RU2353607C2 - Method of obtaining phenylalcanes using olefin isomerisation and paraffin recycling - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining phenylalcanes, which is characterised by including stages: a) dehydration of initial raw material, which contains C₈-C₂₈ paraffins, in dehydration section operating in dehydration conditions, sufficient for paraffin dehydration, and isolating from dehydration section flow of dehydration products, containing mono-olefins and paraffins; b) passing at least part of flow of dehydration products into isomerisation section operating in isomerisation conditions, sufficient for olefin isomerisation and isolating from isomerisation section flow of isomerisation products, which contains mono-olefins and paraffins, where monoolefins in flow of isomerisation products contain from 8 to 28 carbon atoms, and where at least part of monoolefins in flow of dehydration products contain 3 or 4 primary carbon atoms and do not contain quaternary carbon atoms; c) passing phenyl compound and at least part of flow of isomerisation products, which contains mono-olefins, into alkylation section, running alkylation section in alkylation conditions sufficient for alkylation of phenyl compound using mono-olefins in presence of alkylation catalyst obtaining phenylalcanes, which contain molecules including one phenyl part and one aliphatic alkyl part, which contains from 8 to 28 carbon atoms; where at least part of phenylalcanes, formed in alkylation section, contain 2, 3 or 4 primary carbon atoms and do not contain quaternary carbon atoms except any quaternary carbon atom bound with carbon-carbon bond with carbon atom of phenyl part; and where alkylation is characterised by selectivity with respect to obtaining 2-phenylalcanes within the range from 40 to 100 and selectivity with respect to obtaining internal quaternary phenylalcanes less than 10; d) isolating from alkylation section flow of alkylation products, which contains phenylalcanes and contains paraffins of flow directed to recycling; and e) passing of at least part of flow directed to recycling into dehydration section. Claimed invention also relates to composition for obtaining washing substance, containing phenylalcanes, obtained by method described above, to method of obtaining flow of products, which contains phenylalcane sulphonates, which is obtained from phenylalcanes, obtained according to method described above and to washing substance composition.

EFFECT: obtaining washing substances, which satisfy more strict demands to selectivity with respect to 2-phenylalcanes.

15 cl, 3 tbl, 5 ex, 1 dwg

Description

FIELD OF THE INVENTION

The invention generally relates to the alkylation of phenyl compounds with olefins using a solid catalyst, and more particularly, to a process for the selective preparation of specific phenylalkanes using a solid alkylation catalyst.

State of the art

More than thirty years ago, many household detergents were obtained from branched alkylbenzenesulfonates (RABS). RABS are derived from a specific type of alkylbenzenes called branched alkylbenzenes (RAB). Alkylbenzenes (phenylalkanes) are the general category of compounds having an aliphatic alkyl group attached to a phenyl group and described by the general formula (m _i -alkyl _i ) _i -n-phenylalkane. An aliphatic alkyl group consists of an aliphatic alkyl chain, which in the formula (m _i -alkyl _i ) _i -n-phenylalkane means "alkane". Among the chains in the aliphatic alkyl group, the aliphatic alkyl chain is the longest straight chain that contains a carbon atom bonded to the phenyl group. An aliphatic alkyl group may also consist of one or more alkyl branches, each of which is attached to an aliphatic alkyl chain and is indicated in the formula (m _i -alkyl _i ) _i -n-phenylalkane by the corresponding indicator “(m _i -alkyl _i ) _i ”.

Characteristics for RAB are described in US-A-6187981 B1. In short, RAB is characterized by a relatively large number of primary carbon atoms in the aliphatic alkyl group; the phenyl group in the RAB can be attached to any non-primary carbon atom in the aliphatic alkyl chain; and there is a relatively high probability that one of the carbon atoms in the aliphatic alkyl group of the RAB will be a quaternary carbon atom.

If the carbon atom in the alkyl chain is joined to two other carbon atoms in the alkyl side chain, the carbon atom in the alkyl branching group and the carbon atom of the phenyl group, then the resulting alkyl phenylalkane is called a “Quaternary alkylphenylalkane” or simply “Quaternary compound”. Thus, quaternary compounds include alkylphenylalkanes described by the general formula m-alkyl-m-phenylalkane. If the quaternary carbon atom is the second carbon atom from the end of the alkyl side chain, then the resulting 2-alkyl-2-phenylalkane will be called the “terminal quaternary compound”. In the case of any other Quaternary carbon atom along the alkyl side chain, the name "internal Quaternary compound" will occur.

