .

An overview of suitable homogeneous catalysts can be found in EP-A-1 069 101, page 10, line 40 to page 11, line 32, to which reference is made here.

The metathesis can be carried out in the liquid phase or in the gas phase. In the liquid mode, pressure and temperature are selected in the metathesis step so that all reactants are in the liquid phase. The temperature is preferably in a range from about 0 to 150 ° C., particularly preferably 20 to 110 ° C. The pressure is preferably in a range from about 2 to 200 bar, particularly preferably 5 to 40 bar. For metathesis in the gas phase, the temperature is preferably in a range from about 20 to 300 ° C., particularly preferably 50 to 200 ° C. The pressure is then preferably in a range from about 1 to 20 bar, particularly preferably 1 to 5 bar.

If Cs-olefin-containing hydrocarbon mixtures and Cβ-olefin-containing hydrocarbon mixtures, in particular 3-hexene-containing hydrocarbon mixtures, are obtained in step a) of the process according to the invention, these can be used in an integrated process for the preparation of alkylarylsulfonates. The C ₅ -01efin-containing hydrocarbon mixtures are used in the previously described reaction sequence from steps b) to g). The hydrocarbon mixtures containing C ₆ -01efin are used according to an alternative process sequence, comprising the following steps B) to D):

B) dimerization of the C _ß- olefin-containing hydrocarbon mixture and optionally at least part of the C ₅ -0le-fin-containing hydrocarbon mixture over a dimerization catalyst to give a mixture containing Cιo-Cχ-01efine,

C) reaction of the C 1 -C ₂ -01efin mixture obtained in step B) with an aromatic hydrocarbon in the presence of an alkylation catalyst to obtain a mixture of alkyl aromatic compounds, and

D) Sulfonation and neutralization of the mixture obtained in step C).

Processes for the preparation of alkylarylsulfonates which comprise reaction steps B) to D) are described in DE-A-1 003 995 and German patent application 101 48 577, to which reference is made in full here.

In a preferred embodiment, the mixture containing C 1 -C ₂ -efins obtained in step B) can additionally be used (as a so-called cofeed) in process step f) of the process described above.

The invention also relates to an integrated method as described above.

hydroformylation

Suitable catalysts for the hydroformylation in step b) are known and generally comprise a salt or a complex compound of an element of subgroup VIII of the periodic table. The metal of subgroup VIII is preferably selected from cobalt, ruthenium, iridium, rhodium, nickel, palladium and platinum. Salts and in particular complex compounds of rhodium or cobalt are preferably used for the process according to the invention.

Suitable salts are, for example, the hydrides, halides, nitrates, sulfates, oxides, sulfides or the salts with alkyl or aryl carboxylic acids or alkyl or aryl sulfonic acids. Suitable complex compounds are, for example, the carbonyl compounds and carbonyl hydrides of the metals mentioned and complexes with amines, amides, triarylphosphines, trialkylphosphines, tricycloal- kylphosphines, olefins, or dienes as ligands. The ligands can also be used in polymeric or polymer-bound form. Catalyst systems can also be prepared in situ from the salts and ligands mentioned above.

Suitable alkyl radicals of the ligands are the linear or branched C 1 -C ₅ -alkyl radicals described above, in particular C ₅ -C ₅ -alkyl radicals. Cycloalkyl preferably represents C ₃ -C 10 -cycloalkyl, in particular cyclopentyl and cyclohexyl, which can optionally also be substituted by C ₄ -C ₄ alkyl groups. Aryl is preferably understood to mean phenyl (Ph) or naphthyl, optionally with 1, 2, 3 or 4 C 1 -C ₄ alkyl, C 1 -C ₄ alkoxy, for. B. methoxy, halogen, preferably chloride, or hydroxy, which may optionally also be ethoxylated, is substituted.

Suitable rhodium catalysts or catalyst precursors are rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate (rhodium alum), rhodium (II) and Rhodium (III) carboxylate, preferably rhodium (II) and rhodium (III) acetate, rhodium (II) and rhodium (III) -2-ethylhexanoate, rhodium (III) oxide, salts of rhodium (III ) acid and trisammonium hexachlororhodate (III).

Also suitable are rhodium complexes of the general formula RhX _m L ¹ L ² (L ³ ) _n , wherein X is halide, preferably chloride or bromide, alkyl or aryl carboxylate, acetylacetonate, aryl or alkyl sulfonate, in particular phenyl sulfonate and toluenesulfonate, hydride or the diphenyltriazine Anion, where L ¹ , L ² , L ³ independently of one another for CO, olefins, cycloolefins, preferably cyclo-octadiene (COD), dibenzophosphole, benzonitrile, PR ₃ or RP-A-PR ₂ , m for 1, 2 or 3 and n stands for 0, 1 or 2. R (the radicals R can be the same or different) is to be understood as meaning alkyl, cycloalkyl and aryl radicals, preferably phenyl, p-tolyl, m-tolyl, p-ethylphenyl, p-cumyl, pt.-butylpheny1, pC ₁ -C ₄ alkoxyphenyl, preferably p-anisyl, xylyl, mesityl, p-hydroxypheny1, which may optionally also be ethoxylated, isopropyl, -C-C ₄ alkoxy, cyclopentyl or cyclohexyl. A stands for 1,2-ethylene or 1,3-propylene. L ¹ , L ² or L ³ are preferably independently of one another CO, COD, P (phenyl) ₃ , P (i-propyl) ₃ , P (anisyl) ₃ , P (0C ₂ H ₅ ) ₃ , P (cyclohexyl) ₃ , dibenzophosphole or benzonitrile. X preferably represents hydride, chloride, bromide, acetate, tosylate, acetylacetonate or the diphenyltriazine anion, in particular hydride, chloride or acetate.

Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (IΙ) nitrate, their amine or hydrate complexes, cobalt carboxylates, such as cobalt acetate, cobalt ethyl hexa- noat, cobalt naphthenoate, and the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl and hexacobalt hexadecacarbonyl. The cobalt carbonyl complexes and in particular dicobalt 5-octacarbonyl are preferably used for the process according to the invention.

The compounds of rhodium and cobalt mentioned are known in principle and adequately described in the literature, or they can be prepared by a person skilled in the art analogously to the compounds 10 already known. This preparation can also take place in situ, the catalytically active species also being able to be formed from the aforementioned compounds as catalyst precursors only under the hydroformylation conditions.

If a hydroformylation catalyst based on rhodium is used, it is generally used in an amount of 1 to 150 ppm, preferably 1 to 100 ppm. The reaction temperature for a hydroformylation catalyst based on rhodium is generally in the range from room temperature to 200 ° C., preferably 50 to

20 170 ° C.

If a hydroformylation catalyst based on cobalt is used, it is generally used in an amount of 0.0001 to 1.0% by weight, based on the amount of olefins to be hydroformylated. The reaction temperature for a hydroformylation catalyst based on cobalt is generally in the range from about 80 to 250 ° C., preferably from 100 to 220 ° C., particularly preferably from 150 to 200 ° C.

30 The reaction can be carried out at an elevated pressure of about 10 to 650 bar.

The molar ratio of H ₂ : CO is generally about 1: 5 to about 5: 1 and preferably about 1: 1. 35

In step b), a hydroformylation catalyst is preferably used which is capable of hydroformylating linear monoolefins while maintaining a high proportion of n-aldehydes.

As described above, according to a preferred embodiment of the process according to the invention, an olefin-containing hydrocarbon mixture is provided in step a) which has a linear olefin content of at least 80% by weight, particularly preferably at least 90% by weight and in particular at least

45 95 wt .-%, based on the total olefin content. These can be both olefins with terminal double bonds, such as 1-butene, 1-pentene and 1-hexene, and also olefins with internal permanent double bonds, such as 2-butene, 2-pentene, 2-hexene and 3-hexene. In general, the hydroformylation of olefins with more than two carbon atoms leads to the formation of mixtures of isomeric aldehydes due to the possible CO addition to each of the two carbon atoms of a double bond. In addition, double bond isomerization can also occur, ie a shift of internal double bonds to a terminal position and vice versa. In step b) of the process according to the invention, preference is given to hydroformylation compounds.

10 talysators are used which selectively enable the hydroformylation of terminal olefins with high selectivity towards the linear aldehyde. Furthermore, when using olefins with internal double bonds, the hydroformylation catalysts used are intended to shift these doubles.

15 pel bonds to a terminal position and subsequent hydroformylation with high selectivity towards the linear aldehyde. In the context of the present invention, this is understood to mean a hydroformylation catalyst which is used for the hydroformylation of linear monoolefins while obtaining a high

20 hen portion of n-aldehydes (high n-selectivity) is capable.

Hydroformylation catalysts with high n selectivity are known from the prior art. These include complexes of subgroup VIII metals with bis and polyphosphite ligands, such as

25 in US 4,668,651, US 4,748,261, US 4,769,498 and US 4,885,401. These also include complexes of metals of subgroup VIII with bidentate phosphorus atom-containing ligands which have a 1, 1 '-biphenylylene-bridging group or a 1, 1' -binaphthylylene-bridging group, as in the

30 WO 98/19985 and EP-A-0 937 022 are described. Full reference is made here to the ligands mentioned.

In step b), an aldehyde mixture is preferably obtained which, based on the total aldehyde content, contains 0 to 80% by weight of Cs aldehydes,

35 has 20 to 100% by weight of C ₆ aldehydes and 0 to 20% by weight of aldehydes different from the aforementioned aldehydes. In step b), an aldehyde mixture which contains 0 to 50% by weight of C ₅ aldehydes, 50 to 100% by weight of C ₆ aldehydes and 0 to 15% by weight of different aldehydes is particularly preferably obtained. In particular

40 obtained in step b) an aldehyde mixture which contains 0 to 30% by weight

C ₅ aldehydes, 70 to 100 wt .-% C ₆ aldehydes and 0 to 10 wt .-% of different aldehydes.

In step b), an aldehyde mixture is preferably obtained which has an aldehyde content of at least 80% by weight, particularly preferably at least 90% by weight and in particular without branching of the carbon skeleton in the 2-position relative to the carbonyl group. which has at least 95% by weight, based on the total aldehyde content. In step b) it is particularly preferred to obtain an aldehyde mixture which has a linear aldehyde content of at least 80% by weight, in particular at least 90% by weight and especially at least 95% by weight, based on the total aldehyde content. The linear aldehydes are very particularly preferably selected from 1-pentanal, 1-hexanal, 1-heptanal and mixtures thereof.

