Title of Invention	A PROCESS FOR THE PREPARATION OF ALKYLARYLSULFONATES
Abstract	The invention relates to methods for producing alkyl aryl sulphonates by a) reaction of a C<sub>4</sub> olefin mixture on a methathetical catalyst to produce an olefin mixture containing 2 pentene and/or 3 hexene and optionally the separation of 2 pentene and/or 3 hexene, b) dimerisation of the 2 pentene and/or 3 hexene obtained in stage a) on a dimerisation catalyst to obtain a mixture containing C<sub>10</sub>-<sub>12</sub> olefins and the optional separation of said C<sub>10</sub>-<sub>12</sub> olefins, c) reaction of the C<sub>10</sub>-<sub>12</sub> olefin mixtures obtained in stage b) with an aromatic hydrocarbon in the presence of an alkylation catalyst for forming alkyl aromatic compounds, whereby linear olefins can also be added prior to the reaction, d) sulphonation of the alkyl aromatic compound obtained in stage c) and neutralisation of the same to form alkyl aryl sulphonates, whereby linear alkyl benzoles can also be added prior to sulphonation, e) optional mixing of the alkyl aryl sulphonates obtained in stage d) with linear alkyl aryl sulphonates.

Title of Invention

A PROCESS FOR THE PREPARATION OF ALKYLARYLSULFONATES

Abstract

The invention relates to methods for producing alkyl aryl sulphonates by a) reaction of a C4 olefin mixture on a methathetical catalyst to produce an olefin mixture containing 2 pentene and/or 3 hexene and optionally the separation of 2 pentene and/or 3 hexene, b) dimerisation of the 2 pentene and/or 3 hexene obtained in stage a) on a dimerisation catalyst to obtain a mixture containing C10-12 olefins and the optional separation of said C10-12 olefins, c) reaction of the C10-12 olefin mixtures obtained in stage b) with an aromatic hydrocarbon in the presence of an alkylation catalyst for forming alkyl aromatic compounds, whereby linear olefins can also be added prior to the reaction, d) sulphonation of the alkyl aromatic compound obtained in stage c) and neutralisation of the same to form alkyl aryl sulphonates, whereby linear alkyl benzoles can also be added prior to sulphonation, e) optional mixing of the alkyl aryl sulphonates obtained in stage d) with linear alkyl aryl sulphonates.