Thirty years ago, pollution of rivers and lakes with detergents for washing obtained from RABS began. The preparation of detergents from linear alkylbenzenesulfonates (LABS), which are biodegradable faster than RABS, has solved this problem. LABS are made from alkylbenzenes called linear alkylbenzenes (LABs). LAB is described in US-A-6187981 B1. The LAB is characterized by the presence of a linear aliphatic alkyl group containing two primary carbon atoms, and the phenyl group in the LAB is usually attached to any secondary carbon atom of the linear aliphatic alkyl group.

Recent studies have identified a number of modified alkylbenzenesulfonates, referred to herein as MABS. MABSs differ in composition from the alkylbenzenesulfonates RABS and LABS and have improved cleaning performance for washing as well as for cleaning hard surfaces and are excellent in hard water, while their biodegradability is comparable with the corresponding characteristic for LABS. Sulfonation of modified alkylbenzenes (MABs) will produce MABSs. MAB is a phenylalkane having a weakly branched aliphatic alkyl group and a phenyl group, and it is described by the general formula (m _i -alkyl _i ) _i -n-phenylalkan. MAB usually contains two, three or four primary carbon atoms, is characterized by a high level of 2-phenylalkanes and a relatively low level of internal quaternary compounds. US-A-6187981 B1 describes a process for producing MAB by paraffin isomerization, paraffin dehydrogenation and alkylation using paraffin recycling. US-A-5,276,231 describes a process for producing LAB by selectively removing aromatic by-products from a dehydrogenation zone of paraffins, and also describes the recycling of paraffins to the dehydrogenation zone, the selective hydrogenation of any monoolefins in a stream of recycled paraffins, and the selective hydrogenation of diolefin by-products from the dehydrogenation zone.

As for other alkylation methods and adsorption separation methods, which uniquely produce weakly branched or delinearized alkylbenzenes, their examples are international publications Nos. WO 99/05082, WO 99/05084, 99/05241, WO 99/05243 and W0 99/07656, which are hereby incorporated by reference.

Due to the advantages of MABS in comparison with other alkylbenzenesulfonates, a search is carried out for catalysts and methods that would lead to the selective production of MAB with the desired selectivity for the production of 2-phenylalkanes and internal quaternary phenylalkanes.

Disclosure of invention

Describes a method for producing phenylalkanes, in particular modified alkylbenzenes (MAB), as a result of the stages of dehydrogenation of paraffins, isomerization of olefins and alkylation of the phenyl compound, in which paraffins from the stream of alkylation products are recycled to the dehydrogenation step. Paraffins that are sent for recycling can be linear or non-linear paraffins, including weakly branched paraffins. Since the paraffins sent for recycling can be turned into weakly branched olefins, this method leads to the efficient extraction of paraffins from the alkylation product stream and their use in the preparation of valuable phenylalkane products. Thus, this method leads to an increase in the yield of valuable products for a given amount of paraffin feedstock loaded into the process, while preventing difficulties in separating paraffins from monoolefins after the dehydrogenation of paraffins and before the alkylation step.

This method, when used for the alkylation of detergents, results in detergents that meet increasingly stringent selectivity requirements for the production of 2-phenylalkanes and selectivity for the production of internal quaternary phenylalkanes in the preparation of modified alkylbenzenes (MABs). Thus, sulfonation of MAB results in modified linear alkylbenzenesulfonates (MABSs) characterized by improved purification efficiency in hard and / or cold water and biodegradability comparable to the biodegradability of linear alkylbenzenesulfonates.