In step b), in particular, an aldehyde mixture is obtained whose content of 1-hexanal and / or 1-heptanal is at least 80% by weight, particularly preferably at least 90% by weight, in particular at least 95% by weight, based on the total aldehyde content , is.

The aldehyde mixture provided in step b) preferably has a 1-hexanal content of at least 80% by weight, preferably at least 90% by weight, in particular at least 95% by weight, based on the total aldehyde content.

aldol condensation

Two aldehyde molecules C _x - and C _y -aldehyde (x, y = number of carbon atoms) can be condensed to α, ß-unsaturated C _{(x + y)} -aldehydes. For example, two molecules of 1-hexanal can be condensed to 2-butyloct-2-enal.

The aldol condensation in step c) is carried out in a manner known per se, e.g. B. in the presence of an aqueous base as a catalyst. An alkali metal hydroxide, such as KOH or NaOH, or an alkali metal C 1 -C ₄ -alcoholate, such as sodium methoxide, is preferably used as the basic catalyst. The catalyst is generally used in an amount of 0.05 to 25 mol%, preferably 0.1 to 20 mol%, based on the amount of aldehyde used. Alternatively, a heterogeneous basic catalyst such as magnesium and / or aluminum oxide can also be used.

The reaction can either be solvent-free or, preferably, in a solvent. Suitable solvents include C 1 -C ₄ alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol or tert-butanol, and also their mixtures with C ₅ -C ₇ alkanes, such as n-pentane, n-hexane, n-heptane or cyclohexane.

The reaction temperature is preferably 0 to 150 ° C, particularly preferably 20 to 130 ° C and in particular 20 to 110 ° C. The aldol condensation is preferably carried out continuously.

The reaction mixture obtained is then optionally neutralized. The common mineral or organic acids are suitable for this. When using water-immiscible solvents and an aqueous base as a catalyst, neutralization is generally not necessary since the reaction products and any unreacted starting materials collect in the organic phase, while the base remains in the aqueous phase. Furthermore, neutralization is generally not necessary when using a heterogeneous catalyst.

Any water which may be present in the reaction mixture is preferably separated off by means of customary methods, for example by phase separation, the use of drying agents or azeotropic distillation.

In general, the linear aldehydes contained in the aldehyde mixture used are completely converted to the corresponding aldol condensation products under the conditions of the aldol condensation. If the aldehyde mixture used for the aldol condensation still contains fractions of branched aldehydes, for example 2-alkyl-substituted aldehydes from the addition of carbon monoxide to the 2-carbon terminally linear olefins or from the hydroformylation of olefins with internal double bonds, these can, for example be separated from the reaction mixture following the aldol condensation. Furthermore, the aldol condensation can be carried out under conditions which also include branched aldehydes. According to a further suitable embodiment, a product mixture is obtained in step c) which, in addition to condensed, α, β-unsaturated aldehydes, contains unreacted aldehydes of the aldehyde mixture obtained in step b) (preferably branched aldehydes) which are not separated off but together with the ( essentially from the linear aldehydes) condensed α, β-unsaturated aldehydes are used in the hydrogenation step d), at least some of the unreacted aldehydes undergoing an aldol condensation before the hydrogenation.

In step c), an aldehyde mixture is preferably obtained which has a content of condensed α, β-unsaturated aldehydes of at least 80% by weight, preferably at least 90% by weight, based on the total aldehyde content. In step c), an aldehyde mixture is preferably obtained whose content of 2-butyloct-2-enal is at least 80% by weight, particularly preferably at least 90% by weight, based on the total aldehyde content.

hydrogenation

For the hydrogenation in step d), the aldehyde mixture from step c) is reacted with hydrogen in the presence of a suitable hydrogenation catalyst.

Suitable hydrogenation catalysts generally comprise transition metals such as Cr, Mo, W, Mn, Rh, Co, Fe, Ni, Pd, Pt, Cu, Ru, etc., their mixtures, their oxides and their mixed oxides.

These can be used to increase the activity and / or stability on supports such as. B. activated carbon, aluminum oxide or silicon dioxide. When using Fe, Co and Ni in elemental form, these are suitably used as metal sponges in the form of so-called Raney catalysts.

A mixed oxide catalyst is preferably used for a hydrogenation with simultaneous aldol condensation of aldehydes not converted in step c). A particularly preferred catalyst for this process variant comprises nickel (II) oxide, copper (II) oxide, manganese (11 / IV) oxide, sodium oxide and phosphoric acid. The weight ratio of sodium oxide to phosphoric acid to manganese oxide to copper oxide to nickel oxide is preferably 1: 3-4: 5-7: 15-25: 50-70. The weight ratio is particularly preferably 1: 3.2-3.6: 5.5-6.0: 18-22: 58-63.

Preferably at least 80 mol%, particularly preferably at least 95 mol%, of the uncondensed aldehydes used in the hydrogenation react with prior aldolization.

The hydrogenation is preferably carried out at. elevated temperatures and pressure. The hydrogenation temperature is preferably 80 to 200 ° C, 100 to 180 ° C and in particular 100 to 150 ° C. The hydrogen pressure is preferably in a range from 100 to 300 bar, particularly preferably from 150 to 250 bar.