Full Text	The present invention relates to a process for the preparation of alkylarylsulfonates, to alkylarylsulfonates obtainable by the process, and to alkylaryls obtainable in the process as intermediate, to the use of the alkylarylsulfonates as surfactants, preferably in detergents and cleaners, and to detergents and cleaners comprising these alkylarylsulfonates. Alkylbenzenesulfonates (ABS) have been used for a long time as surfactants in detergents and cleaners. Following the use initially of surfactants based on tetrapropylene, which, however, had poor biodegradability, alkylbenzenesulfonates which are as linear as possible (LAS) have since been prepared and used. However, linear alkylbenzenesulfonates do not have adequate property profiles in all areas of application. First, for example, it would be advantageous to improve their low-temperature washing properties or their properties in hard water. Likewise desirable is the ready ability to be formulated, derived from the viscosity of the sulfonates and their solubility. These improved properties are obtained by slightly branched compounds or mixtures of slightly branched compounds with Unear compounds, although it is imperative to achieve the correct degree of branching and/or the correct degree of mixing. Too much branching adversely affects the biodegradability of the products. Products which are too linear have a negative effect on the viscosity and the solubility of the sulfonates. Moreover, the proportion of terminal phenylalkanes (2-phenylalkanes and 3-phenylalkanes) relative to internal phenylalkanes (4-, 5-, 6- etc. phenylalkanes) plays a role for the product properties, A 2-phenyl fraction of about 30% and a 2- and 3-phenyl fraction of about 50% can be advantageous with regard to product quality (solubility, viscosity, washing properties). Surfactants with very high 2- and 3-phenyl contents can have the considerable disadvantage that the processability of the products suffers as a result of a sharp increase in the viscosity of the sulfonates. Moreover, the solubility behavior may not be optimum. Thus, for example, the Krafft point of a solution of LAS with very high or very low 2- or 3-phenyl fractions is up to 10-20°C higher than in the case of the optimal choice of the 2-and 3-phenyl fraction. The process according to the invention offers the essential advantage that, as a result of the combination of metathesis and dimerization, a unique olefin mixture is obtained which, following alleviation of an aromatic, sulfonation and neutralization, produces a surfactant notable for its combination of excellent application properties (solubility, viscosity, stability against water hardness, washing properties, biodegradability). With regard to the biodegradability of alkylarylsulfonates, compounds which are adsorbed less strongly to clarification sludge than traditional LAS are particularly advantageous. For this reason, alkylbenzenesulfonates which are branched to a certain degree have been developed. For example, US 3,442,964 describes the dimerization of C5-8-hydrocarbons in the presence of a cracking catalyst coated with a transition metal, giving predominantly olefins having two or more branches. These olefins are subsequently alkylated with benzene to give a nonlinear alkylbenzene. For example, a mixture of hexenes is dimerized over a silicon dioxide-aluminum oxide cracking catalyst and then alkylated using HF as catalyst. WO 88/07030 relates to olefins, alkylbenzenes and alkylbenzenesulfonates which can be used in detergents and cleaners. In the process, propene is dimerized to give hexene, which in turn is dimerized to give largely linear dodecene isomers. Benzene is then alkylated in the presence of aluminum halides and hydrofluoric acid. US 5,026,933 describes the dimerization of propene or butene to give monoolefins, where at least 20% of C12-olefms which have a degree of branching of from 0.8 to 2.0 methyl groups/alkyl chain and have only methyl groups as branches. Aromatic hydrocarbons are alkylated over a shape-selective catalyst, preferably dealuminated MOR. WO 99/05241 relates to cleaners which comprise branched alkylarylsulfonates as surfactants. The alkylarylsulfonates are obtained by dimerization of olefins to give vinylidine olefins, and subsequent alkylation of benzene over a shape-selective catalyst, such as MOR or BEA. This is followed by sulfonation. The olefins hitherto used for the alkylation partly have too high or too low a degree of branching or do not produce an optimal ratio of terminal to internal phcnylalkanes. Alternatively, they are prepared from costly starting materials, such as, for example, propene or alpha-olefins, and sometimes the proportion of the olefin fractions which is of interest for the preparation of surfactants is only about 20%. This leads to costly work-up steps. The object of the present invention is to provide a process for the preparation of alkylarylsulfonates which are at least partially branched and thus have advantageous properties for use in detergents and cleaners compared with known compounds. In particular, they should have a suitable profile of properties of biodegradability, insensitivity toward water hardness, solubility and viscosity during the preparation and during use. In addition, the alkylarylsulfonates should be preparable in a cost-effective manner. We have found that this object is achieved according to the invention by a process for the preparation of alkylarylsulfonates by a) reaction of a C4-olefin mixture over a metathesis catalyst for the preparation of an olefin mixture comprising 2-pentene and/or 3-hexene, and optional removal of 2-pentene and/or 3-hexene, b) dimerization of the 2-pentene and/or 3-hexene obtained in stage a) over a dimerization catalyst to give a mixture containing C10-12-olefins, and optional removal of the C10-12-olcfins, c) reaction of the C10-12-olcfin mixtures obtained in stage b) with an aromatic hydrocarbon in the presence of alkylating catalyst to form alkylaromatic compounds, where, prior to the reaction, additional linear olefins may be added, d) sulfonation of the alkylaromatic compounds obtained in stage c), and neutralization to give alkylarylsulfonates, where, prior to the sulfonation, linear alkylbenzenes may additionally be added, e) optional mixing of the alkylarylsulfonates obtained in stage d) with linear alkylarylsulfonates. The combination of a metathesis of C4-olenns with a subsequent dimerization and alkylation of aromatic hydrocarbons permits the use of cost-effective starting materials and of preparation processes which make the desired products accessible in high yields. According to the invention, it has been found that the metathesis of C4-olefms produces products which can be dimerized to give slightly branched C10-12-olefm mixtures. These mixtures can be used advantageously in the alkylation of aromatic hydrocarbons, giving products which, following sulfonation and neutralization, result in surfactants which have excellent properties, in particular with regard to the sensitivity toward hardness-forming ions, the solubility of the sulfonates, the viscosity of the sulfonates and their washing properties. Moreover, the present process is extremely cost-effective since the product streams can be designed flexibly such that no byproducts are produced. Starting from a C4-stream, the metathesis according to the invention produces linear, internal olefins which are then converted into branched olefins via the dimerization step. Stage a) of the process according to the invention is the reaction of a C4-olefin mixture over a metathesis catalyst for the preparation of an olefin mixture comprising 2-pentene and/or 3-hexene, and optional removal of 2-pentene and/or 3-hexene, The metathesis can be carried out, for example, as described in WO 00/39058 or DE-A-100 13 253. In the specific case of the metathesis of acyclic olefins, a distinction is made between self-metathesis in which an olefin is converted into a mixture of two olefins of differing molar masses (for example: propene -> ethene + 2-butene), and cross- or cometathesis, which is a reaction of two different olefins (propene + 1-butene -> ethene + 2-pentene). If one of the reactants is ethene, this is generally referred to as ethenolysis. Suitable metathesis catalysts are, in principle, homogeneous and heterogeneous transition metal compounds, in particular those of transition groups VI to VIII of the Periodic Table of the Elements, and homogeneous and heterogeneous catalyst systems in which these compounds are present. Various metathesis processes starting from C4 streams can be used according to the invention. DE-A-199 32 060 relates to a process for the preparation of C5/C6-olefins by reaction of a feed stream which comprises 1-butene, 2-butene and isobutene to give a mixture of C2-6-olefins. In this process, propene, in particular, is obtained from butenes. In addition, hexene and methylpentene are discharged as products. No ethene is added in the metathesis. If desired, ethene formed in the metathesis is returned to the reactor. The preferred process for the preparation of optionally propene and hexene from a raffinate II feed stream comprising olefinic C4-hydrocarbons comprises a) carrying out a metathesis reaction in the presence of a metathesis catalyst which comprises at least one compound of a metal of transition group VIb, Vllb or VIII of the Periodic Table of the Elements, in the course of which, butenes present in the feed stream are reacted with ethene to give a mixture comprising ethene, propene, butenes, 2-pentene, 3-hexene and butanes, where, based on the butenes, up to 0,6 mol equivalents of ethene may be used, b) first separating the product stream thus obtained by distillation into optionally a low-boiling fraction A comprising C2-C3-olefms, and into a high-boiling fraction comprising C4-C6-olefins and butanes, c) then separating the low-boiling fraction A optionally obtained from b) by distillation into a fraction comprising ethene and a fraction comprising propene, where the fraction comprising ethene is returned to the process step a), and the fraction comprising propene is discharged as product, d) then separating the high-boiling fraction obtained from b) by distillation into a low-boiling fraction B comprising butenes and butanes, an intermediate-boiling fraction C comprising 2-pentene, and a high-boiling fraction D comprising 3-hexene, e) where the fractions B and optionally C are completely or partly returned to the process step a), and the fraction D and optionally C are discharged as product. The individual streams and fractions can comprise said compounds or consist thereof. In cases where they consist of the streams or compounds, the presence of relatively small amounts of other hydrocarbons is not ruled out. In this process, in a single-stage reaction procedure, a fraction consisting of C4-olefins, preferably n-butenes and butanes, is reacted in a metathesis reaction optionally with variable amounts of ethene over a homogeneous or, preferably, heterogeneous metathesis catalyst to give a product mixture of (inert) butanes, unreacted 1-butene, 2-butene, and the metathesis products ethene, propene, 2-pentene and 3-hexene, The desired products 2-pentene and/or 3-hexene are discharged, and the products which remain and unreacted compounds are completely or partly returned to the metathesis. They are preferably returned as completely as possible, with only small amounts being discharged in order to avoid accumulation. Ideally, there is no accumulation and all compounds apart from 3-hcxene are returned to the metathesis. According to the invention, up to 0.6, preferably up to 0.5, molar equivalents of ethene, based on the butenes in the C4 feed stream, are used. Thus, only small amounts of ethene compared with the prior art are used. If no additional ethene is introduced, only up to at most about 1.5%, based on the reaction products, of ethene form, which is recirculated, see DE-A-199 32 060. According to the invention, it is also possible to use larger amounts of ethene, the amounts used being significantly lower than in the known processes for the preparation of propene. In addition, the maximum possible amounts of C4 products and optionally C5 products present in the reactor discharge are recirculated according to the invention. This applies in particular to the recirculation of unreactcd 1-butene and 2-butene, and optionally of 2-pentene formed. If small amounts of isobutene are still present in the C4 feed stream, small amounts of branched hydrocarbons may also be formed. The amount of branched C5- and C6-hydrocarbons which may additionally be formed in the metathesis product is dependent on the isobutene content in the C4 feed and is preferably kept as low as possible ( In order to illustrate the process according to the invention in more detail in a plurality of variations, the reaction which takes place in the metathesis reactor is divided into three important individual reactions: Depending on the respective demand for the target products propene and 3-hexenc (the designation 3-hexene includes any isomers formed), and/or 2-pentene, the external mass balance of the process can be influenced in a targeted way by means of variable use of ethene and by shifting the equilibrium by recirculation of certain substrcams. Thus, for example, the yield of 3-hexene is increased by suppressing the cross-metathesis of 1-butene with 2-butene by recirculation of 2-pentene to the metathesis step, so that no or extremely little 1-butene is consumed here. During the self-metathesis of 1-butene to 3-hexene, which then preferably proceeds, ethene is additionally formed, which reacts in a subsequent reaction with 2-butene to give the desired product propene. Olefin mixtures which comprise 1-butene and 2-butene and optionally isobutene are obtained, inter alia, as C4 fraction in various cracking processes, such as steam cracking or fluid catalytic cracking. As an alternative, it is possible to use butene mixtures as are produced during the dehydrogenation of butanes or by dimerization of ethene. Butanes present in the C4 fraction have inert behavior. Dienes, alkynes or enynes are removed using customary methods such as extraction or selective hydrogenation prior to the metathesis step according to the present invention. The butene content of the C4 fraction used in the process is 1 to 100% by weight, preferably 60 to 90% by weight. The butene content is here based on 1-butene, 2-butene and isobutene. Preference is given to using a C4 fraction produced during steam clicking or fluid catalytic cracking or during the dehydrogenation of butane. Here, the C4 fraction used is preferably raffinate II, the C4 stream being freed from undesirable impurities by appropriate treatment over adsorber guard beds, preferably over high-surface-area aluminum oxides or molecular sieves, prior to the metathesis reaction. The low-boiling fraction A optionally obtained from step b), which comprises C2-C3-olefins, is separated by distillation into a fraction comprising ethene and a fraction comprising propene. The fraction comprising ethene is then recirculated to process step a), i,e. the metathesis, and the fraction comprising propene is discharged as product. In step d, the separation into low-boiling fraction B, intermediate-boiling fraction C and high-boiling fraction D can, for example, be carried out in a dividing wall column. Here, the low-boiling fraction B is obtained at the top, the intermediate-boiling fraction C is obtained via a middle outlet and the high-boiling fraction D is -obtained as bottoms. In order to be able to better handle the differing amounts of products produced in the flexibly controlled process, it is, however, advantageous to carry out a two-stage separation of the high-boiling fraction obtained from b). Preferably, the high-boiling fraction obtained from b) is firstly separated by distillation into a low-boiling fraction B comprising butenes and butanes, and a high-boiling fraction comprising 2-pentene and 3-hexene. The high-boiling fraction is then separated by distillation into fractions C and D. The two embodiments are explained in more detail in Figures 1 and 2, The metathesis reaction is here preferably carried out in the presence of heterogeneous metathesis catalysts which are not or only slightly isomerization-active and are selected from the class of transition metal compounds of metals of group VIb, Vllb or VIII of the Periodic Table of the Elements applied to inorganic supports. The preferred metathesis catalyst used is rhenium oxide on a support, preferably on y-aluminum oxide or on Al203/B203/Si02 mixed supports. In particular, the catalyst used is Re207/Y-Al203 with a rhenium oxide content of from 1 to 20% by weight, preferably 3 to 15% by weight, particularly preferably 6 to 12% by weight. The metathesis is, when carried out in a liquid phase, preferably carried out at a temperature of from 0 to 150°C, particularly preferably 20 to 80°C, and at a pressure of from 2 to 200 bar, particularly preferably 5 to 30 bar. If the metathesis is carried out in the gas phase, the temperature is preferably 20 to 300°C, particularly preferably 50 to 200°C, The pressure in this case is preferably 1 to 20 bar, particularly preferably 1 to 5 bar. The preparation of C5/C6-olefins and optionally propenc from steam cracker or refinery C4 streams may comprise the substeps (1) to (4): (1) removal of butadiene and acetylenic compounds by optional extraction of butadiene with a butadiene-selective solvent and subsequently /or selective hydrogenation of butadienes and acetylenic impurities present in crude C4 fraction to give a reaction product which comprises n-butenes and isobutene and essentially no butadienes and acetylenic compounds, (2) removal of isobutene by reaction of the reaction product obtained in the previous stage with an alcohol in the presence of an acidic catalyst to give an ether, removal of the ether and the alcohol, which can be carried out simultaneously with or after the etherification, to give a reaction product which comprises n-butenes and optionally oxygen-containing impurities, it being possible to discharge the ether formed or back-cleave it to obtain pure isobutene, and to follow the etherification step by a distillation step for the removal of isobutene, where, optionally, introduced C3-, i-C4- and C5-hydrocarbons can also be removed by distillation during the work-up of the ether, or oligomerization or polymerization of isobutene from the reaction product obtained in the previous stage in the presence of an acidic catalyst whose acid strength is suitable for the selective removal of isobutene as oligoisobutene or poly isobutene, to give a stream containing 0 to 15%) of residual isobutene, (3) removal of the oxygen-containing impurities from the product of the preceding steps over appropriately selected adsorber materials. (4) metathesis reaction of the resulting raffinate II stream as described. The substep of selective hydrogenation of butadiene and acetylenic impurities present in crude C4 fraction is preferably carried out in two stages by bringing the crude C4 fraction in the liquid phase into contact with a catalyst which comprises at least one metal selected from the group consisting of nickel, palladium and platinum on a support, preferably palladium on aluminum oxide, at a temperature of from 20 to 200°C, a pressure of from 1 to 50 bar, a volume flow rate of from 0.5 to 30 m3 of fresh feed per m3 of catalyst per hour and a ratio of recycle to feed stream of from 0 to 30 with a molar ratio of hydrogen to diolefms of from 0.5 to 50, to give a reaction product in which, apart from isobutene, the n-butenes 1-butcne and 2-butene are present in a molar ratio of from 2:1 to 1:10, preferably from 2:1 to 1:3, and essentially no dioletlns and acetylenic compounds are present. For a maximum yield of hexene, 1-butene is preferably present in excess, and for a high protein yield, 2-butene is preferably present in excess. This means that the overall molar ratio in the first case can be 2:1 to 1:1 and in the second case 1:1 to 1:3. The substep of butadiene extraction from crude C4 fraction is preferably carried out using a butadiene-selective solvent selected from the class of polar-aprotic solvents, such as acetone, furfural, acetonitrile, dimethylacetamide, dimethylformamide and N-methylpyrrolidone, to give a reaction product in which, following subsequent selective hydrogenation/ isomerization, the n-butenes 1-butene and 2-butene are present in a molar ratio 2:1 to 1:10, preferably from 2:1 to 1:3. The substep of isobutene etherification is preferably carried out in a three-stage reactor cascade using methanol or isobutanol, preferably isobutanol, in the presence of an acidic ion exchanger, in which the stream to be etherified flows through flooded fixed-bed catalysts from top to bottom, the rector inlet temperature being 0 to 60°C, preferably 10 to 50°C, the outlet temperature being 25 to 85°C, preferably 35 to 75°C, the pressure being 2 to 50 bar, preferably 3 to 20 bar, and the ratio of isobutanol to isobutene being 0.8 to 2.0, preferably 1.0 to 1.5, and the overall conversion corresponding to the equilibrium conversion. The substep of isobutene removal is preferably carried out by oligomerization or polymerization of isobutene starting from the reaction mixture obtained after the above-described stages of butadiene extraction and/or selective hydrogenation, in the presence of a catalyst selected from the class of homogeneous and heterogeneous Broensted or Lewis acids, see DE-A-lOO 13 253, Selective hydrogenation of crude C4 fraction Alkynes, alkynenes and alkadienes are undesired substances in many industrial syntheses owing to their tendency to polymerize or their pronounced tendency to form complexes with transition metals. They sometimes have a very strong adverse effect on the catalysts used in these reactions. The C4 stream of a steam cracker contains a high proportion of polyunsaturated compounds such as 1,3-butadiene, 1 -butyne (ethylacctylene) and butenyne (vinylacctylene). Depending on the downstream processing present, the polyunsaturated compounds are either extracted (butadiene extraction) or are selectively hydrogenated. In the former case, the residual content of polyunsaturated compounds is typically 0.05 to 0,3% by weight, and in the latter case is typically 0.1 to 4.0% by weight. Since the residual amounts of polyunsaturated compounds likewise interfere in the further processing, a further concentration by selective hydrogenation to values Alternative; Extraction of butadiene from crude C4 fraction The preferred method of isolating butadiene is based on the physical principle of extractive distillation. The addition of selective organic solvents lowers the volatility of specific components of a mixture, in this case butadiene. For this reason, these remain with the solvent in the bottom of the distillation column, while the accompanying substances which were not previously able to be separated off by distillation can be taken off at the top. Solvents used for the extractive distillation are mainly acetone, furfural, acetonitrile, dimethylacetaminde, dimethylformamide (DMF) and N-methylpyrrolidone (NMP). Extractive distillations arc particularly suitable for butadiene-rich C4 cracker fractions having a relatively high proportion of alkynes, including methylacetylene, ethylacctylene and \ inytacctylene, and methylallene. The simplified principle of solvent extraction from crude C4 fraction can be described as follows: the completely vaporized C4 fraction is fed to an extraction column at its lower end. The solvent (DMF, NMP) flows from the top in the opposite direction to the gas mixture and on its Way downwards becomes laden with the more soluble butadiene and small amounts of butenes. At the lower end of thc extraction column, part of the pure butadiene which has been isolated is fed in in order to drive out the butenes as far as possible. The butenes leave the separation column at the top. In a further column, referred to as a degasser, the butadiene is freed from the solvent by boiling out and is subsequently purified by distillation. The reaction product from an extractive butadiene distillation is usually fed to the second stage of a selective hydrogenation in order to reduce the residual butadiene content to values of Ihc C4 stream remaining after butadiene has been separated off is referred to as C4 raffinate or raffmatc I and comprises mainly the components isobutene, 1-butene, 2-butenes, and n- and isobutancs. Separating off isobutene from raffinate I In the further separation of the C4 stream, isobutene is preferably isolated next since it differs from the other C4 components by virtue of its branching and its higher reactivity. Apart from the possibility of a shape-selective molecular sieve separation, by means of which isobutene can be isolated in a purity of 99% and n-butenes and butane adsorbed on the molecular sieve pores can be desorbed again using a higher-boiling hydrocarbon this is carried out in the first instance by distillation using a so-called deisobutenizer, by means of which isobutene is separated off together with 1-butene and isobutene at the top, and 2-butenes and n-butane together with residual amounts of iso- and 1-butene remain in the bottoms, or extractively by reaction of isobutene with alcohols over acidic ion exchangers. Methanol (-> MTBH) or isobutanol (IBTBE) are preferably used for ihis purpose. The preparation of MTBE from methanol and isobutene is carried out at 30 to 100°C and at a pressure slightly above atmospheric pressure in the liquid phase ()\ er acidic ion exchangers. The process is carried out either in two reactors or in a twp-stage shaft reactor in order to achieve virtually complete isobutene conversion ( ' 99%). The pressure-dependant azeotrope formation between methanol and NllRl' requires a multistage pressure distillation to isolate pure MTBE, or is acliieved by relatively new technology using methanol adsorption on adsorber resins. All other components of the C4 fraction remain unchanged. Since small proportions of diolefins and acetylenes can shorten the life of the ion exchanger as a result of polymer formation, preference is given to using bifunctional PD-containing ion exchangers, in the case of which, in the presence of small amounts (^f hydrogen, only diolefins and acetylenes are hydrogenated. The cthvrification of the isobutene remains uninlluenced by this. MTBI- serves primarily to increase the octane number of gasoline. MTBE and IBTBE can alternatively be back-cleaved in the gas phase at 150 to 300°C over acidic oxides to obtain pure isobutene. /\ further possibility for separating off isobutene from raffinate I consists in the direct synthesis of oligo/polyisobutene. In this way it is possible, over acidic homogeneous and heterogeneous catalysts, such as e.g, tungsten trioxide and titanium dioxide, and at isobutene conversions up to 95%, to obtain a product stream which has a residual isobutene content of a maximum of 5%i, Feed purification of the raffinate 11 stream over adsorber materials To improve the operation life of catalysts used for the subsequent metathesis step, it is necessary, as described above, to use a feed purification (guard bed) for removing catalyst poisons, such as, for example, water, oxygen-containing compounds, sulfur or sulfur compounds or organic halides. Processes for adsorption or adsorptive purification are described, for example in W. Kast, Adsorption aus der Gasphase, VCH, Weinheim (1988). The use a zeolitic adsorbents is described in D.W. Breck, Zeolite Molecular Sieves Wire New York (1974). The resulting reaction product is referred to as nullinate 1 and in addition to isobutene, has 1-butene and 2-butene in a molar ratio at from 2:1 to 1:10, preferably from 2:1 to 1:3. The raffinate II stream which remains is virtually free from containing compounds, organic chlorides and sulfur compounds. • acetonitrile(pentacarbonyl)tungsten in J. Catal. 1975, 38, 482-484: trichloro(nitrosyl)molybdenum(II) as catalyst precursor in Z. Chem. iT-i ; ; 284-285; • W(CO)5PPH3/EtAlCl2 in J. Catal. 1974, 34,196-202; • WCyn-BuLi in J. Catal 1973, 28, 300-303; • WCyn-BuLi in J. Catal. 