It seems that MAB and MABS obtained by the methods described herein are not products obtained by the methods of the prior art in which paraffins are not recycled, and that in the dehydrogenation zone the degree of conversion of branched paraffins may exceed the degree of conversion of normal ( linear) paraffins, and / or that the conversion of heavier paraffins may exceed the conversion of lighter paraffins. Since in this case the degree of paraffin conversion is limited by equilibrium, the product stream from the dehydrogenation zone may contain more linear and / or lighter paraffins. Thus, the concentration of linear paraffins and / or lighter paraffins in the paraffin stream sent for recycling may increase. This, in turn, can lead to an increase in the concentration and, ultimately, to an increase in the degree of conversion of linear and / or lighter paraffins in the dehydrogenation zone until the removal rate of linear and / or lighter paraffins from the technological process as a result passage of dehydrogenation and subsequent alkylation will not be equal to the rate of introduction of these paraffins into the dehydrogenation zone from the paraffinic feedstock and the paraffin stream sent for recycling. Accordingly, for a given degree of conversion of olefins in the alkylation zone, the aliphatic alkyl chain of the MAB product of the present invention will retain a greater similarity in the number of carbon atoms with the paraffin feedstock compared to what is the case in prior art methods. Compared with the method of the present invention, prior art methods shift the distribution of the number of carbon atoms in the aliphatic alkyl groups of the MAB towards larger amounts of carbon atoms. After sulfonation, the MABS products of the present invention tend to maintain a distribution over the number of carbon atoms in the aliphatic alkyl chain similar to that found for paraffin feed. Thus, in the case of a given combination of feedstock, the methods of the present invention can lead to specific MAB and MABS products having an aliphatic alkyl chain characterized by a specially developed level of branching, which may differ from the products obtained in the prior art methods.

The implementation of the invention

Two types of feed used in the process of interest are a paraffinic compound and a phenyl compound. Paraffin feedstock may contain unbranched (linear) or normal paraffin molecules characterized by the total number of carbon atoms per paraffin molecule in the range from 8 to 28, and in other embodiments from 8 to 15, from 10 to 15 and from 11 to 13 atoms carbon. Two carbon atoms per one unbranched paraffin molecule are primary carbon atoms, and the remaining carbon atoms are secondary carbon atoms.

In addition to unbranched paraffins, other acyclic compounds can be loaded into the process in question. These other acyclic compounds in the process under consideration can be loaded either in paraffin feedstock containing unbranched paraffins, or by using one or more other streams that enter the process in question. One such acyclic compound is weakly branched paraffin, which, as used herein, refers to paraffin having a total number of carbon atoms in the range of 8 to 28, three or four carbon atoms of which are primary carbon atoms, and none of the other atoms carbon is not a quaternary carbon atom. A weakly branched paraffin may have a total number of carbon atoms in the range from 8 to 15, and in another embodiment, from 10 to 15 carbon atoms and in another embodiment, from 11 to 13 carbon atoms. A weakly branched paraffin generally includes an aliphatic alkane described by the general formula (p _i -alkyl _i ) _i -alkane. A weakly branched paraffin consists of the longest straight chain in a weakly branched paraffin — an aliphatic alkyl chain called “alkane” in the formula (p _i -alkyl _i ) _i -alkane. A weakly branched paraffin also consists of one or more alkyl branching groups, denoted by the corresponding indicator “(p _i -alkyl _i ) _i ”, the subscript “i” being equal to the number of alkyl branching groups, and each corresponding alkyl branching group is attached to a carbon atom with the number p _i in the aliphatic alkyl chain. In an aliphatic alkyl chain, the numbering goes from one end to the other in the direction that allows us to assign the lowest possible numbers to carbon atoms having alkyl branching groups.

The alkyl branching group or the alkyl branching groups of the lightly branched paraffin can be selected from methyl, ethyl and propyl groups, with shorter and normal branches being preferred. Weakly branched paraffins, either having two alkyl branching groups or containing four primary carbon atoms, may comprise less than 40% (mol.), And in another embodiment less than 25% (mol.) Of the total number of weakly branched paraffins. Weakly branched paraffins, either having one alkyl branching group or containing three primary carbon atoms, may comprise more than 70% (mol.) Of the total number of weakly branched monoolefins. Any alkyl branching group may be attached to any carbon atom in an aliphatic alkyl chain.

The feedstock fed to the process may include paraffins and more highly branched than slightly branched paraffins. However, after dehydrogenation, such highly branched paraffins tend to form highly branched monoolefins, which after alkylation tend to lead to the formation of RAB. For example, paraffin molecules containing at least one quaternary carbon atom, after dehydrogenation followed by alkylation, tend to produce phenylalkanes containing quaternary carbon atoms and lacking a phenyl group. Preferably, the loading of these highly branched paraffins loaded into the process is minimized. When calculated on the number of moles of a paraffin molecule containing at least one quaternary carbon atom, in the paraffin feedstock or in all the paraffins loaded into the process, usually less than 10%, preferably less than 5%, more preferably less than 2%, and most preferably less than 1%.