Working up is also carried out in a manner known per se. The reaction mixture is preferably separated from the catalyst by distillation and fractionated using the customary distillation devices mentioned above. The fractionation is preferably carried out via surface rectifiers, in particular with packed columns which are filled with bulk material, such as Raschig-Rin genes, saddle bodies, Pall® rings, wire spirals, etc., or systematically arranged column internals, such as tissue packs, can be filled. The rectification is preferably carried out under reduced pressure.

The process according to the invention advantageously does not require the use of olefins produced by an additional isomerization step in the hydroformylation step b). Internal olefins either isomerize under the hydroformylation conditions to α-olefins or to other internal olefins which are hydroformylated, or are hydroformylated as such. According to the invention, the branched aldehydes that are formed and are less reactive in the aldol reaction do not have to be discarded or isomerized in a costly manner, as is otherwise customary. Advantageously, in a mixture with the linear aldehydes, they can be subjected to the subsequent steps of aldolization c) and hydrogenation d), with them also at least partially aldolizing in the last step and being hydrogenated to the corresponding alcohols. The method according to the invention thus uses by-products which are otherwise regarded as disruptive or worthless in an optimized manner.

The invention further relates to the mixtures of saturated alcohols obtainable by the process according to the invention.

The alcohol mixture obtained in step d) preferably has a hydroxide number in the range from 200 to 500 mg KOH / g product, particularly preferably from 250 to 350 mg KOH / g product.

The alcohol mixtures according to the invention preferably have an average degree of branching in the range from 1 to 2.5, particularly preferably 1 to 2, in particular 1 to 1.5 and especially 1 to 1.2.

The number of methyl groups in one molecule of the alcohol minus 1 is defined as the degree of branching (V). The average degree of branching is the statistical number average ∑njNi / Σnj the degree of branching in a sample. The average number of methyl groups in the molecules of a sample can easily be determined using iH-ΝMR spectroscopy. For this, z. B. in the case of mixtures of alcohols of the same number of carbon atoms, the signal area corresponding to the methyl protons is divided by three and compared to the signal area of the methylene protons of the CH ₂ OH group divided by two. In the case of mixtures of alcohols with different numbers of carbon atoms, the number-average chain length is also required. The determination of the average degree of branching can also be calculated from the composition of the alcohol mixture determined by chromatography.

The alcohol mixtures according to the invention are advantageously suitable as intermediates for the preparation of alkylarylsulfonates. These alkylarylsulfonates are characterized by very good cold-washing properties and improved stability against hard water. Their biodegradability corresponds to that of linear alkylbenzenesulfonates and is better than that of branched alkylbenzenesulfonates known from the prior art, in particular those based on propylene tetramers.

The alcohol mixtures according to the invention are furthermore advantageously suitable for the functionalization for the preparation of surface-active alkoxylate mixtures. These advantageously have generally better application properties, such as. B. a comparable biodegradability, a reduced foaming power or an improved gel behavior, than alkoxilates, which are based on alcohol mixtures known from the prior art.

The hydrogenation preferably takes place as completely as possible so that the carbonyl number of the alcohol mixtures obtained by the process according to the invention is generally low. In general, the alcohol mixtures according to the invention have a carbonyl number of at most 5.

Likewise, the number of carbon-carbon double bonds in the alcohol mixtures obtained by the process according to the invention is generally very small. The alcohol mixtures according to the invention preferably have an iodine number of at most 1 mg iodine / g, particularly preferably of at most 0.5 mg iodine / g and in particular of at most 0.2 mg iodine / g.

An alcohol mixture is preferably obtained in step d), the content of 2-butyloctanol of which is at least 80% by weight, particularly preferably at least 90% by weight, based on the total alcohol content.

dehydration

If desired, the alcohol mixtures obtained in step d) can be dehydrated to an olefin mixture which essentially contains olefins having 10 to 14 carbon atoms before they are used for the alkylation in step f). The dehydration can be carried out by customary processes known to the person skilled in the art. Suitable processes are described in J. March, Advanced Organic Chemistry, 4th edition, John Wiley & Sons, pp. 1011-1012 (1992) and the literature cited therein, to which reference is made in full here. According to a suitable embodiment, the dehydration is carried out in the presence of H ₂ S0 ₄ or H ₃ P0 as dehydrating reagents. The dehydration is preferably carried out as gas phase elimination in the presence of a metal oxide such as Al ₂ 0 ₃ , Cr ₂ 0 ₃ , Ti0 ₂ or W0 ₃ or in the presence of a sulfide or zeolite. The is preferred

Gas phase elimination in the presence of A1 ₂ 0 ₃ . The temperature in the gas phase elimination is preferably in a range from about 150 to 500 ° C.

As a rule, isomerization occurs simultaneously when alcohols are dehydrated to olefins. In the dehydration of 2-butyloctanol, 5-methylundec-4-ene and 5-methylundec-5-ene are obtained in addition to the primary reaction product 2-butyloct-l-ene.

Another object of the invention are the olefin mixtures obtained in step e).

The olefin mixtures according to the invention obtained in step e) preferably have an average degree of branching in the range from 1 to 2.5, particularly preferably 1 to 2.0, in particular 1 to, 1.5 and especially 1 to 1.2. The degree of branching of the olefins is defined as the number of carbon atoms in a molecule which are linked to 3 carbon atoms plus twice the number of carbon atoms which are linked to 4 carbon atoms.