1972, 26, 455-458; FR 2 726 563: 03ReO[AI(OR)(L)xO]nRe03 where R = Ci-C4o-hydrocarbon, n - 1-10, X ^ 0 or 1 and L ^ solvent, EP-A'191 0 675, EP-A-129 0 474, BE 899897: catalyst systems comprising tungsten, 2-substituted phenoxide radicals and 4 other ligands, including a halogen, alkyl or carbene group, FR 2 499 083: catalyst system comprising a tungsten, molybdenum or rhenium oxo transition metal complex with a Lewis acid, US 4,060,468: catalyst system comprising a tungsten salt, an oxygen-containing aromatic compound, e.g. 2,6-dichlorophenol and, if desired, molecular oxygen, BE 776,564: catalyst system comprising a transition metal salt, an organometallic compound and an amine. To improve the cycle time of the catalysts used, especially of the supported catalysts, it is advisable to purify the feed over adsorber beds (guard beds). The guard bed serves here to dry the C4 stream and to remove substances which may act as catalyst poisons in the subsequent metathesis step. The preferred adsorber materials are Selexsorb CD and CDO and 3A and NaX molecular sieves (13X). The purification is carried out in drying towers at temperatures and pressures which are preferably chosen such that all of the components are present in the liquid phase. Optionally, the purification step is used for preheating the feed for the subsequent methathesis step. It may be advantageous to combine two or more purification steps with one another or to connect them in series. Pressure and temperature in the metathesis step is chosen such that all reactants are present in the liquid phase (usually - 0 to 150°C, preferably 20 to 80°C; p = 2 to 200 bar). Alternatively, it may, however, be advantageous, particularly in the case of feed streams having a relatively high isobutene content, to carry out the reaction in the gas phase and/or to use a catalyst which has lower acidity. The reaction is generally complete after from 1 s to 1 h, preferably after 30 s to 30 min. It may be carried out continuously or batchwise in reactors such as For the dimerization, preference is given to using the interned linear rentenes and hexenes present in the metathesis product. Particular prcference is given to using 3-hexene. Within the scope of the above details, the dimerizarion cataly and the reaction conditions are preferably chosen such that al least SO" of the components of the dimcrization mixture have one branch, or two branches on adjaeent carbon atoms, in the range from 1/4 to 3/4, preferably from 1 a lo 23 of the chian length of their main chain. A very characteristic feature of the olefin mixtures prepared according to the invention is their high proportion - generally greater than 75%, in particular greater than 80% - of components with branches, and the low proportion - generally below 25%, in particular below 20% - of unbranched olefins. A further characteristic is that, at the branching sites of the main chain, predominantly groups having (y-4) and (y-5) carbon atoms are bonded, where y is the number of carbon atoms of the monomer used for the dimerization. The value (y-5) = 0 means that no side chain is present. In the case of the C12-olefin mixtures prepared according to the invention, the main chain preferably carries methyl or ethyl groups at the branching points. The position of the methyl and ethyl groups on the main chain is likewise characteristic: in the case of mono-substitution, the methyl or ethyl groups are in the position P = (n/2)m of the main chain, where n is the length of the main chain and m is the number of carbon atoms in the side groups, and in the case of disubstitution products, one substituent is in the position P and the other is on the adjacent carbon atom P+1. The proportions of monosubstitution products (single branching) in the olefin mixture prepared according to the invention are characteristically in total in the range from 40 to 75% by weight, and the proportions of double-branched components are in the range from 5 to 25% by weight. The olefin mixtures obtainable by the above process (cf. WO 00/39058) are valuable intermediates particularly for the preparation, described below, of branched alkylaromatics for the preparation of surfactants. Stage c) In stage c), the C10-12-olefm mixture obtained in stage b) is reacted with an aromatic hydrocarbon in the presence of an alkylation catalyst to form alkylaromatic compounds. Here preference is given to usingan alkylation catalyst which leads to alkylaromatic compounds which have in the alkyl radical, one to three carbon atoms with an H/C index of 1. Where a fixed-bed reactor is used, the reactant can be introducted either in cocurrent or in countercurrent. Realization as a catalytic distillation is also possible. The reactants are either in the liquid and/or in the gasoons state. The reaction temperature is chosen such that, on the one hand, as complete as possible a conversion of the olefin takes place and, on the other hand, the fewest possible by-products arise. The choice of temperature also depends decisively on the catalyst chosen. Reaction temperatures between 50°C and 500°C (preferably 80 to 350°C, particularly preferably 80-250°C) can also be used. The pressure of the reaction depends on the procedure chosen (reactor type) and is between 0.1 and 100 bar, and the space velocity (WHSV) is chosen between 0.1 and 100. The reactants can optionally be diluted with inert substances. Inert substances arc preferably paraffins. The ratio of aromatic compound : olefin is usually set between 1;1 and 100:1 (preferabty 2:1-20:1). Aromatic feed substances All aromatic hydrocarbons of the formula Ar-R are possible, where Ar is a monocyclic or bicyclic aromatic hydrocarbon radical, and R is chosen from If C10, preferably C1-3-alkyl, OH, OR etc., preferably H or C10-alkyl Preference is given to benzene and toluene. Stage d) In stage d), the alkylaromatic compounds obtained in stage c) are sulfonated and neutralized to give alkylarylsulfonates. The alkylaryls are converted into alkylarylsulfonates by 1) sulfonation (e.g. with SO3, oleum, chlorosulfonic acid, etc., preferably with SO3) and 2) neutralization (e.g. with Na, K, NH4, Mg compounds, preferably with Na compounds). Sulfonation and neutralization are adequately described in the literature and are carried out in accordance with the prior art. The sulfonation is preferably carried out in a falling-film reactor, but can also bo carried out in a stirred-lank reactor. The sulfonation with SO3 is to be preferred over the sulfonation with oleum. Noncxhaustive examples of customary ingredients of detergents and cleaners according to the invention are listed below. Bleach Examples are alkali metal perborates or alkali metal carbonate perhydratcs, in particular the sodium salts. One example of an organic peracid which can be used is peracetic acid, which is preferably used in commercial textile washing or commercial cleaning. Bleach or textile detergent compositions which can be used advantageously comprise C1-12-percarboxylic acids, C8-16-dipercarboxylic acids, imidopercarboxylic acids or aryldipercarboxylic acids. Preferred examples of acids which can be used are peracetic acid, linear or branched ectane-, nonanc-, dccanc-or dodecane-monoper-acids, decane- and dodecane-diperacid, mono- and diperphthalic acids, -isophthalic acids and -terephthalic acids. phthalimidopercaproic acid and terephthaloyldipercaproic acid. It is likcwisc possible to use polymeric peracids, for example those which contain the acrylic acid basic building blocks in which a peroxy function is present. The pcrcarboxylic acids may be used as free acids or as salts of the acids, preferably alkali metal or alkaline earth metal salts. Bleach activator Bleach catalysts are, for example, quatemized imines and sulfonimincs. as described, for example, in US 5,360,568, US 5,360,569 and EP-A-0 453 003. and also manganese complexes as described, for example, in WO-A 94/21777. Futhcr metal-containing bleach catalysts which may be used are described in EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 272. Bleach activators are, for example, compounds from the classes of substance below: textile treatment at low temperatures, and also those which are suitable in a number of temperature ranges up to and including the traditional range of the boil wash Anionic surfactants Suitable anionic surfactants arc the linear andA)r slightly branched alkylben/enesulfonates (LAS) according to the invention. Further suitable anionic surfactants are. tor example, fatty alcohol sulfates of tatty alcohols having 8 to 22. preferably 10 to 18, carbon atoms, e.g. C9- to C11-alcohol sulfates, C12 to C13-alcohol sulfates, cetyl sulfate, niyrisiy! sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate. Further suitable anionic surfactants arc sulfated ethoxylated C^- to C22-aIcohols (alkyl ether sulfates) or soluble salts thereof. Compounds of this type are prepared, for example, by firstly alkoxylating a C8- to C22-alcohol preferably a C10-C18-alcohol e.g. a fatty alcohol, and then sulfating the alkoxylation product. For the alkoxylation, preference is given to using ethylene oxide, in which case 2 to 50 mol, preferably 3 to 20 mol, of ethylene oxide are used per mole of fatty alcohol. The alkoxylation of the alcohols can, however, also be carried out using propylene oxide on its own and optionally butylene oxide. Also suitable are those alkoxylatcd C8- to C22-alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide. The alkoxylatcd CK to C2:-alcohols may contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in random distribution. Further suitable anionic surfactants are N-acylsarcosinates having aliphatic saturated or unsaturated C8- to C25-acyl radicals, preferably C10 to C20-acyl radicals, e.g. N-oleoylsarcosinate. The anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal salts, such as sodium, potassium and lithium and ammonium salts such as, for example, hydroxyethylammonium, di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium salts. The detergents according to the invention preferably comprise C10- to C13-linear and/or slightly branched alkvlbenzenesulfonates (LAS). Nonionic surfactants Suitable nonionic surfactants arc. for example, alkoxylated C8- to C22-alcohols, such as fatlv alcohol alkoxvlatcs or oxo alcohol alkoxvlates. The alkoxylation can be carried out with ethylene oxide, propylene oxide and/or bulylene oxide-Surfactants which can be used here are any alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide in added form. Block polymers of ethylene oxide, propylene oxide and/or butylene oxide are also suitable here, or addition products which contain said alkylene oxides in random distribution. Per mole of alcohol 2 to 50 mok preferably 3 to 20 mol of at least one alkylene oxide are used. The alkylene oxide used is preferably ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms. A further class of suitable nonionic surfactants are alkylphenol ethoxylates having C6-C14-alkyl chains and 5 to 30 mol of ethylene oxide units. Another class of nonionic surfactants are alkyl polyglucosides having 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain. These compounds contain at most 1 to 20, preferably 1.1 to 5, glucoside units. Another class of nonionic surfactants are N-alkvl-ulucamides of the structure II or III The detergents according to the invention preferably comprise C10C16-alcohols ethoxylated with 3-12 mol of ethylene oxide, particularly preferably elhoxylated fattv alcohols -as nonionic surfactants. Organic cobuilders Examples of suitable low molecular weight polycarboxylates as organic cobuilders are: C4- to C20-di-, -tri- and -tetracarboxylic acids, such as, for example, succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetra-carboxylic acid and alkyl- and alkenylsuccinic acids having C2- to C16-alkyl or -alkenyl radicals; C4- to C10-hydroxycarboxylic acids, such as, tor example, malic acid, tartaric acid, gluconic acid, glucaric acid, citric acid, lactobionic acid and sucrose mono-, -di-and -tricarboxylic acid; aminopolycarboxylates, such as, for example, nitrilo-triacetic acid, methylglycinediacetic acid, alaninediaeetic acid, ethylenediamineietraacetic acid and serinediacetic acid; salts of phosphonic acids, such as, for example, hydroxyethanediphosphonic acid, ethylenediaminctetra(methylenephosphonate) and diethylenetriaminepenta- (methylenephosphonate). Examples of suitable oligomeric or polymeric polycarboxylates as organic cobuilders are: oligomaleic acids, as described, for example, in EP-A-451 508 and EP-A-396 303; CO- and terpolymers of unsaturated C4-C8-dicarboxyUc acids, where, as comonomers, monoethylenically unsaturated monomers from group (i) in amounts of up to 95% by weight from group (ii) in amounts of up to 60% by weight from group (iii) in amounts of up to 20?^) by weight may be present in copolymerized form. Examples of suitable unsaturated C4-C8-dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid. The group (i) includes monoethylenically unsaturated C3-C8-monocarboxylic acids, such as, for example, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. Preference is given to usintz acrylic acid and methacrylic acid from group (i). The group (ii) includes monoethylenically unsaturated C2-C22-oIeflns, vinyl alky! ethers having C\|-Cs-alkyl groups, styrenc, vinyl esters of C1-C8 carboxylic acids, (meth)acrylamide and vinylpyrrolidone. Preference is given to using C2-C6-oletms. vinyl alkyl ethers having C1-C4-alkyl groups, vinyl acetate and vinyl propionate from group (ii). The group (iii) includes (meth)acrylic esters of C1-C8-alcohols, (meth)acrylonitrile, (meth)acrylamides of C1-C8-amines, N-vinylformamide and vinylimidazole. If the polymers of group (ii) contain vinyl esters in copolymerized form, these may also be present partly or completely in hydrolyzed form to give vinyl alcohol structural units. Suitable co- and terpolymers are known, for example, from US-A 3 887 806 and DE-A 43 13 909. As copolymers of dicarboxylic acids, suitable organic cobuilders are preferably: copolymers of maleic acid and acrylic acid in the weight ratio 10:90 to 95:5, particularly preferably those in the weight ratio 30:70 to 90:10 having molar masses of from 10 000 to 150 000; terpolymers of maleic acid, acrylic acid and a vinyl ester of a Ci-Crcarboxylic acid in the weight ratio 10(maleic acid):9()(acrylic acid + vinyl ester) to 95(maleic acid):5(acrylic acid f- vinyl ester), where the weight ratio of acrylic acid to vinyl ester can vary in the range from 20:80 to 80:20. and particularly preferably terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate in the weight ratio 20(maleic acid):80{acrylic acid + vinyl ester) to 90(maleic acid):10(acrylic acid + vinyl ester), where the weight ratio of acrylic acid to the vinyl ester can vary in the range from 30:70 to 70:30; copolymers of maleic acid with C2-C8-olefms in the molar ratio 40:60 to 80:20, where copolymers of maleic acid with ethylene, propylene or isobutane in the molar ratio 50:50 are particularly preferred. Graft polymers of unsaturated carboxylic acids to low molecular weight carbohydrates or hydrogenated carbohydrates, cf. IJS-A 5,227,446, DE-A-44 15 623, DE-A-43 13 909. are likewise suitable as organic cobuilders. Examples of suitable unsaturated carboxylic acids in this connection are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, and mixtures of acrylic acid and maleic acid which are grafted on in amounts of from 40 to 95% by weight, based on the component to be grafted. For the modification, it is additionally possible for up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers to be present in copolymerized form. Suitable modifying monomers are the abovementioned monomers of groups (ii) and (iii). Suitable graft bases are degraded polysaccharides, such as, for example, acidic or enzymaticaliy degraded starches, inulins or cellulose, reduced (hydrogenated or reductively aminated) degraded polysaccharides, such as, for example, mannitol, sorbitol, aminosorbitol and glucamine, and also polyalkylene glycols having molar masses up to Mw = 5 000, such as, for example, polyethylene glycols, ethylene oxide/propylene oxide or ethylene oxide/butylene oxide block copolymers, random ethylene oxide/propylene oxide or ethylene oxide/butylene oxide copolymers. alkoxylated mono- or polybasic C1-C22-alcohols. cf. US-A 4.746,456. From this group, preference is given to using grafted degraded or degraded reduced starches and grafted polyethylene oxides, in which case 20 to 80% by weight of monomers, based on the graft component, are used in the graft polymerization. I'or the grafting, preference is given to using a mixture of maleic acid and acr\lic acid in the weight ratio from 90:10 to 10:90. Polyglyoxylic acids as organic cobuilders are described, for example, in EP-B-001 004, US-A 5,399,286, DH-A-4106 355 and r:P-A-656 914. Hie end-groups of the polyglyoxylic acids may have different structures. Polyamidocarboxylic acids and modified polyamidocarboxylic acids as organic cobuilders are known, for example, from EP-A-454 126, r;P-B-511 037. WO-A 94/01486 and EP-A-581 452. As organic cobuilders, preference is also given to using polyaspartic acid or cocondensates of aspartic acid with further amino acids, C4-C25-mono- or -dicarboxylic acids and/or C4-C25-mono- or -diamines. Particular preference is given to using polyaspartic acids prepared in phosphorus-containing acids and modified with C6,-C22-mono- or -dicarboxylic acids or with C6-'C22-mono' or -diamines. Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds as organic cobuilders are known, for example, from WO-A 93 22362 and WO-A 92/16493. Such carboxyl-containing condensates usually have molar masses up to 10 000, preferably up to 5 000. Antiredeposition agents and soil release polymers Suitable soil release polymers and/or antiredeposition agents for detergents are, for example: polyesters of polyethylene oxides with ethylene glycol and/or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids; polyesters of polyethylene oxides terminally capped at one end with di- and/or polyhydric alcohols and dicarboxylic acid. Such polyesters are known, for example from US-A 3,557.039, GB-A 1 154 730, EP-A-185 427. EP-A-241 984. t:P-A-24I 985. EP-A-272 033 and US-A 5 J 42.020. Further suitable soil release polymers are amphiphilic graft or copolymers of vinyl and/or acrylic esters on polyalkylene oxides (of: US-A 4,746,456, US-A 4,846,995, DE-A-37 11 299, US-A 4,904,408, US-A 4,846.994 and US-A 4,849.126) or modified celluloses, such as, for example, methylcellulose, hydroxypropylcellulose or carboxymethylcellulose. Color-transfer inhibitors Examples of the color-transfer inhibitors used are homo- and copolymers of vinylpyrrolidone. vinylimidazole, vinyloxazolidone and 4-vinylpyridine N-oxide having molar masses of from 15 000 to 100 000, and crosslinked finely divided polymers based on these monomers. The use mentioned here of such polymers is known. cf. DE-B-22 32 353, DE-A-28 14 287, DE-A-28 14 329 and DE-A-43 16 023. Enzymes Suitable enzymes are, for example, proteases, amylases, lipases and cellulases. in particular proteases. It is possible to use two or more enzymes in combinadon. In addition to use in detergents and cleaners for the domestic washing of textiles, the detergent compositions which can be used according to the invention can also be used in the sector of commercial textile washing and of commercial cleaning. In this field of use. peracetic acid is usually used as bleach, which is added to the wash liquor as an aqueous solution. Use in textile detergents A typical pulverulent or granular hcavv-dutv detergent accordina to the invention may, for example, have the following composition: 0.5 to 50% by weight, preferably 5 to 30% by weight, of at least one' anionic and/or nonionic surfactant, 0.5 to 60% by weight, preferably 15 to 40% by weight, oi' at least niu.-inorganic builder, 0 to 20% by weight, preferably 0.5 to 8% by weight, of at least one organic cobuilder. 2 to 35% by weight, preferably 5 to 30% by weight, of an inorganic bloaclv 0.1 to 20% by weight, preferably 0.5 to 10% by weight, o'i a bleach activator, optionally in a mixture with further bleach activators. 0 to 1% by weight, preferably up to at most 0.5% by weight, of a bleach catalyst, 0 to 5%) by weight, preferably 0 to 2.5% by weight, of a polymeric color-transfer inhibitor, 0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, of protease. 0 to K5% by weight, preferably 0.1 to 1.0% by w^Mght, of lipase, 0 to 1.5% by weight, preferably 0.2 to 1.0%) by weight, of a soil release polymer, ad 100% with customary auxiliaries and adjuncts and water. Inorganic builders preferably used in detergents are sodium carbonate, sodium hydrogen carbonate, zeolite A and P. and amorphous and crystalline Na silicates. Organic cobuilders preferably used in detergents are acrylic acid;nia!c:c copolymers, acrylic acid/maleic acidVinyl ester terpolymers and citric acid. Inorganic bleaches preferably used in detergents are sodium perborate and sodium carbonate perhydrate. Example 3 2-Pentene from the rafflnate II metathesis was dimerized continuously as in example 2 over an Ni heterogeneous eatalyst. Fractional distillation of the product gave a decene fraction with a purity of 99.5%. Example 4 A mixture of 2-pentene and 3-hexene from the raffmate II methathesis was dimerized as in example 2 and example 3, Fractional distillation of the product gave a decene/undecene/dodecene fraction with a purity of 99.5% Example 5 The C12-olefin fraction from example 2 is alkylated with benzene in the molar ratio 1:10. For this, the reaction mixture is introduced into an autoclave (300 ml) which is equipped with a stirrer and a catalyst basket. 25% by weight, based on the mass of the olefin, of zeolite mordenith catalyst (MOR) are introduced into the catalyst basket. The autoclave is sealed and flushed twice with nitrogen (N2). The autoclave is then heated to 180°C. The reaction mixture is then reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas chromatography-mass spectrometry coupling. Excess benzene and low-boiling components are distilled off, and the alkylaryl mixture obtained is analyzed by means of gas chromatography-mass spectrometry coupling and C "'-NMR. Example 6 A 2 1 four-necked flask fitted with magnetic stirrer, thermometer, dropping funnel, gas inlet frit and gas outlet is charged with 1 900 g of SO3-depleted oleum. This flask is connected via the gas outlet to a 1 1 three-necked flask via a Viton hose. This 1 1 flask fitted with paddle stirrer, thermometer, gas inlet frit and gas outlet is charged with the alkylbenzene mixture from example 5. The depleted oleum is brought to 120°C in the SO3-developer, and the oleum (65% strength) is added via a dropping funnel over the course of 30 minutes. Using a stream of nitrogen of 80 1/h. the SO3 gas is stripped out and passed into the alkylbenzene via a 6 mm inlet tube. The temperature of the alkvlbenzene/alkvlbenzenesulfonic acid mixture increases slowly to 40°C and is maintained at 40°C using cooling water. 1 he residual gas is removed by suction using a water-jet pump. The molar ratio of SOj/alkylbenzene is 1.01:1. After a postreaction time of 4 h, the alkylbenzene-sulfonic acid formed is stabilized with 0.4% by weight of water and then neutralized with NaOK to give the alkylbenzenesulfonate. Example 7 A mixture of the C10-/C11/C12-olenn fractions from example 4 is alkylated with benzene in the molar ratio 1:10. For this, the reaction mixture is introduced into an autoclave (300 ml) which is provided with a stirrer and a catalyst basket. 25% by weight, based on the mass of the olefin, of zeolite mordenite catalyst (MOR) are introduced into the catalvst basket. The autoclave is sealed and Hushed twice with nitrogen (N2). The autoclave is then heated to 200°C]. The reaction mixture is reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas chromatography-mass spectrometry coupling. Excess benzene and low-boiling fractions are distilled off, and the alkylaryl mixture obtained is analyzed by means of gas chromatography-mass spectrometry coupling and C'-^^NMR. Example 8 The alkylbenzene mixture from example 7 is converted to the alkylbenzenesulfonate analogously to the description in example 6. Example 9 A mixture of the C10-/C11-/C12-olefin fractions from example 4 is alkylated with benzene in the molar ratio 1:2. For this, the reaction mixture is introduced into an autoclave (300 ml) which is provided with a stirrer and a catalyst basket. 5% by weight, based on the mass of the olefin, of zeolite ZSM-12 eatalyst are introduced into the eatalyst basket. The autoclave is sealed and Hushed twice with nitrogen (Ni). The autoclave is then heated to 18()°C. The reaction mixture is reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas ehromatography-mass spectrometry coupling. Excess benzene and low-boiling fractions are distilled off. and the alkylaryl mixture obtained is analyzed by means of gas chromatography-mass spectrometry coupling and C '-NMR. Example 10 '["he alkylbenzene mixture from example 9 is converted to the alkylbenzenesulfonate analogously to the description in example 6. Example 11 A C12-olefin fraction from example 2 is alkylated with benzene in the molar ratio 1:4. For this, the reaction mixture is introduced into an autoclave (300 ml) which is provided with a stirrer and a catalyst basket. 10% by weight, based on the mass of the olefin, of zeofite beta (BBA) catalyst are introduced into the catalyst basket. The autoclave is sealed and Hushed twice with nitrogen (NT). The autoclave is then heated to 180°C. The reaction mixture is reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas chromatography-mass spectrometry coupling. Excess benzene and low-boiling fractions are distilled off and the resuUing alkylaryl mixture is analyzed by means of gas chromatography-mass spectrometry coupling and C'^-NMR. Example 12 The alkylbenzene mixture from example 11 is converted to the alkylbenzenesulfonate analogously to the description in example 6. Example 13 A mixture of the C10-/C11-/C12-olenn fractions from example 4 is alkylated with benzene in the molar ratio 1:4. I'or this, the reaction mixture is introduced into an autoclave (300 ml) which is provided with a stirrer and a catalyst basket. 10% by weight, based on the mass of the olefin, of zeolite MCM-22 catalyst are introduced into the catalyst basket. The autoclave is scaled and flushed twice with nitrogen (N2) The autoclave is then heated to 200°C. The reaction mixture is reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas chromatography-mass spectrometry coupling. Excess benzene and low-boiling fractions are distilled off, and the resulting alkylaryl mixture is analyzed by means of gas chromatography-mass spectrometry coupling and C13-NMR. Example 14 I 1/h of oleum (65%) in concentrated sulfuric acid is introduced into a heated (120'C) 10 1 four-necked flask using a pump. 130 1/h of dry air are passed through the sulfuric acid via a frit; this air strips out the SO3. The S03-enriched stream of air (about 4% of SO3) is brought into contact with an alkylbenzene mixture from example 13 in a 2 m-long falling-film reactor, at approximately 40-50°C (10-15°C double-jacket water cooling), and sulfonates this mixture. The molar ratio oi' S03/alkylbenzene is 1.01:1. The reaction time in the falling-film reactor is approximately 10 sec. The product is pumped to an afterripening container where it remains for approximately 4-8 h. The sulfonic acid is then stabilized with 0.4% by weight of water and neutralized with NaOH to give the alkylbenzenesulfonate. Example 15 A C12-olefin fraction from example 2 is alkylated with benzene in the molar ratio 1:10. Thus, the reaction mixture is introduced into a four-necked flask (2 1), which is provided with a stirrer, a thermometer, a reflux condenser with a gas offtake and a dropping funnel. The flask is charged with benzene and AICI3, the temperature is increased to 80°C. and the olefin mixture is metered in slowly. The reaction mixture is allerreacted for 1/2 h, then cooled, any catalyst particles are llltered from the reaction mixture, and the reaction mixture is neutralized with NaOH, Washing with water is then carried out, and the product is dried. Excess benzene and low-boiling fractions are distilled off, and the resulting alkylaryl mixture is analyzed by means of gas chromatography-mass spectrometry coupling and C13-NMR. Example 16 The alkylben/ene mixture from example 15 is converted to the alkylbenzenesulfonate analogously to the description in example 6. "as enclosed to IPER" We claim: 1. A process for the preparation of alkylarylsulfonates by a) reaction of a C4-olefin mixture over a metathesis catalyst for the preparation of an olefin mixture comprising 2-pentene and/or 3-hexene, and optional removal of 2-pentene and/or 3-hexene, b) dimerization of the 2-pentene and/or 3-hexene obtained in stage a) over a dimerization catalyst to give a mixture containing C10-12-olefins. and optional removal of the C10-12-olefms, c) reaction of the C10-12-olefin mixtures obtained in stage b) with an aromatic hydrocarbon in the presence of an alkylating catalyst to form alkylaromatic compounds. d) sulfonation of the alkylaromatic compounds obtained in stage c), and neutralization to give alkylarylsulfonates. 2. A process as claimed in claim 1, wherein the metathesis catalyst in stage a) is chosen from compounds of a metal of transition groups VIb, Vllb or VIII of the Periodic Table of the Elements. 3. A process as claimed in either of claims 1 or 2, wherein, in stage b), a dimerization catalyst is used which contains at least one element from transition group VIII of the Periodic Table of the Elements, and the catalyst composition and the reaction conditions are chosen such that a dimer mixture is obtained which contains less than 10% by weight of compounds which have a structural element of the formula I (vinylidene group) 4. A process as claimed in any of claims 1 to 3, wherein the olefins obtained in stage b) have a proportion of unbranched olefins of less than 25% by weight, 5. A process as claimed in any of claims 1 to 4, wherein at least 80% of the olefins obtained in stage b) have one branch or two branches on adjacent carbon atoms in the range from 1/4 to 3/4, preferably from 1/3 to 2/3, of the chain length of their main chain. 6. A process as claimed in any of claims I to 5, wherein, in stage c), an alkylating catalyst is used which leads to alkylaromatic compounds which have, in the alkyl radical, 1 to 3 carbon atoms with an H/C index of 1. 7. An alkylaryl as intermediate obtainable in the process as claimed in any of claims 1 to 6. 8. An alkylarylsulfonate obtainable by a process as claimed in any of claims 1 to 6. 9. The use of an alkylarylsulfonate as claimed in claim 8 as surfactant. 10. The use as claimed in claim 9 in detergents or cleaners. 11. A detergent or cleaner comprising, in addition to customary ingredients, an alkylarylsulfonate as claimed in claim 8. 12. A process for the preparation of alkylarylsulfonates substantially as herein described and exemplified. 13. A detergent or cleaner substantially as herein described and exemplified.