Paraffin feedstock is usually a mixture of linear and weakly branched paraffins containing different amounts of carbon atoms. You can use any suitable method for producing paraffin feedstock. One method leads to the production of paraffin feedstock by recovering unbranched (linear) hydrocarbons or weakly branched hydrocarbons from the oil fraction corresponding to the boiling point of kerosene. Proven commercial methods for this separation are the UOP Molex ™ method for liquid-phase adsorption separation of normal paraffins from isoparaffins and cycloparaffins and the UOP Kerosene Isosiv ™ method for vapor-phase adsorption separation of normal paraffins from abnormal paraffins. The feed streams into these aforementioned separation processes contain branched paraffins, which are more highly branched than weakly branched paraffins.

Well-known analytical methods of the current level of gas chromatography can determine the composition of such mixtures of linear, slightly branched and branched paraffins, which act as a paraffin feedstock or feed stream for the aforementioned adsorption separation processes. H. Schuiz, et al., Chromatographia 1, 1968, p. 315 describes a suitable method for identifying components in complex mixtures of paraffins using a gas chromatograph with temperature programming.

In the alkylation of detergents, the phenyl compound in the phenyl feed includes benzene. The phenyl compound in the phenyl feedstock may be an alkylated or otherwise substituted derivative with a higher molecular weight than benzene, including toluene, ethylbenzene, xylene, phenol, naphthalene and the like, but these alkylation products may be less suitable precursors of detergents in comparison with alkyl benzenes.

The process in question can be divided into a dehydrogenation step, an isomerization step, and an alkylation step. The present invention is not limited to any one specific process flow diagram for the dehydrogenation step. The configuration of the dehydrogenation step can be made essentially by the method described in US-A-6187981 B1. Any suitable dehydrogenation catalyst may be used. The catalyst may be a layered composition comprising an inner core and an outer layer bonded to the inner core, where the outer layer comprises a heat-resistant inorganic oxide with uniform dispersion of at least one platinum group metal on it (group VIII (IUPAC 8-10)) and at least one promoter metal, and where at least one modifier metal is dispersed on the catalyst composition. The outer layer is associated with the inner core to the extent that the attrition loss can become less than 10% (wt.) When calculated on the mass of the outer layer. Such a catalyst composition is described in US Pat. No. 6,177,381. The dehydrogenation conditions are selected so as to minimize cracking and formation of polyolefin by-products.

Despite the fact that, under dehydrogenation conditions, olefin skeleton isomerization may take place, its passage during the dehydrogenation step is not a requirement of the present invention, since olefins undergo isomerization in the isomerization step described later in this document. Reducing the dehydrogenation temperature can minimize skeleton isomerization. Skeleton isomerization under dehydrogenation conditions means isomerization, which leads to an increase in the number of primary carbon atoms in a paraffin or olefin molecule. The monoolefin-containing dehydrogenation product stream from the paraffin dehydrogenation step is usually a mixture of olefins and unreacted paraffins, corresponding in their skeleton to the paraffins loaded in the dehydrogenation step.

The minimum isomerization of the skeleton of paraffins and olefins in the dehydrogenation step corresponds to a skeleton isomerization of less than 15% (mol.), And preferably less than 10% (mol.) Of paraffins and olefins. Thus, if the bulk of the paraffins in the feed will be linear (unbranched) compounds, then it is preferable that the bulk of the olefins would also be linear (unbranched) olefins.

The linear monoolefins in the dehydrogenation reaction product stream are passed into the skeleton isomerization zone, where linearity is reduced and the number of primary carbon atoms in the olefin molecules is regulated. Isomerization of the skeleton of the molecule may include an increase in the number of methyl branching groups in the aliphatic chain by 1 or 2. Since the total number of carbon atoms in the olefin molecule remains the same, each additional methyl branching group leads to a decrease in the aliphatic chain by one carbon atom.