The olefin mixtures according to the invention are advantageously suitable for the preparation of alkylarylsulfonates.

In a suitable embodiment, the olefin mixtures obtained in steps a) to e) of the process according to the invention are mixed with at least one further olefin or an olefin mixture not prepared by the process according to the invention before their further use. Pure Cιo-Ci ₄ -01efine are suitable for this addition. Also suitable for this addition are olefin mixtures, such as those obtained by dimerizing C ₄ -C ₆ olefin mixtures by the dimerization processes described above. These include, in particular, the C ₁₀ -C ₂ olefins obtained by dimerization of C ₆ -01efin-containing hydrocarbon mixtures after the previously described dimerization step B). For the addition continued linear and branched C _l ₄ olefin mixtures from other sources are described o-Ci as the previously surrounded. The following are preferably suitable as sources for linear olefin mixtures:

a) olefins from an ethene oligomerization, e.g. B. the Shell 5 Higher Olefin Process (SHOP, see Weissermel-Arpe, Industrial Organic Chemistry, 3rd ed., Pp. 93-94),

b) olefins from a high-temperature Fischer-Tropsch process,

10 c) olefins from paraffin dehydrogenation z. B. via the PACOL DEFINE process. The paraffins preferably originate from a SORBEX or MOLEX process with raw materials from a low-temperature Fischer-Tropsch process or from petroleum distillates,

15 d) olefins from the dehydration of linear alcohols, obtained for example from native sources or by hydrogenation of fatty acids from native sources.

The olefin mixtures used for the alkylation in step f) preferably contain 5 to 100% by weight, particularly preferably 20 to 100% by weight and in particular 50 to 100% by weight of one after steps a) to e) des Process obtained olefin mixture according to the invention.

The olefin mixtures used for the alkylation in step f) preferably contain 0 to 95% by weight, particularly preferably 0 to 80% by weight and in particular 0 to 50% by weight of an olefin mixture which is obtained by dimerizing C ₄ -C ₆ -01 refine was obtained. This is preferably the one described above

30 dimerization step B) Cιo -Cι ₂ -olefin mixture obtained.

The olefin mixtures used for the alkylation in step f) preferably contain 0 to 95% by weight, particularly preferably 0 to 80% by weight and in particular 0 to 20% by weight of a mixture which differs from the 35 previously described olefin mixtures and which essentially linear Cιo-Cχ ₄ olefins contains.

The olefin mixtures used for the alkylation in step f) preferably contain 0 to 95% by weight, particularly preferably 0 to 40 80% by weight, in particular 0 to 50% by weight and very particularly preferably 0 to 20% by weight of one from the previously described olefin mixtures, a mixture which contains essentially branched C ₁ -C ₄ -olefins.

45 In step e), an olefin mixture is preferably obtained whose 5-methylundec-4-ene and / or 5-methylundec-5-ene content is at least 80% by weight, particularly preferably at least 90% by weight, based on the total olefin content , is.

alkylation

Suitable processes for the alkylation of aromatic rings by reaction with at least one alcohol or olefin in the presence of an alkylation catalyst are known in principle and are referred to as Friedel-Crafts alkylation. Suitable Friedel-Crafts alkylation processes are described in J. March, Advanced Organic Chemistry, 4th edition, John Wiley & Sons, pp. 534-539 and the literature listed therein, to which reference is made here in full.

Generally suitable alkylation catalysts are Lewis acids and protonic acids.

A heterogeneous alkylation catalyst is preferably used in the process according to the invention. Suitable heterogeneous catalysts can be of natural or synthetic origin. These include, for example, dimensionally stable and supported heterogeneous catalysts, such as metal (mixed) oxide catalysts, layered silicates and clays. If desired, the catalyst properties can be modified by methods known from the literature, such as ion exchange, steaming, blocking of acidic centers. The catalysts used are preferably acidic in character. The catalysts used can be present both as a powder and as a shaped body. If the catalysts are used as shaped bodies, care must be taken to ensure sufficient porosity. The production of shaped catalyst bodies can be carried out by customary processes known to the person skilled in the art, such as, for. B. tableting or extruding.

Possible heterogeneous catalysts for the alkylation are:

Beta (e.g. WO 98/09929, US 5,877,370, US 4,301,316,

US 4,301,317) faujasite (CN 1169889), layered silicates, clays (EP 711600), fluorinated mordenite (WO 00/23405), mordenite

(EP 466558), ZSM-12, ZSM-20, ZSM-38, mazzite, zeolite L, cancriticite, gmelinite, offretite, MCM-22, etc. Preferred are shape-selective 12-ring zeolites. Mordenite and faujasite are very particularly preferred. According to a preferred embodiment, the alkylation is carried out in such a way that the aromatics (the aromatic mixture), the alcohol mixture obtained in step d) or the olefin mixture obtained in step e), if appropriate after adding further olefins, as described above, in a suitable manner Allow reaction zone to react by bringing it into contact with the catalyst, work up the reaction mixture after the reaction and thus win the valuable products.