Full Text

The present invention relates to a process for the preparation of alkylarylsulfonates, to alkylarylsulfonates obtainable by the process, and to alkylaryls obtainable in the process as intermediate, to the use of the alkylarylsulfonates as surfactants, preferably in detergents and cleaners, and to detergents and cleaners comprising these alkylarylsulfonates.
Alkylbenzenesulfonates (ABS) have been used for a long time as surfactants in detergents and cleaners. Following the use initially of surfactants based on tetrapropylene, which, however, had poor biodegradability, alkylbenzenesulfonates which are as linear as possible (LAS) have since been prepared and used. However, linear alkylbenzenesulfonates do not have adequate property profiles in all areas of application.
First, for example, it would be advantageous to improve their low-temperature washing properties or their properties in hard water. Likewise desirable is the ready ability to be formulated, derived from the viscosity of the sulfonates and their solubility. These improved properties are obtained by slightly branched compounds or mixtures of slightly branched compounds with Unear compounds, although it is imperative to achieve the correct degree of branching and/or the correct degree of mixing. Too much branching adversely affects the biodegradability of the products. Products which are too linear have a negative effect on the viscosity and the solubility of the sulfonates.
Moreover, the proportion of terminal phenylalkanes (2-phenylalkanes and 3-phenylalkanes) relative to internal phenylalkanes (4-, 5-, 6- etc. phenylalkanes) plays a role for the product properties, A 2-phenyl fraction of about 30% and a 2-