The skeleton isomerization step sufficiently reduces the linearity of the dehydrogenation reaction product stream, so that after use in the alkylation the phenylalkylalkylate will meet the requirements for the content of primary carbon atoms, selectivity for the production of 2-phenylalkanes and selectivity for the production of internal quaternary phenylalkanes. The skeleton isomerization for olefins of the feedstock can be carried out by any method known in the art and using any known catalyst. Suitable catalysts include ferrierite, ALPO-31, SAPO-11, SAPO-31, SAPO-41, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM -48, ZSM-50, ZSM-57, MeAPO-11, MeAPO-31, MeAPO-41, MeAPSO-11, MeAPSO-31, MeAPSO-41, MeAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41 , ELAPSO-11, ELAPSO-31, ELAPSO-41, lomontite, cancrinite, offretite, the hydrogen form of stilbite, the magnesium or calcium form of mordenite, and the magnesium or calcium form of partite. Suitable MeAPSO-31 catalysts include MgAPSO-31. Many natural zeolites, such as ferrierite, which are characterized by an initially reduced pore size, can be converted into forms suitable for isomerization of the skeleton of olefins by removing the associated alkali metal or alkaline earth metal by conducting ammonium ion exchange and calcination to obtain a substantially hydrogen form, such as it is offered in USA-4795623 and US-A-4924027. However, the H-form of mordenite is not a suitable catalyst for isomerizing the skeleton of an olefin feedstock. Catalysts and conditions for isomerizing the skeleton of an olefin feedstock are described in US-A-5510306; US-A-5082956; and US-A-5741759. Skeleton isomerization conditions include conditions in which at least part or all of the hydrocarbons come into contact with the skeleton isomerization catalyst in the liquid phase. The isomerization temperature is in the range of 50 to 400 ° C (122 to 752 ° F). If the isomerization catalyst will contain a metal of group VIII (IUPAC 8-10), then the isomerization conditions will include a molar ratio between hydrogen and hydrocarbon greater than 0.01: 1.

The flow of isomerization products upon receipt of the MAB contains a weakly branched monoolefin. A weakly branched monoolefin refers to a monoolefin having a total number of carbon atoms ranging from 8 to 28, three or four carbon atoms of which are primary carbon atoms, and none of the remaining carbon atoms is a quaternary carbon atom. A weakly branched monoolefin may have a total number of carbon atoms ranging from 8 to 15, preferably from 10 to 15 carbon atoms, and more preferably from 11 to 13 carbon atoms. The flow of isomerization products is characterized by a concentration of weakly branched monoolefins in excess of 25% (mol.).

A weakly branched monoolefin generally includes an aliphatic alkene described by the general formula (p _i -alkyl _i ) _i- q-alkene, with the longest straight chain aliphatic alkenyl comprising a carbon-carbon double bond, referred to as “alkene”. A weakly branched monoolefin also consists of one or more alkyl branching groups attached to an aliphatic alkenyl chain and designated respectively as “(p _i -alkyl _i ) _i ” in the formula. The double bond is located in the aliphatic alkenyl chain between the carbon atoms with numbers q and (q + 1). In the aliphatic alkenyl chain, the numbering goes from one end in the direction that allows you to assign the lowest numbers to the carbon atoms forming the double bond.

The weakly branched monoolefin may be an alpha monoolefin or a vinylidene monoolefin, but preferably it is an internal monoolefin. As used herein, the term "alpha olefins" means olefins described by the formula R-CH = CH ₂ . The term "internal olefins" includes disubstituted internal olefins described by the formula R-CH = CH-R; trisubstituted internal olefins described by the formula RC (R) = CH-R; and tetrasubstituted olefins described by the formula RC (R) = C (R) -R. Disubstituted internal olefins include internal beta olefins described by the formula R — CH═CH — CH ₃ . As used herein, the term “vinylidene olefins” means olefins described by the formula RC (R) = CH ₂ . In the preceding formulas, R represents an alkyl group, which may be identical to or different from the other alkyl group (s) in each formula. If the weakly branched monoolefin is an internal monoolefin, then, as long as the definition of the term “internal olefin” allows, any two carbon atoms in the aliphatic alkenyl chain can participate in the formation of a double bond. Suitable weakly branched monoolefins include octenes, nonenes, decenes, undecenes, dodecenes, tridecenes, tetradecenes, pentadecenes, hexadecenes, heptadecenes, octadecenes, nonadenecenes, eicosenoses, henosecosenes, hetakosecosenes, tricenoses, triquenoses, tricenoses, tricenoses.

In the general case, the alkyl branching group or the alkyl branching groups in the weakly branched monoolefin are methyl, ethyl and propyl groups, with shorter and normal branches being preferred. Preferably, the weakly branched monoolefin has only one alkyl branching group, but two alkyl branching groups are also possible. Weakly branched monoolefins, either having two alkyl branching groups or containing four primary carbon atoms, may comprise less than 40% (mol.), And preferably less than 30% (mol.) Of the total number of weakly branched monoolefins, while the remaining weakly branched monoolefins have one alkyl branching group. Weakly branched monoolefins, either having one alkyl branching group or containing three primary carbon atoms, may comprise more than 70% (mol.) Of the total number of weakly branched monoolefins. US-A-6187981 describes analytical methods for determining the composition of a mixture of weakly branched monoolefins.