Suitable reaction zones are e.g. B. tubular reactors or stirred tanks. If the catalyst is in solid form, it can be used, for example, as a slurry, as a fixed bed or as a fluidized bed. Tubular reactors with circulation are preferred for the use of fixed bed catalysts. Jet loop reactors and loop reactors with crossflow filtration are preferred for the use of catalyst suspensions.

Execution as a catalytic distillation is also possible.

The reactants are either in a liquid and / or in a gaseous state.

The reaction temperature is chosen so that the highest possible space-time yield is achieved on the one hand and the complete conversion of the olefin takes place as possible and on the other hand as few by-products as possible are formed. The choice of temperature control also depends crucially on the chosen catalyst. Reaction temperatures between 50 ° C and 500 ° C (preferably 80 to 350 ° C, particularly preferably 80 to 250 ° C) can be used.

The pressure in the reaction zone depends on the chosen procedure (reactor type) and is generally between 0.1 and 100 bar, preferably 10 to 50 bar. The catalyst load (WHSV) is, for example, between 0.1 and 100 [kg feed / kg catalyst / h], preferably 0.1 to 10.

The reactants can be diluted with inert substances. Inert substances are preferably paraffins which originate from the hydrocarbon mixture used in step a).

The ratio of aromatic: olefin is preferably in a range from 1: 1 to 100: 1, particularly preferably 2: 1 to 30: 1, in particular 3: 1 to 20: 1. Aromatic hydrocarbons of the formula Ar-R _x are suitable, where Ar is a monocyclic or bicyclic aromatic hydrocarbon radical, R is H, Cι_s-, preferably Cι_ ₃ -alkyl, OH, OR etc., preferably H or C; ι_ ₃ alkyl is selected and x represents an integer from 1 to 3. Benzene and toluene are preferred.

The invention also relates to the mixtures of alkylaromatic compounds obtainable by the process according to the invention. These are advantageously suitable as intermediates for the production of alkylarylsulfonates and other surface-active compounds. The alkyl aromatic compounds according to the invention have a characteristic proportion of primary, secondary, tertiary and quaternary carbon atoms in the alkyl radical. This is reflected in the number of carbon atoms in the alkyl radical with an H / C index from 0 to 3. The H / C index defines the number of protons per carbon atom in the alkyl radical. Preferably, the mixtures according to the invention exhibit al _¬ kylaromatischer compounds only a small proportion of C-Ato men on of 0 in the alkyl radical with a H / C index. The proportion of carbon atoms in the alkyl radical with an H / C index of 0 on average of all compounds is preferably <15%, particularly preferably <10%. The proportion of carbon atoms in the alkyl radical with an H / C index of 0, which are simultaneously bound to the aromatics, is preferably at least 80%, particularly preferably at least 90% and in particular at least 95% of all carbon atoms in the alkyl radical with a H / C index of 0.

The mixtures of alkylaromatic compounds according to the invention preferably have on average 1 to 3, particularly preferably 1 to 2.5, in particular 1 to 2, carbon atoms in the side chain with an H / C index of 1. The proportion of compounds with 3 and more carbon atoms of this type is preferably at most 30%, particularly preferably at most 20% and in particular at most 10%.

The proportion of carbon atoms which have a specific H / C index can be controlled by a suitable choice of the catalyst used. Preferred catalysts with which advantageous H / C distributions are achieved are mordenite, beta zeolite, L zeolite and faujasite. Mordenite and faujasite are very particularly preferred.

Sulfonation and neutralization

The sulfonation and neutralization is carried out using customary methods, as described, for example, in J. March, Advanced Organic Chemistry, 4th edition, Verlag John Wiley & Sons, 1992, pp. 528-529 and the literature cited there. This includes the reaction with oleum, SO ₃ and chlorosulfonic acid.

The neutralization can be carried out, for example, with alkali and alkaline earth hydroxides, such as NaOH, KOH, Mg (OH) ₂ ; Alkali and alkaline earth carbonates, alkali and alkaline earth hydrogen carbonates and with ammonia.

The alkylarylsulfonates according to the invention are preferably used as surfactants, in particular in detergents and cleaning agents. The invention also relates to a washing and cleaning agent containing, in addition to alkylarylsulfonates, at least one liquid or solid carrier and optionally conventional ingredients.

Examples of suitable additives include:

Builders and cobuilders, for example polyphosphates, zeolites, polycarboxylates, phosphonates, citrates, complexing agents,

ionic surfactants, for example alkylbenzene sulfonates, α-olefin sulfonates and other alcohol sulfates / ether sulfates, including the C ₁₃ -Ci5 alcohol sulfates / ether sulfates according to the invention, sulfosuccinates,

- Other nonionic surfactants, for example alkylamine alkoxy latex and alkyl polyglucoside, amphoteric surfactants, e.g. B. alkyl amine oxides, betaines, the inventive C ₃ -C ₅ alkyl polyglucosides,

- optical brighteners,

Color transfer inhibitors, e.g. B. polyvinyl pyrrolidone,

- adjusting means, e.g. B. sodium sulfate, magnesium sulfate,

Soil release agents, e.g. B. polyether / ester, carboxymethyl cellulose,

Incrustation inhibitors, e.g. B. polyacrylates, copolymers of acrylic acid and maleic acid,

Bleaching systems consisting of bleaching agents, e.g. B. perborate or percarbonate, plus bleach activators, e.g. B. tetraacetylthylenediamine, plus bleach stabilizers,

Perfume, Foam damper, e.g. B. silicone oils, alcohol propoxylates (especially in liquid detergents),

Enzymes, e.g. B. amylases, lipases, proteases or carboxylases,

Alkaline dispenser, e.g. B. pentasodium metasilicate or sodium carbonate.