and 3-phenyl fraction of about 50% can be advantageous with regard to product quality (solubility, viscosity, washing properties).
Surfactants with very high 2- and 3-phenyl contents can have the considerable disadvantage that the processability of the products suffers as a result of a sharp increase in the viscosity of the sulfonates.
Moreover, the solubility behavior may not be optimum. Thus, for example, the Krafft point of a solution of LAS with very high or very low 2- or 3-phenyl fractions is up to 10-20°C higher than in the case of the optimal choice of the 2-and 3-phenyl fraction.
The process according to the invention offers the essential advantage that, as a result of the combination of metathesis and dimerization, a unique olefin mixture is obtained which, following alleviation of an aromatic, sulfonation and neutralization, produces a surfactant notable for its combination of excellent application properties (solubility, viscosity, stability against water hardness, washing properties, biodegradability). With regard to the biodegradability of alkylarylsulfonates, compounds which are adsorbed less strongly to clarification sludge than traditional LAS are particularly advantageous.
For this reason, alkylbenzenesulfonates which are branched to a certain degree have been developed.
For example, US 3,442,964 describes the dimerization of C5-8-hydrocarbons in the presence of a cracking catalyst coated with a transition metal, giving predominantly olefins having two or more branches. These olefins are subsequently alkylated with benzene to give a nonlinear alkylbenzene. For example, a mixture of hexenes is dimerized over a silicon dioxide-aluminum oxide cracking catalyst and then alkylated using HF as catalyst.
WO 88/07030 relates to olefins, alkylbenzenes and alkylbenzenesulfonates which can be used in detergents and cleaners. In the process, propene is dimerized to give hexene, which in turn is dimerized to give largely linear dodecene isomers.

Benzene is then alkylated in the presence of aluminum halides and hydrofluoric acid.
US 5,026,933 describes the dimerization of propene or butene to give monoolefins, where at least 20% of C12-olefms which have a degree of branching of from 0.8 to 2.0 methyl groups/alkyl chain and have only methyl groups as branches. Aromatic hydrocarbons are alkylated over a shape-selective catalyst, preferably dealuminated MOR.
WO 99/05241 relates to cleaners which comprise branched alkylarylsulfonates as surfactants. The alkylarylsulfonates are obtained by dimerization of olefins to give vinylidine olefins, and subsequent alkylation of benzene over a shape-selective catalyst, such as MOR or BEA. This is followed by sulfonation.
The olefins hitherto used for the alkylation partly have too high or too low a degree of branching or do not produce an optimal ratio of terminal to internal phcnylalkanes. Alternatively, they are prepared from costly starting materials, such as, for example, propene or alpha-olefins, and sometimes the proportion of the olefin fractions which is of interest for the preparation of surfactants is only about 20%. This leads to costly work-up steps.
The object of the present invention is to provide a process for the preparation of alkylarylsulfonates which are at least partially branched and thus have advantageous properties for use in detergents and cleaners compared with known compounds. In particular, they should have a suitable profile of properties of biodegradability, insensitivity toward water hardness, solubility and viscosity during the preparation and during use. In addition, the alkylarylsulfonates should be preparable in a cost-effective manner.
We have found that this object is achieved according to the invention by a process
for the preparation of alkylarylsulfonates by
a) reaction of a C4-olefin mixture over a metathesis catalyst for the
preparation of an olefin mixture comprising 2-pentene and/or 3-hexene, and
optional removal of 2-pentene and/or 3-hexene,

b) dimerization of the 2-pentene and/or 3-hexene obtained in stage a) over a dimerization catalyst to give a mixture containing C10-12-olefins, and optional removal of the C10-12-olcfins,
c) reaction of the C10-12-olcfin mixtures obtained in stage b) with an aromatic hydrocarbon in the presence of alkylating catalyst to form alkylaromatic compounds, where, prior to the reaction, additional linear olefins may be added,
d) sulfonation of the alkylaromatic compounds obtained in stage c), and neutralization to give alkylarylsulfonates, where, prior to the sulfonation, linear alkylbenzenes may additionally be added,
e) optional mixing of the alkylarylsulfonates obtained in stage d) with linear alkylarylsulfonates.
The combination of a metathesis of C4-olenns with a subsequent dimerization and alkylation of aromatic hydrocarbons permits the use of cost-effective starting materials and of preparation processes which make the desired products accessible in high yields.
According to the invention, it has been found that the metathesis of C4-olefms produces products which can be dimerized to give slightly branched C10-12-olefm mixtures. These mixtures can be used advantageously in the alkylation of aromatic hydrocarbons, giving products which, following sulfonation and neutralization, result in surfactants which have excellent properties, in particular with regard to the sensitivity toward hardness-forming ions, the solubility of the sulfonates, the viscosity of the sulfonates and their washing properties. Moreover, the present process is extremely cost-effective since the product streams can be designed flexibly such that no byproducts are produced. Starting from a C4-stream, the metathesis according to the invention produces linear, internal olefins which are then converted into branched olefins via the dimerization step.
Stage a) of the process according to the invention is the reaction of a C4-olefin mixture over a metathesis catalyst for the preparation of an olefin mixture comprising 2-pentene and/or 3-hexene, and optional removal of 2-pentene and/or 3-hexene, The metathesis can be carried out, for example, as described in WO 00/39058 or DE-A-100 13 253.

In the specific case of the metathesis of acyclic olefins, a distinction is made between self-metathesis in which an olefin is converted into a mixture of two olefins of differing molar masses (for example: propene -> ethene + 2-butene), and cross- or cometathesis, which is a reaction of two different olefins (propene + 1-butene -> ethene + 2-pentene). If one of the reactants is ethene, this is generally referred to as ethenolysis.
Suitable metathesis catalysts are, in principle, homogeneous and heterogeneous transition metal compounds, in particular those of transition groups VI to VIII of the Periodic Table of the Elements, and homogeneous and heterogeneous catalyst systems in which these compounds are present.
Various metathesis processes starting from C4 streams can be used according to the invention.
DE-A-199 32 060 relates to a process for the preparation of C5/C6-olefins by reaction of a feed stream which comprises 1-butene, 2-butene and isobutene to give a mixture of C2-6-olefins. In this process, propene, in particular, is obtained from butenes. In addition, hexene and methylpentene are discharged as products. No ethene is added in the metathesis. If desired, ethene formed in the metathesis is returned to the reactor.
The preferred process for the preparation of optionally propene and hexene from a raffinate II feed stream comprising olefinic C4-hydrocarbons comprises

a) carrying out a metathesis reaction in the presence of a metathesis catalyst which comprises at least one compound of a metal of transition group VIb, Vllb or VIII of the Periodic Table of the Elements, in the course of which, butenes present in the feed stream are reacted with ethene to give a mixture comprising ethene, propene, butenes, 2-pentene, 3-hexene and butanes, where, based on the butenes, up to 0,6 mol equivalents of ethene may be used,
b) first separating the product stream thus obtained by distillation into optionally a low-boiling fraction A comprising C2-C3-olefms, and into a high-boiling fraction comprising C4-C6-olefins and butanes,
c) then separating the low-boiling fraction A optionally obtained from b) by distillation into a fraction comprising ethene and a fraction comprising propene, where the fraction comprising ethene is returned to the process step a), and the fraction comprising propene is discharged as product,
d) then separating the high-boiling fraction obtained from b) by distillation into a low-boiling fraction B comprising butenes and butanes, an intermediate-boiling fraction C comprising 2-pentene, and a high-boiling fraction D comprising 3-hexene,
e) where the fractions B and optionally C are completely or partly returned to the process step a), and the fraction D and optionally C are discharged as product.
The individual streams and fractions can comprise said compounds or consist thereof. In cases where they consist of the streams or compounds, the presence of relatively small amounts of other hydrocarbons is not ruled out.
In this process, in a single-stage reaction procedure, a fraction consisting of C4-olefins, preferably n-butenes and butanes, is reacted in a metathesis reaction optionally with variable amounts of ethene over a homogeneous or, preferably, heterogeneous metathesis catalyst to give a product mixture of (inert) butanes, unreacted 1-butene, 2-butene, and the metathesis products ethene, propene, 2-pentene and 3-hexene, The desired products 2-pentene and/or 3-hexene are discharged, and the products which remain and unreacted compounds are completely or partly returned to the metathesis. They are preferably returned as completely as possible, with only small amounts being discharged in order to avoid

accumulation. Ideally, there is no accumulation and all compounds apart from 3-hcxene are returned to the metathesis.
According to the invention, up to 0.6, preferably up to 0.5, molar equivalents of ethene, based on the butenes in the C4 feed stream, are used. Thus, only small amounts of ethene compared with the prior art are used.
If no additional ethene is introduced, only up to at most about 1.5%, based on the reaction products, of ethene form, which is recirculated, see DE-A-199 32 060. According to the invention, it is also possible to use larger amounts of ethene, the amounts used being significantly lower than in the known processes for the preparation of propene.
In addition, the maximum possible amounts of C4 products and optionally C5 products present in the reactor discharge are recirculated according to the invention. This applies in particular to the recirculation of unreactcd 1-butene and 2-butene, and optionally of 2-pentene formed.
If small amounts of isobutene are still present in the C4 feed stream, small amounts of branched hydrocarbons may also be formed.
The amount of branched C5- and C6-hydrocarbons which may additionally be formed in the metathesis product is dependent on the isobutene content in the C4 feed and is preferably kept as low as possible ( In order to illustrate the process according to the invention in more detail in a plurality of variations, the reaction which takes place in the metathesis reactor is divided into three important individual reactions:

Depending on the respective demand for the target products propene and 3-hexenc (the designation 3-hexene includes any isomers formed), and/or 2-pentene, the external mass balance of the process can be influenced in a targeted way by means of variable use of ethene and by shifting the equilibrium by recirculation of certain substrcams. Thus, for example, the yield of 3-hexene is increased by suppressing the cross-metathesis of 1-butene with 2-butene by recirculation of 2-pentene to the metathesis step, so that no or extremely little 1-butene is consumed here. During the self-metathesis of 1-butene to 3-hexene, which then preferably proceeds, ethene is additionally formed, which reacts in a subsequent reaction with 2-butene to give the desired product propene.
Olefin mixtures which comprise 1-butene and 2-butene and optionally isobutene are obtained, inter alia, as C4 fraction in various cracking processes, such as steam cracking or fluid catalytic cracking. As an alternative, it is possible to use butene mixtures as are produced during the dehydrogenation of butanes or by dimerization of ethene. Butanes present in the C4 fraction have inert behavior. Dienes, alkynes or enynes are removed using customary methods such as extraction or selective hydrogenation prior to the metathesis step according to the present invention.
The butene content of the C4 fraction used in the process is 1 to 100% by weight, preferably 60 to 90% by weight. The butene content is here based on 1-butene, 2-butene and isobutene.
Preference is given to using a C4 fraction produced during steam clicking or fluid catalytic cracking or during the dehydrogenation of butane.

Here, the C4 fraction used is preferably raffinate II, the C4 stream being freed from undesirable impurities by appropriate treatment over adsorber guard beds, preferably over high-surface-area aluminum oxides or molecular sieves, prior to the metathesis reaction.
The low-boiling fraction A optionally obtained from step b), which comprises C2-C3-olefins, is separated by distillation into a fraction comprising ethene and a fraction comprising propene. The fraction comprising ethene is then recirculated to process step a), i,e. the metathesis, and the fraction comprising propene is discharged as product.
In step d, the separation into low-boiling fraction B, intermediate-boiling fraction C and high-boiling fraction D can, for example, be carried out in a dividing wall column. Here, the low-boiling fraction B is obtained at the top, the intermediate-boiling fraction C is obtained via a middle outlet and the high-boiling fraction D is -obtained as bottoms.
In order to be able to better handle the differing amounts of products produced in the flexibly controlled process, it is, however, advantageous to carry out a two-stage separation of the high-boiling fraction obtained from b). Preferably, the high-boiling fraction obtained from b) is firstly separated by distillation into a low-boiling fraction B comprising butenes and butanes, and a high-boiling fraction comprising 2-pentene and 3-hexene. The high-boiling fraction is then separated by distillation into fractions C and D. The two embodiments are explained in more detail in Figures 1 and 2,
The metathesis reaction is here preferably carried out in the presence of heterogeneous metathesis catalysts which are not or only slightly isomerization-active and are selected from the class of transition metal compounds of metals of group VIb, Vllb or VIII of the Periodic Table of the Elements applied to inorganic supports.
The preferred metathesis catalyst used is rhenium oxide on a support, preferably on y-aluminum oxide or on Al203/B203/Si02 mixed supports.