Other ingredients known to a person skilled in the art can also be included.

Liquid detergents can also contain solvents, e.g. As ethanol, isopropanol, 1,2-propylene glycol or butylene glycol.

Gel-shaped detergents also contain thickeners, such as. B. polysaccharides and weakly cross-linked polycarboxylates (e.g. the Carbopol® brands from BF Goodrich).

Additional additives are required for tablet-type detergents. These are, for example, tableting aids, e.g. B. polyethylene glycols with molecular weights> 1000 g / mol or polymer dispersions. Tablet disintegrants, e.g. B. cellulose derivatives, crosslinked polyvinylpyrrolidone, crosslinked polacrylate or combinations of acids, eg. B. citric acid, with sodium carbonate.

In cleaners for hard surfaces, e.g. B. acidic cleaners, alkaline cleaners, neutral cleaners, machine dishwashing, metal degreasing, glass cleaners, floor cleaners, to name but a few, the non-ionic C ₃ -Ci ₅ alcohol alkoxylates according to the invention are combined with those listed below in amounts from 0.01 to 40% by weight, preferably 0.1 to 20% by weight, of additives present.

ionic surfactants, such as. B. the Cι ₃ -Ci ₅ alcohol sulfate / ether sulfates according to the invention, alkylbenzenesulfonates, α-olefin sulfonates, other alcohol sulfates / ether sulfates, sulfosuccinates

other nonionic surfactants, e.g. B. alkylamine alkoxylates and alkyl polyglucosides, also the ^c i3-Ci5-alkyl polyglucosides according to the invention

- amphoteric surfactants, e.g. B. alkylamine oxides, betaines - Builders, e.g. B. polyphosphates, polycarboxylates, phosphonates, complexing agents

Dispersants, e.g. B. naphthalenesulfonic acid condensates, polycarboxylates

pH regulating compounds, e.g. B. alkalis such as NaOH, KOH or pentasodium metasilicate or acids, such as hydrochloric acid, phosphoric acid, amidosulfuric acid, citric acid

Enzymes, e.g. B. lipases, amylases, proteases, carboxylases

Perfume

- dyes

Biocides, e.g. B. isothiazolinones, 2-bromo-2-nitro-l, 3-propanediol

- Bleaching systems consisting of bleaching agents, e.g. B. perborate, percarbonate, plus bleach activators, e.g. B. tetraacetylethylene diamine, plus bleach stabilizers

Solubilizers, e.g. B. cumene sulfonates, toluenesulfonates, short-chain fatty acids, phosphoric acid alkyl / aryl esters

Solvents, e.g. B. short chain alkyl oligoglycols, alcohols such as ethanol or propanol, aromatic solvents such as toluene or xylene, N-alkylpyrrolidones, alkylene carbonates

- Thickeners, such as B. Polysaccharides and weakly cross-linked polycarboxylates (eg the Carbopol® brands from BF Goodrich).

These hard surface cleaners are usually, but not exclusively, aqueous and are in the form of microemulsions, emulsions or solutions.

If they are in solid form, adjusting devices as described above can also be used.

Additional additives are required for tablet-type cleaners. These are, for example, tableting aids, e.g. B. polyethylene glycols with molecular weights> 1000 g / mol or polymer dispersions. Also needed are tablet explosives, e.g. B. cellulose derivatives, crosslinked polyvinylpyrrolidone, crosslinked polyacrylates or combinations of acids, e.g. B. citric acid, with sodium carbonate.

The invention is illustrated by the following non-limiting examples.

Examples

example 1

1-Butyloctanol is alkylated with benzene in a molar ratio of 1:10. For this purpose, the reaction mixture is introduced into an autoclave (300 ml) which is equipped with a stirrer. 27% by weight, based on the mass of the alcohol, of catalyst zeolite mordenite (MOR) are added to the reaction mixture. The autoclave is closed and flushed twice with nitrogen (N ₂ ). The autoclave is then heated to 180 ° C. The reaction mixture is allowed to react for 20 hours, then cooled, any catalyst particles are filtered out of the reaction mixture and the reaction mixture is analyzed by means of gas chromatography.

The cis-alkylaryl mixture obtained was purified by distillation and analyzed by means of gas chromatography-mass spectrometry coupling and ¹ H / ¹³ C-NMR.

Example 2

A tubular reactor located in a forced air oven was treated with 32 g of catalyst grit (60% H-mordenite with SiO: AlO ₃ = 24.5 - shaped with 40% Pural SB, Condea) with a grain size of 0.7 to 1.0 mm filled and activated for 6 h at 500 ° C. The mixture was then cooled, flooded with a feed of benzene: butyl octanol (10: 1 molar), loaded with 0.30 g / gκ _at ⁿ and a circulation flow ten times higher was set. Finally, the reactor was heated to 200 ° C (single-phase liquid, 30 bar hydraulic pressure) and the content of starting materials and products in the outlet stream was detected by means of GC using time resolution. The cis-alkylaryl mixture obtained was purified by distillation and analyzed by means of gas chromatography-mass spectrometry coupling and ¹ H / ¹³ C-NMR.