In particular, the catalyst used is Re207/Y-Al203 with a rhenium oxide content of from 1 to 20% by weight, preferably 3 to 15% by weight, particularly preferably 6 to 12% by weight.
The metathesis is, when carried out in a liquid phase, preferably carried out at a temperature of from 0 to 150°C, particularly preferably 20 to 80°C, and at a pressure of from 2 to 200 bar, particularly preferably 5 to 30 bar.
If the metathesis is carried out in the gas phase, the temperature is preferably 20 to 300°C, particularly preferably 50 to 200°C, The pressure in this case is preferably 1 to 20 bar, particularly preferably 1 to 5 bar.
The preparation of C5/C6-olefins and optionally propenc from steam cracker or refinery C4 streams may comprise the substeps (1) to (4):
(1) removal of butadiene and acetylenic compounds by optional extraction of butadiene with a butadiene-selective solvent and subsequently /or selective hydrogenation of butadienes and acetylenic impurities present in crude C4 fraction to give a reaction product which comprises n-butenes and isobutene and essentially no butadienes and acetylenic compounds,
(2) removal of isobutene by reaction of the reaction product obtained in the previous stage with an alcohol in the presence of an acidic catalyst to give an ether, removal of the ether and the alcohol, which can be carried out simultaneously with or after the etherification, to give a reaction product which comprises n-butenes and optionally oxygen-containing impurities, it being possible to discharge the ether formed or back-cleave it to obtain pure isobutene, and to follow the etherification step by a distillation step for the removal of isobutene, where, optionally, introduced C3-, i-C4- and C5-hydrocarbons can also be removed by distillation during the work-up of the ether, or oligomerization or polymerization of isobutene from the reaction product obtained in the previous stage in the presence of an acidic catalyst whose acid strength is suitable for the selective removal of isobutene as oligoisobutene or poly isobutene, to give a stream containing 0 to 15%) of residual isobutene,
(3) removal of the oxygen-containing impurities from the product of the preceding steps over appropriately selected adsorber materials.

(4) metathesis reaction of the resulting raffinate II stream as described.
The substep of selective hydrogenation of butadiene and acetylenic impurities present in crude C4 fraction is preferably carried out in two stages by bringing the crude C4 fraction in the liquid phase into contact with a catalyst which comprises at least one metal selected from the group consisting of nickel, palladium and platinum on a support, preferably palladium on aluminum oxide, at a temperature of from 20 to 200°C, a pressure of from 1 to 50 bar, a volume flow rate of from 0.5 to 30 m3 of fresh feed per m3 of catalyst per hour and a ratio of recycle to feed stream of from 0 to 30 with a molar ratio of hydrogen to diolefms of from 0.5 to 50, to give a reaction product in which, apart from isobutene, the n-butenes 1-butcne and 2-butene are present in a molar ratio of from 2:1 to 1:10, preferably from 2:1 to 1:3, and essentially no dioletlns and acetylenic compounds are present. For a maximum yield of hexene, 1-butene is preferably present in excess, and for a high protein yield, 2-butene is preferably present in excess. This means that the overall molar ratio in the first case can be 2:1 to 1:1 and in the second case 1:1 to 1:3.
The substep of butadiene extraction from crude C4 fraction is preferably carried out using a butadiene-selective solvent selected from the class of polar-aprotic solvents, such as acetone, furfural, acetonitrile, dimethylacetamide, dimethylformamide and N-methylpyrrolidone, to give a reaction product in which, following subsequent selective hydrogenation/ isomerization, the n-butenes 1-butene and 2-butene are present in a molar ratio 2:1 to 1:10, preferably from 2:1 to 1:3.
The substep of isobutene etherification is preferably carried out in a three-stage reactor cascade using methanol or isobutanol, preferably isobutanol, in the presence of an acidic ion exchanger, in which the stream to be etherified flows through flooded fixed-bed catalysts from top to bottom, the rector inlet temperature being 0 to 60°C, preferably 10 to 50°C, the outlet temperature being 25 to 85°C, preferably 35 to 75°C, the pressure being 2 to 50 bar, preferably 3 to 20 bar, and the ratio of isobutanol to isobutene being 0.8 to 2.0, preferably 1.0 to 1.5, and the overall conversion corresponding to the equilibrium conversion.

The substep of isobutene removal is preferably carried out by oligomerization or polymerization of isobutene starting from the reaction mixture obtained after the above-described stages of butadiene extraction and/or selective hydrogenation, in the presence of a catalyst selected from the class of homogeneous and heterogeneous Broensted or Lewis acids, see DE-A-lOO 13 253,
Selective hydrogenation of crude C4 fraction
Alkynes, alkynenes and alkadienes are undesired substances in many industrial syntheses owing to their tendency to polymerize or their pronounced tendency to form complexes with transition metals. They sometimes have a very strong adverse effect on the catalysts used in these reactions.
The C4 stream of a steam cracker contains a high proportion of polyunsaturated compounds such as 1,3-butadiene, 1 -butyne (ethylacctylene) and butenyne (vinylacctylene). Depending on the downstream processing present, the polyunsaturated compounds are either extracted (butadiene extraction) or are selectively hydrogenated. In the former case, the residual content of polyunsaturated compounds is typically 0.05 to 0,3% by weight, and in the latter case is typically 0.1 to 4.0% by weight. Since the residual amounts of polyunsaturated compounds likewise interfere in the further processing, a further concentration by selective hydrogenation to values Alternative; Extraction of butadiene from crude C4 fraction
The preferred method of isolating butadiene is based on the physical principle of extractive distillation. The addition of selective organic solvents lowers the volatility of specific components of a mixture, in this case butadiene. For this reason, these remain with the solvent in the bottom of the distillation column, while the accompanying substances which were not previously able to be separated off by distillation can be taken off at the top. Solvents used for the extractive distillation are mainly acetone, furfural, acetonitrile, dimethylacetaminde, dimethylformamide (DMF) and N-methylpyrrolidone (NMP). Extractive

distillations arc particularly suitable for butadiene-rich C4 cracker fractions having a relatively high proportion of alkynes, including methylacetylene, ethylacctylene and \ inytacctylene, and methylallene.
The simplified principle of solvent extraction from crude C4 fraction can be described as follows: the completely vaporized C4 fraction is fed to an extraction column at its lower end. The solvent (DMF, NMP) flows from the top in the opposite direction to the gas mixture and on its Way downwards becomes laden with the more soluble butadiene and small amounts of butenes. At the lower end of thc extraction column, part of the pure butadiene which has been isolated is fed in in order to drive out the butenes as far as possible. The butenes leave the separation column at the top. In a further column, referred to as a degasser, the butadiene is freed from the solvent by boiling out and is subsequently purified by distillation.
The reaction product from an extractive butadiene distillation is usually fed to the second stage of a selective hydrogenation in order to reduce the residual butadiene content to values of Ihc C4 stream remaining after butadiene has been separated off is referred to as C4 raffinate or raffmatc I and comprises mainly the components isobutene, 1-butene, 2-butenes, and n- and isobutancs.
Separating off isobutene from raffinate I
In the further separation of the C4 stream, isobutene is preferably isolated next since it differs from the other C4 components by virtue of its branching and its higher reactivity. Apart from the possibility of a shape-selective molecular sieve separation, by means of which isobutene can be isolated in a purity of 99% and n-butenes and butane adsorbed on the molecular sieve pores can be desorbed again using a higher-boiling hydrocarbon this is carried out in the first instance by distillation using a so-called deisobutenizer, by means of which isobutene is separated off together with 1-butene and isobutene at the top, and 2-butenes and n-butane together with residual amounts of iso- and 1-butene remain in the bottoms, or extractively by reaction of isobutene with alcohols over acidic ion

exchangers. Methanol (-> MTBH) or isobutanol (IBTBE) are preferably used for
ihis purpose.
The preparation of MTBE from methanol and isobutene is carried out at 30 to 100°C and at a pressure slightly above atmospheric pressure in the liquid phase ()\ er acidic ion exchangers. The process is carried out either in two reactors or in a twp-stage shaft reactor in order to achieve virtually complete isobutene conversion ( ' 99%). The pressure-dependant azeotrope formation between methanol and NllRl' requires a multistage pressure distillation to isolate pure MTBE, or is acliieved by relatively new technology using methanol adsorption on adsorber resins. All other components of the C4 fraction remain unchanged. Since small proportions of diolefins and acetylenes can shorten the life of the ion exchanger as a result of polymer formation, preference is given to using bifunctional PD-containing ion exchangers, in the case of which, in the presence of small amounts (^f hydrogen, only diolefins and acetylenes are hydrogenated. The cthv*rification of the isobutene remains uninlluenced by this.
MTBI- serves primarily to increase the octane number of gasoline. MTBE and IBTBE can alternatively be back-cleaved in the gas phase at 150 to 300°C over acidic oxides to obtain pure isobutene.
/\ further possibility for separating off isobutene from raffinate I consists in the direct synthesis of oligo/polyisobutene. In this way it is possible, over acidic homogeneous and heterogeneous catalysts, such as e.g, tungsten trioxide and titanium dioxide, and at isobutene conversions up to 95%, to obtain a product stream which has a residual isobutene content of a maximum of 5%i,
Feed purification of the raffinate 11 stream over adsorber materials
To improve the operation life of catalysts used for the subsequent metathesis step, it is necessary, as described above, to use a feed purification (guard bed) for removing catalyst poisons, such as, for example, water, oxygen-containing compounds, sulfur or sulfur compounds or organic halides.

Processes for adsorption or adsorptive purification are described, for example in
W. Kast, Adsorption aus der Gasphase, VCH, Weinheim (1988). The use a
zeolitic adsorbents is described in D.W. Breck, Zeolite Molecular Sieves Wire New York (1974).

The resulting reaction product is referred to as nullinate 1 and in addition to isobutene, has 1-butene and 2-butene in a molar ratio at from 2:1 to 1:10, preferably from 2:1 to 1:3.

The raffinate II stream which remains is virtually free from containing compounds, organic chlorides and sulfur compounds.

• acetonitrile(pentacarbonyl)tungsten in J. Catal. 1975, 38, 482-484:
trichloro(nitrosyl)molybdenum(II) as catalyst precursor in Z. Chem. iT-i ; ; 284-285;

• W(CO)5PPH3/EtAlCl2 in J. Catal. 1974, 34,196-202;
• WCyn-BuLi in J. Catal 1973, 28, 300-303;
• WCyn-BuLi in J. Catal. 1972, 26, 455-458;
FR 2 726 563: 03ReO[AI(OR)(L)xO]nRe03 where R = Ci-C4o-hydrocarbon, n -
1-10, X ^ 0 or 1 and L ^ solvent,
EP-A'191 0 675, EP-A-129 0 474, BE 899897: catalyst systems comprising
tungsten, 2-substituted phenoxide radicals and 4 other ligands, including a halogen,
alkyl or carbene group,
FR 2 499 083: catalyst system comprising a tungsten, molybdenum or rhenium oxo
transition metal complex with a Lewis acid,
US 4,060,468: catalyst system comprising a tungsten salt, an oxygen-containing
aromatic compound, e.g. 2,6-dichlorophenol and, if desired, molecular oxygen,
BE 776,564: catalyst system comprising a transition metal salt, an organometallic
compound and an amine.
To improve the cycle time of the catalysts used, especially of the supported catalysts, it is advisable to purify the feed over adsorber beds (guard beds). The guard bed serves here to dry the C4 stream and to remove substances which may act as catalyst poisons in the subsequent metathesis step. The preferred adsorber materials are Selexsorb CD and CDO and 3A and NaX molecular sieves (13X). The purification is carried out in drying towers at temperatures and pressures which are preferably chosen such that all of the components are present in the liquid phase. Optionally, the purification step is used for preheating the feed for the subsequent methathesis step. It may be advantageous to combine two or more purification steps with one another or to connect them in series.
Pressure and temperature in the metathesis step is chosen such that all reactants are present in the liquid phase (usually - 0 to 150°C, preferably 20 to 80°C; p = 2 to 200 bar). Alternatively, it may, however, be advantageous, particularly in the case of feed streams having a relatively high isobutene content, to carry out the reaction in the gas phase and/or to use a catalyst which has lower acidity.
The reaction is generally complete after from 1 s to 1 h, preferably after 30 s to 30 min. It may be carried out continuously or batchwise in reactors such as

For the dimerization, preference is given to using the interned linear rentenes and hexenes present in the metathesis product. Particular prcference is given to using 3-hexene.

Within the scope of the above details, the dimerizarion cataly and the reaction conditions are preferably chosen such that al least SO" of the components of the dimcrization mixture have one branch, or two branches on adjaeent carbon atoms, in the range from 1/4 to 3/4, preferably from 1 a lo 23 of the chian length of their main chain.

A very characteristic feature of the olefin mixtures prepared according to the invention is their high proportion - generally greater than 75%, in particular greater than 80% - of components with branches, and the low proportion - generally below 25%, in particular below 20% - of unbranched olefins. A further characteristic is that, at the branching sites of the main chain, predominantly groups having (y-4) and (y-5) carbon atoms are bonded, where y is the number of carbon atoms of the monomer used for the dimerization. The value (y-5) = 0 means that no side chain is present.
In the case of the C12-olefin mixtures prepared according to the invention, the main chain preferably carries methyl or ethyl groups at the branching points.
The position of the methyl and ethyl groups on the main chain is likewise characteristic: in the case of mono-substitution, the methyl or ethyl groups are in the position P = (n/2)m of the main chain, where n is the length of the main chain and m is the number of carbon atoms in the side groups, and in the case of disubstitution products, one substituent is in the position P and the other is on the adjacent carbon atom P+1. The proportions of monosubstitution products (single branching) in the olefin mixture prepared according to the invention are characteristically in total in the range from 40 to 75% by weight, and the proportions of double-branched components are in the range from 5 to 25% by weight.
The olefin mixtures obtainable by the above process (cf. WO 00/39058) are valuable intermediates particularly for the preparation, described below, of branched alkylaromatics for the preparation of surfactants.
Stage c)
In stage c), the C10-12-olefm mixture obtained in stage b) is reacted with an aromatic hydrocarbon in the presence of an alkylation catalyst to form alkylaromatic compounds.

Here preference is given to usingan alkylation catalyst which leads to alkylaromatic compounds which have in the alkyl radical, one to three carbon atoms with an H/C index of 1.

Where a fixed-bed reactor is used, the reactant can be introducted either in cocurrent or in countercurrent. Realization as a catalytic distillation is also possible.
The reactants are either in the liquid and/or in the gasoons state.

The reaction temperature is chosen such that, on the one hand, as complete as possible a conversion of the olefin takes place and, on the other hand, the fewest possible by-products arise. The choice of temperature also depends decisively on the catalyst chosen. Reaction temperatures between 50°C and 500°C (preferably 80 to 350°C, particularly preferably 80-250°C) can also be used.
The pressure of the reaction depends on the procedure chosen (reactor type) and is between 0.1 and 100 bar, and the space velocity (WHSV) is chosen between 0.1 and 100.
The reactants can optionally be diluted with inert substances. Inert substances arc preferably paraffins.
The ratio of aromatic compound : olefin is usually set between 1;1 and 100:1 (preferabty 2:1-20:1).
Aromatic feed substances
All aromatic hydrocarbons of the formula Ar-R are possible, where Ar is a monocyclic or bicyclic aromatic hydrocarbon radical, and R is chosen from If C10, preferably C1-3-alkyl, OH, OR etc., preferably H or C10-alkyl Preference is given to benzene and toluene.
Stage d)
In stage d), the alkylaromatic compounds obtained in stage c) are sulfonated and neutralized to give alkylarylsulfonates.
The alkylaryls are converted into alkylarylsulfonates by
1) sulfonation (e.g. with SO3, oleum, chlorosulfonic acid, etc., preferably with SO3) and
2) neutralization (e.g. with Na, K, NH4, Mg compounds, preferably with Na compounds).
Sulfonation and neutralization are adequately described in the literature and are carried out in accordance with the prior art. The sulfonation is preferably carried

out in a falling-film reactor, but can also bo carried out in a stirred-lank reactor. The sulfonation with SO3 is to be preferred over the sulfonation with oleum.

Noncxhaustive examples of customary ingredients of detergents and cleaners according to the invention are listed below.
Bleach
Examples are alkali metal perborates or alkali metal carbonate perhydratcs, in particular the sodium salts.
One example of an organic peracid which can be used is peracetic acid, which is preferably used in commercial textile washing or commercial cleaning.
Bleach or textile detergent compositions which can be used advantageously
comprise C1-12-percarboxylic acids, C8-16-dipercarboxylic acids,
imidopercarboxylic acids or aryldipercarboxylic acids. Preferred examples of acids which can be used are peracetic acid, linear or branched ectane-, nonanc-, dccanc-or dodecane-monoper-acids, decane- and dodecane-diperacid, mono- and diperphthalic acids, -isophthalic acids and -terephthalic acids. phthalimidopercaproic acid and terephthaloyldipercaproic acid. It is likcwisc possible to use polymeric peracids, for example those which contain the acrylic acid basic building blocks in which a peroxy function is present. The pcrcarboxylic acids may be used as free acids or as salts of the acids, preferably alkali metal or alkaline earth metal salts.
Bleach activator
Bleach catalysts are, for example, quatemized imines and sulfonimincs. as described, for example, in US 5,360,568, US 5,360,569 and EP-A-0 453 003. and also manganese complexes as described, for example, in WO-A 94/21777. Futhcr metal-containing bleach catalysts which may be used are described in EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 272.
Bleach activators are, for example, compounds from the classes of substance below:

textile treatment at low temperatures, and also those which are suitable in a number of temperature ranges up to and including the traditional range of the boil wash

Anionic surfactants
Suitable anionic surfactants arc the linear andA)r slightly branched alkylben/enesulfonates (LAS) according to the invention.
Further suitable anionic surfactants are. tor example, fatty alcohol sulfates of tatty alcohols having 8 to 22. preferably 10 to 18, carbon atoms, e.g. C9- to C11-alcohol sulfates, C12 to C13-alcohol sulfates, cetyl sulfate, niyrisiy! sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
Further suitable anionic surfactants arc sulfated ethoxylated C^- to C22-aIcohols (alkyl ether sulfates) or soluble salts thereof. Compounds of this type are prepared, for example, by firstly alkoxylating a C8- to C22-alcohol preferably a C10-C18-alcohol e.g. a fatty alcohol, and then sulfating the alkoxylation product. For the alkoxylation, preference is given to using ethylene oxide, in which case 2 to 50 mol, preferably 3 to 20 mol, of ethylene oxide are used per mole of fatty alcohol. The alkoxylation of the alcohols can, however, also be carried out using propylene oxide on its own and optionally butylene oxide. Also suitable are those alkoxylatcd C8- to C22-alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide. The alkoxylatcd CK to C2:-alcohols may contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in random distribution.
Further suitable anionic surfactants are N-acylsarcosinates having aliphatic saturated or unsaturated C8- to C25-acyl radicals, preferably C10 to C20-acyl radicals, e.g. N-oleoylsarcosinate.
The anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal salts, such as sodium, potassium and lithium and ammonium salts such as, for example, hydroxyethylammonium, di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium salts.
The detergents according to the invention preferably comprise C10- to C13-linear and/or slightly branched alkvlbenzenesulfonates (LAS).

Nonionic surfactants
Suitable nonionic surfactants arc. for example, alkoxylated C8- to C22-alcohols, such as fatlv alcohol alkoxvlatcs or oxo alcohol alkoxvlates. The alkoxylation can be carried out with ethylene oxide, propylene oxide and/or bulylene oxide-Surfactants which can be used here are any alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide in added form. Block polymers of ethylene oxide, propylene oxide and/or butylene oxide are also suitable here, or addition products which contain said alkylene oxides in random distribution. Per mole of alcohol 2 to 50 mok preferably 3 to 20 mol of at least one alkylene oxide are used. The alkylene oxide used is preferably ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.
A further class of suitable nonionic surfactants are alkylphenol ethoxylates having C6-C14-alkyl chains and 5 to 30 mol of ethylene oxide units.
Another class of nonionic surfactants are alkyl polyglucosides having 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain. These compounds contain at most 1 to 20, preferably 1.1 to 5, glucoside units.
Another class of nonionic surfactants are N-alkvl-ulucamides of the structure II or
III

The detergents according to the invention preferably comprise C10C16-alcohols ethoxylated with 3-12 mol of ethylene oxide, particularly preferably elhoxylated fattv alcohols -as nonionic surfactants.
Organic cobuilders
Examples of suitable low molecular weight polycarboxylates as organic cobuilders are:
C4- to C20-di-, -tri- and -tetracarboxylic acids, such as, for example, succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetra-carboxylic acid and alkyl- and alkenylsuccinic acids having C2- to C16-alkyl or -alkenyl radicals;
C4- to C10-hydroxycarboxylic acids, such as, tor example, malic acid, tartaric acid, gluconic acid, glucaric acid, citric acid, lactobionic acid and sucrose mono-, -di-and -tricarboxylic acid;
aminopolycarboxylates, such as, for example, nitrilo-triacetic acid, methylglycinediacetic acid, alaninediaeetic acid, ethylenediamineietraacetic acid and serinediacetic acid;
salts of phosphonic acids, such as, for example, hydroxyethanediphosphonic acid, ethylenediaminctetra(methylenephosphonate) and diethylenetriaminepenta-
(methylenephosphonate).
Examples of suitable oligomeric or polymeric polycarboxylates as organic cobuilders are:
oligomaleic acids, as described, for example, in EP-A-451 508 and EP-A-396 303;
CO- and terpolymers of unsaturated C4-C8-dicarboxyUc acids, where, as comonomers, monoethylenically unsaturated monomers

from group (i) in amounts of up to 95% by weight from group (ii) in amounts of up to 60% by weight from group (iii) in amounts of up to 20*?^) by weight may be present in copolymerized form.
Examples of suitable unsaturated C4-C8-dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid.
The group (i) includes monoethylenically unsaturated C3-C8-monocarboxylic acids, such as, for example, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. Preference is given to usintz acrylic acid and methacrylic acid from group (i).
The group (ii) includes monoethylenically unsaturated C2-C22-oIeflns, vinyl alky! ethers having C|-Cs-alkyl groups, styrenc, vinyl esters of C1-C8 carboxylic acids, (meth)acrylamide and vinylpyrrolidone. Preference is given to using C2-C6-oletms. vinyl alkyl ethers having C1-C4-alkyl groups, vinyl acetate and vinyl propionate from group (ii).
The group (iii) includes (meth)acrylic esters of C1-C8-alcohols, (meth)acrylonitrile, (meth)acrylamides of C1-C8-amines, N-vinylformamide and vinylimidazole.
If the polymers of group (ii) contain vinyl esters in copolymerized form, these may also be present partly or completely in hydrolyzed form to give vinyl alcohol structural units. Suitable co- and terpolymers are known, for example, from US-A 3 887 806 and DE-A 43 13 909.
As copolymers of dicarboxylic acids, suitable organic cobuilders are preferably:
copolymers of maleic acid and acrylic acid in the weight ratio 10:90 to 95:5, particularly preferably those in the weight ratio 30:70 to 90:10 having molar masses of from 10 000 to 150 000;

terpolymers of maleic acid, acrylic acid and a vinyl ester of a Ci-Crcarboxylic acid in the weight ratio 10(maleic acid):9()(acrylic acid + vinyl ester) to 95(maleic acid):5(acrylic acid f- vinyl ester), where the weight ratio of acrylic acid to vinyl ester can vary in the range from 20:80 to 80:20. and particularly preferably
terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate in the weight ratio 20(maleic acid):80{acrylic acid + vinyl ester) to 90(maleic acid):10(acrylic acid + vinyl ester), where the weight ratio of acrylic acid to the vinyl ester can vary in the range from 30:70 to 70:30;
copolymers of maleic acid with C2-C8-olefms in the molar ratio 40:60 to 80:20, where copolymers of maleic acid with ethylene, propylene or isobutane in the molar ratio 50:50 are particularly preferred.
Graft polymers of unsaturated carboxylic acids to low molecular weight carbohydrates or hydrogenated carbohydrates, cf. IJS-A 5,227,446, DE-A-44 15 623, DE-A-43 13 909. are likewise suitable as organic cobuilders.
Examples of suitable unsaturated carboxylic acids in this connection are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, and mixtures of acrylic acid and maleic acid which are grafted on in amounts of from 40 to 95% by weight, based on the component to be grafted.
For the modification, it is additionally possible for up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers to be present in copolymerized form. Suitable modifying monomers are the abovementioned monomers of groups (ii) and (iii).
Suitable graft bases are degraded polysaccharides, such as, for example, acidic or enzymaticaliy degraded starches, inulins or cellulose, reduced (hydrogenated or reductively aminated) degraded polysaccharides, such as, for example, mannitol, sorbitol, aminosorbitol and glucamine, and also polyalkylene glycols having molar masses up to Mw = 5 000, such as, for example, polyethylene glycols, ethylene oxide/propylene oxide or ethylene oxide/butylene oxide block copolymers, random

ethylene oxide/propylene oxide or ethylene oxide/butylene oxide copolymers. alkoxylated mono- or polybasic C1-C22-alcohols. cf. US-A 4.746,456.
From this group, preference is given to using grafted degraded or degraded reduced starches and grafted polyethylene oxides, in which case 20 to 80% by weight of monomers, based on the graft component, are used in the graft polymerization. I'or the grafting, preference is given to using a mixture of maleic acid and acr\lic acid in the weight ratio from 90:10 to 10:90.
Polyglyoxylic acids as organic cobuilders are described, for example, in EP-B-001 004, US-A 5,399,286, DH-A-4106 355 and r:P-A-656 914. Hie end-groups of the polyglyoxylic acids may have different structures.
Polyamidocarboxylic acids and modified polyamidocarboxylic acids as organic cobuilders are known, for example, from EP-A-454 126, r;P-B-511 037. WO-A 94/01486 and EP-A-581 452.
As organic cobuilders, preference is also given to using polyaspartic acid or cocondensates of aspartic acid with further amino acids, C4-C25-mono- or -dicarboxylic acids and/or C4-C25-mono- or -diamines. Particular preference is given to using polyaspartic acids prepared in phosphorus-containing acids and modified with C6,-C22-mono- or -dicarboxylic acids or with C6-'C22-mono' or -diamines.
Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds as organic cobuilders are known, for example, from WO-A 93 22362 and WO-A 92/16493. Such carboxyl-containing condensates usually have molar masses up to 10 000, preferably up to 5 000.
Antiredeposition agents and soil release polymers
Suitable soil release polymers and/or antiredeposition agents for detergents are, for example:

polyesters of polyethylene oxides with ethylene glycol and/or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;
polyesters of polyethylene oxides terminally capped at one end with di- and/or polyhydric alcohols and dicarboxylic acid.
Such polyesters are known, for example from US-A 3,557.039, GB-A 1 154 730, EP-A-185 427. EP-A-241 984. t:P-A-24I 985. EP-A-272 033 and US-A 5 J 42.020.
Further suitable soil release polymers are amphiphilic graft or copolymers of vinyl and/or acrylic esters on polyalkylene oxides (of: US-A 4,746,456, US-A 4,846,995, DE-A-37 11 299, US-A 4,904,408, US-A 4,846.994 and US-A 4,849.126) or modified celluloses, such as, for example, methylcellulose, hydroxypropylcellulose or carboxymethylcellulose.
Color-transfer inhibitors
Examples of the color-transfer inhibitors used are homo- and copolymers of vinylpyrrolidone. vinylimidazole, vinyloxazolidone and 4-vinylpyridine N-oxide having molar masses of from 15 000 to 100 000, and crosslinked finely divided polymers based on these monomers. The use mentioned here of such polymers is known. cf. DE-B-22 32 353, DE-A-28 14 287, DE-A-28 14 329 and DE-A-43 16 023.
Enzymes
Suitable enzymes are, for example, proteases, amylases, lipases and cellulases. in particular proteases. It is possible to use two or more enzymes in combinadon.
In addition to use in detergents and cleaners for the domestic washing of textiles, the detergent compositions which can be used according to the invention can also be used in the sector of commercial textile washing and of commercial cleaning. In this field of use. peracetic acid is usually used as bleach, which is added to the wash liquor as an aqueous solution.