Example 3

In an electrically heated gas phase reactor, 200 ml of γ-Al ₂ O ₃ catalyst (4 mm strands) were overlaid with 30 ml of quartz rings as the evaporator section. At 250 ° C and a catalyst load of 0.10 kg / L _Kat h 1-butyl octanol together with 100 NL / h nitrogen was passed over the catalyst from top to bottom. passes. The reaction discharge was condensed in a receiver with cooling with dry ice / acetone. The reaction was carried out for 80 hours. The reaction outputs collected had a constant composition over the entire period. The selectivity to the various 5-methylundecene isomers was consistently> 90% with a mass yield of> 90%. The olefins formed could all be hydrogenated to 5-methylundecane.

Example 4

A tube reactor located in a forced air oven was treated with 32 g of catalyst chippings (60% H-mordenite with SiO ₂ : Al ₂ O ₃ = 24.5 - shaped with 40% Pural SB, from Condea) with a grain size of 0.7 to 1.0 mm filled and activated for 6 h at 500 ° C. The mixture was then cooled, flooded with a feed of benzene: 5-methylundecene from experiment 3 (4: 1 molar), loaded with 0.35 g / gκat ⁿ and a circulation current set ten times higher. Finally, the reactor was heated to 160 ° C (single-phase liquid, 30 bar hydraulic pressure) and the content of starting materials and products in the outlet stream was detected in a time-resolved manner by means of GC. The cis-alkylaryl mixture obtained was purified by distillation and analyzed by means of gas chromatography-mass spectrometry coupling and ¹ H / ¹³ C-NMR.

Claims

claims

1. A process for the preparation of alkylarylsulfonates, in which

b) the monoolefin mixture is hydroformylated by reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to give an aldehyde mixture,

d) the mixture obtained in step c) is hydrogenated with hydrogen in the presence of a hydrogenation catalyst to give a mixture of saturated alcohols having 10 to 14 carbon atoms,

g) the mixture of alkyl aromatic compounds obtained in step f) is sulfonated and neutralized.

2. The method according to claim 1, wherein the hydrocarbon mixture provided in step a) has a linear monoolefins content of at least 80% by weight, based on the total olefin content.

3. The method according to claim 2, wherein the content of linear pentenes and / or hexenes is at least 80% by weight, based on the total olefin content.

4. The method according to any one of the preceding claims, in which to provide the olefin-containing hydrocarbon mixture in step a) a 1-butene and 2-butene containing C ₄ -hydrocarbon mixture is subjected to metathesis on a metathesis catalyst and the reaction mixture obtained is separated, a Stream containing 2-pentene for use in step b) and optionally at least one further stream containing monoolefin is obtained.

5. The method according to any one of the preceding claims, in which in step a) a Cs-olefin-containing and a C _ß- olefin-containing hydrocarbon mixture is obtained, the Cg-olefin-containing hydrocarbon mixture being used in a process comprising:

B) dimerization of the C _ß-olefin containing hydrocarbon mixture and optionally at least a portion of the Cs-olefin-containing hydrocarbon mixture at a di- merisierungskatalysator to a Cιo-Cι ₂ olefins containing mixture,

C) reaction of the Cιo-Cχ ₂ olefin mixture obtained in step B) with an aromatic hydrocarbon in the presence of an alkylation catalyst to obtain a mixture of alkyl aromatic compounds, and

D) Sulfonation and neutralization of the mixture obtained in step C).

6. The method according to any one of the preceding claims, in which in step b) a hydroformylation catalyst is used which is capable of hydroformylating linear monoolefins to obtain a high proportion of n-aldehydes.

7. The method according to any one of the preceding claims, in which in step c) a product mixture is obtained which, in addition to condensed α, β-unsaturated aldehydes, contains unreacted aldehydes of the aldeyde mixture obtained in step b), at least some of the unreacted aldehydes in Step d) undergoes an aldol condensation before the hydrogenation.

8. The method according to any one of the preceding claims, additionally comprising the addition of at least one further olefin or olefin mixture to the olefin mixture obtained in step e).

9. A mixture of saturated alcohols having 10 to 14 carbon atoms, obtainable by a process comprising steps a) to d) as defined in any one of claims 1 to 7.

10. A mixture according to claim 9, obtainable by a process as defined in claim 7, wherein in step a) an olefin-containing hydrocarbon mixture is provided which essentially contains monoolefins having 6 carbon atoms.

15 11. olefin mixture which essentially contains olefins having 10 to 14 carbon atoms, obtainable by a process comprising the steps a) to e) and optionally the addition of at least one further olefin or olefin mixture, as defined in one of claims 1 to 8.

20

12. A mixture of alkyl aromatic compounds obtainable by a process comprising steps a) to f) as defined in any one of claims 1 to 8.

25 13. Alkylarylsulfonates, obtainable by a process according to any one of claims 1 to 8.

14. Use of alkylarylsulfonates according to claim 13 as surfactants.

30

15. Use according to claim 14 in washing and cleaning agents.

16. Washing and cleaning agent containing at least one alkylarylsulfonate according to claim 13 and at least one liquid or solid carrier.

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