Use in textile detergents
A typical pulverulent or granular hcavv-dutv detergent accordina to the invention may, for example, have the following composition:
0.5 to 50% by weight, preferably 5 to 30% by weight, of at least one' anionic and/or nonionic surfactant,
0.5 to 60% by weight, preferably 15 to 40% by weight, oi' at least niu.-inorganic builder,
0 to 20% by weight, preferably 0.5 to 8% by weight, of at least one organic cobuilder.
2 to 35% by weight, preferably 5 to 30% by weight, of an inorganic bloaclv 0.1 to 20% by weight, preferably 0.5 to 10% by weight, o'i a bleach activator, optionally in a mixture with further bleach activators. 0 to 1% by weight, preferably up to at most 0.5% by weight, of a bleach catalyst,
0 to 5%) by weight, preferably 0 to 2.5% by weight, of a polymeric color-transfer inhibitor,
0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, of protease. 0 to K5% by weight, preferably 0.1 to 1.0% by w^Mght, of lipase, 0 to 1.5% by weight, preferably 0.2 to 1.0%) by weight, of a soil release polymer, ad 100% with customary auxiliaries and adjuncts and water.
Inorganic builders preferably used in detergents are sodium carbonate, sodium hydrogen carbonate, zeolite A and P. and amorphous and crystalline Na silicates.
Organic cobuilders preferably used in detergents are acrylic acid;nia!c:c copolymers, acrylic acid/maleic acidVinyl ester terpolymers and citric acid.
Inorganic bleaches preferably used in detergents are sodium perborate and sodium carbonate perhydrate.

Example 3
2-Pentene from the rafflnate II metathesis was dimerized continuously as in example 2 over an Ni heterogeneous eatalyst. Fractional distillation of the product gave a decene fraction with a purity of 99.5%.
Example 4
A mixture of 2-pentene and 3-hexene from the raffmate II methathesis was dimerized as in example 2 and example 3, Fractional distillation of the product gave a decene/undecene/dodecene fraction with a purity of 99.5%
Example 5
The C12-olefin fraction from example 2 is alkylated with benzene in the molar ratio 1:10. For this, the reaction mixture is introduced into an autoclave (300 ml) which is equipped with a stirrer and a catalyst basket. 25% by weight, based on the mass of the olefin, of zeolite mordenith catalyst (MOR) are introduced into the catalyst basket. The autoclave is sealed and flushed twice with nitrogen (N2). The autoclave is then heated to 180°C. The reaction mixture is then reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas chromatography-mass spectrometry coupling. Excess benzene and low-boiling components are distilled off, and the alkylaryl mixture obtained is analyzed by means of gas chromatography-mass spectrometry coupling and C "'-NMR.
Example 6
A 2 1 four-necked flask fitted with magnetic stirrer, thermometer, dropping funnel, gas inlet frit and gas outlet is charged with 1 900 g of SO3-depleted oleum. This flask is connected via the gas outlet to a 1 1 three-necked flask via a Viton hose. This 1 1 flask fitted with paddle stirrer, thermometer, gas inlet frit and gas outlet is charged with the alkylbenzene mixture from example 5.
The depleted oleum is brought to 120°C in the SO3-developer, and the oleum (65% strength) is added via a dropping funnel over the course of 30 minutes. Using a

stream of nitrogen of 80 1/h. the SO3 gas is stripped out and passed into the
alkylbenzene via a 6 mm inlet tube. The temperature of the
alkvlbenzene/alkvlbenzenesulfonic acid mixture increases slowly to 40°C and is
maintained at 40°C using cooling water. 1 he residual gas is removed by suction
using a water-jet pump.
The molar ratio of SOj/alkylbenzene is 1.01:1.
After a postreaction time of 4 h, the alkylbenzene-sulfonic acid formed is stabilized
with 0.4% by weight of water and then neutralized with NaOK to give the
alkylbenzenesulfonate.
Example 7
A mixture of the C10-/C11/C12-olenn fractions from example 4 is alkylated with benzene in the molar ratio 1:10. For this, the reaction mixture is introduced into an autoclave (300 ml) which is provided with a stirrer and a catalyst basket. 25% by weight, based on the mass of the olefin, of zeolite mordenite catalyst (MOR) are introduced into the catalvst basket. The autoclave is sealed and Hushed twice with nitrogen (N2). The autoclave is then heated to 200°C]. The reaction mixture is reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas chromatography-mass spectrometry coupling.
Excess benzene and low-boiling fractions are distilled off, and the alkylaryl mixture obtained is analyzed by means of gas chromatography-mass spectrometry coupling and C'-^^NMR.
Example 8
The alkylbenzene mixture from example 7 is converted to the alkylbenzenesulfonate analogously to the description in example 6.
Example 9
A mixture of the C10-/C11-/C12-olefin fractions from example 4 is alkylated with benzene in the molar ratio 1:2. For this, the reaction mixture is introduced into an autoclave (300 ml) which is provided with a stirrer and a catalyst basket. 5% by

weight, based on the mass of the olefin, of zeolite ZSM-12 eatalyst are introduced into the eatalyst basket. The autoclave is sealed and Hushed twice with nitrogen (Ni). The autoclave is then heated to 18()°C. The reaction mixture is reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas ehromatography-mass spectrometry coupling.
Excess benzene and low-boiling fractions are distilled off. and the alkylaryl mixture obtained is analyzed by means of gas chromatography-mass spectrometry coupling and C '-NMR.
Example 10
'["he alkylbenzene mixture from example 9 is converted to the alkylbenzenesulfonate analogously to the description in example 6.
Example 11
A C12-olefin fraction from example 2 is alkylated with benzene in the molar ratio 1:4. For this, the reaction mixture is introduced into an autoclave (300 ml) which is provided with a stirrer and a catalyst basket. 10% by weight, based on the mass of the olefin, of zeofite beta (BBA) catalyst are introduced into the catalyst basket. The autoclave is sealed and Hushed twice with nitrogen (NT). The autoclave is then heated to 180°C. The reaction mixture is reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas chromatography-mass spectrometry coupling. Excess benzene and low-boiling fractions are distilled off and the resuUing alkylaryl mixture is analyzed by means of gas chromatography-mass spectrometry coupling and C'^-NMR.
Example 12
The alkylbenzene mixture from example 11 is converted to the alkylbenzenesulfonate analogously to the description in example 6.

Example 13
A mixture of the C10-/C11-/C12-olenn fractions from example 4 is alkylated with benzene in the molar ratio 1:4. I'or this, the reaction mixture is introduced into an autoclave (300 ml) which is provided with a stirrer and a catalyst basket. 10% by weight, based on the mass of the olefin, of zeolite MCM-22 catalyst are introduced into the catalyst basket. The autoclave is scaled and flushed twice with nitrogen (N2) The autoclave is then heated to 200°C. The reaction mixture is reacted for 12 h, then cooled, any catalyst particles are filtered from the reaction mixture, and the reaction mixture is analyzed by means of gas chromatography-mass spectrometry coupling.
Excess benzene and low-boiling fractions are distilled off, and the resulting alkylaryl mixture is analyzed by means of gas chromatography-mass spectrometry coupling and C13-NMR.
Example 14
I 1/h of oleum (65%) in concentrated sulfuric acid is introduced into a heated (120'C) 10 1 four-necked flask using a pump. 130 1/h of dry air are passed through the sulfuric acid via a frit; this air strips out the SO3. The S03-enriched stream of air (about 4% of SO3) is brought into contact with an alkylbenzene mixture from example 13 in a 2 m-long falling-film reactor, at approximately 40-50°C (10-15°C double-jacket water cooling), and sulfonates this mixture. The molar ratio oi' S03/alkylbenzene is 1.01:1. The reaction time in the falling-film reactor is approximately 10 sec. The product is pumped to an afterripening container where it remains for approximately 4-8 h. The sulfonic acid is then stabilized with 0.4% by weight of water and neutralized with NaOH to give the alkylbenzenesulfonate.
Example 15
A C12-olefin fraction from example 2 is alkylated with benzene in the molar ratio 1:10. Thus, the reaction mixture is introduced into a four-necked flask (2 1), which is provided with a stirrer, a thermometer, a reflux condenser with a gas offtake and a dropping funnel. The flask is charged with benzene and AICI3, the temperature is increased to 80°C. and the olefin mixture is metered in slowly. The reaction

mixture is allerreacted for 1/2 h, then cooled, any catalyst particles are llltered from the reaction mixture, and the reaction mixture is neutralized with NaOH, Washing with water is then carried out, and the product is dried. Excess benzene and low-boiling fractions are distilled off, and the resulting alkylaryl mixture is analyzed by means of gas chromatography-mass spectrometry coupling and C13-NMR.
Example 16
The alkylben/ene mixture from example 15 is converted to the alkylbenzenesulfonate analogously to the description in example 6.

"as enclosed to IPER"
We claim:
1. A process for the preparation of alkylarylsulfonates by
a) reaction of a C4-olefin mixture over a metathesis catalyst for the preparation of an olefin mixture comprising 2-pentene and/or 3-hexene, and optional removal of 2-pentene and/or 3-hexene,
b) dimerization of the 2-pentene and/or 3-hexene obtained in stage a) over a dimerization catalyst to give a mixture containing C10-12-olefins. and optional removal of the C10-12-olefms,
c) reaction of the C10-12-olefin mixtures obtained in stage b) with an aromatic hydrocarbon in the presence of an alkylating catalyst to form alkylaromatic compounds.
d) sulfonation of the alkylaromatic compounds obtained in stage c), and neutralization to give alkylarylsulfonates.

2. A process as claimed in claim 1, wherein the metathesis catalyst in stage a) is chosen from compounds of a metal of transition groups VIb, Vllb or VIII of the Periodic Table of the Elements.
3. A process as claimed in either of claims 1 or 2, wherein, in stage b), a dimerization catalyst is used which contains at least one element from transition group VIII of the Periodic Table of the Elements, and the catalyst composition and the reaction conditions are chosen such that a dimer mixture is obtained which contains less than 10% by weight of compounds which have a structural element of the formula I (vinylidene group)

4. A process as claimed in any of claims 1 to 3, wherein the olefins obtained in stage b) have a proportion of unbranched olefins of less than 25% by weight,
5. A process as claimed in any of claims 1 to 4, wherein at least 80% of the olefins obtained in stage b) have one branch or two branches on adjacent carbon atoms in the range from 1/4 to 3/4, preferably from 1/3 to 2/3, of the chain length of their main chain.
6. A process as claimed in any of claims I to 5, wherein, in stage c), an alkylating catalyst is used which leads to alkylaromatic compounds which have, in the alkyl radical, 1 to 3 carbon atoms with an H/C index of 1.
7. An alkylaryl as intermediate obtainable in the process as claimed in any of claims 1 to 6.
8. An alkylarylsulfonate obtainable by a process as claimed in any of claims 1 to 6.
9. The use of an alkylarylsulfonate as claimed in claim 8 as surfactant.
10. The use as claimed in claim 9 in detergents or cleaners.
11. A detergent or cleaner comprising, in addition to customary ingredients, an alkylarylsulfonate as claimed in claim 8.

12. A process for the preparation of alkylarylsulfonates substantially as herein described and exemplified.
13. A detergent or cleaner substantially as herein described and exemplified.

Documents:

222-chenp-2003-abstract.pdf

222-chenp-2003-claims filed.pdf

222-chenp-2003-claims granted.pdf

222-chenp-2003-correspondnece-others.pdf

222-chenp-2003-correspondnece-po.pdf

222-chenp-2003-description(complete)filed.pdf

222-chenp-2003-description(complete)granted.pdf

222-chenp-2003-form 1.pdf

222-chenp-2003-form 18.pdf

222-chenp-2003-form 26.pdf

222-chenp-2003-form 3.pdf

222-chenp-2003-form 5.pdf

222-chenp-2003-other document.pdf

222-chenp-2003-pct.pdf

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Patent Number

212385

Indian Patent Application Number

222/CHENP/2003

PG Journal Number

07/2008

Publication Date

15-Feb-2008

Grant Date

03-Dec-2007

Date of Filing

05-Feb-2003

Name of Patentee

BASF AKTIENGESELLSCHAFT

Applicant Address

D-67056 Ludwigshafen,

Inventors:

#	Inventor's Name	Inventor's Address
1	Dr. Heiko MAAS	Elisabethstrasse 1, 68165 Mannheim,
2	Dr. Thomas NARBESHUBER	Lameystrasse 18, 68165 Mannheim,
3	Dr. Michael ROPER	Pegauer Strasse 10, 67157 Wachenheim,

PCT International Classification Number

C07C 303/06

PCT International Application Number

PCT/EP2001/009297

PCT International Filing date

2001-08-10

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	100 39 995.9	2000-08-11	Germany