In addition to the weakly branched monoolefin, other acyclic compounds may come into contact with the alkylation catalyst. The isomerization product stream or one or more other streams may bring these other acyclic compounds into contact with the catalyst. Other acyclic compounds include linear (linear) olefins and monoolefins, including linear and non-linear paraffins. Unbranched (linear) olefins that can come into contact with the zeolite can have a total number of carbon atoms per paraffin molecule in the range from 8 to 28, preferably from 8 to 15, and more preferably from 10 to 14 carbon atoms. The unbranched olefin may be an alpha monoolefin, but preferably it is an internal monoolefin. In the presence of a linear olefin in the isomerization product stream together with weakly branched monoolefins, the linear olefin content in the isomerization product stream is preferably less than or equal to 75% (mol.) Of the total amount of monoolefins, and more preferably less than 60% (mol.) of the total number of monoolefins.

Due to the possible presence of linear monoolefins, the total stream of isomerization products on average may contain less than 3 or 3 to 4 primary carbon atoms per monoolefin molecule in the stream of isomerization products. Depending on the relative ratios between the amounts of linear and weakly branched monoolefins, the flow of isomerization products or the sum of all monoolefins that come into contact with the zeolite may contain from 2.25 to 4 primary carbon atoms per monoolefin molecule.

Linear and / or non-linear paraffins, if any, which may come into contact with the zeolite, with or without isomerization product stream, can be characterized by the total number of carbon atoms per paraffin molecule in the range from 8 to 28 carbon atoms, preferably from 8 to 15 carbon atoms, and more preferably 10 to 14 carbon atoms. Such linear and nonlinear paraffins are not supposed to have a significant effect on the course of the alkylation stage, but play the role of a diluent. However, the presence of such diluents in the alkylation reactor generally results in higher volumetric costs for process streams, which may necessitate the use of larger equipment and more catalyst in the alkylation reaction loop and larger product recovery plants. The isomerization product stream preferably does not contain unacceptable concentrations of impurities or poisons that would lead to difficulties in the alkylation step. Some impurities can be removed using well-known steps, such as removal by distillation and selective hydrogenation to convert polyolefins to monoolefins. In the case of monoalkylation of the phenyl compound using a weakly branched olefin, the stream of isomerization products will preferably contain a slight, if any, dimer of this particular weakly branched olefin.

The concentration of monoolefins, which are more highly branched in comparison with weakly branched monoolefins, in the stream of isomerization products is preferably minimized in order to prevent their conversion to RAB as a result of alkylation. For example, the isomerization product stream may contain monoolefin molecules containing at least one quaternary carbon atom, which upon alkylation will tend to produce phenylalkanes containing a quaternary carbon atom that is not bound to the phenyl moiety. Monoolefins containing at least one quaternary carbon atom preferably comprise less than 10% (mol.), And more preferably less than 1% (mol.) Of the flow of isomerization products or the sum of all monoolefins that come into contact with the catalyst.

The product of the skeleton isomerization step includes weakly branched monoolefins, and it can supply olefins to the alkylation section. Accordingly, the isomerization product stream can generally be a mixture of unreacted paraffins, linear (unbranched) olefins and branched monoolefins, which usually fall into the range of C ₈ -C ₂₈ , preferably in the range of C ₈ -C ₁₅ , and more preferably in the range of C ₁₀ -C ₁₅ . From 20 to 60% (mol.) Of the total amount of monoolefins in the flow of isomerization products are linear (unbranched) olefins. The monoalkyl branched olefins in the isomerization product stream are preferably monomethylalkenes. The level of dialkyl-branched olefins in the isomerization product stream in three embodiments of this invention is less than 30% (mol.), Ranging from 10% (mol.) To 20% (mol.) And less than 10% (mol.) isomerization product stream. The flow of isomerization products can be obtained from part or an aliquot of the product from the stage of isomerization of the skeleton. An aliquot of the product from the skeleton isomerization step is a fraction of the product from the skeleton isomerization step, which is essentially characterized by the same composition as the product from the skeleton isomerization step.

In the olefin isomerization step, in addition to the olefin isomerization, paraffin skeleton isomerization can also take place. Any resulting non-linear paraffins in the isomerization product stream are passed together with normal (linear) paraffins through the alkylation step described later in this application and recycled to the dehydrogenation step, where they are mixed with the paraffins supplied with the paraffin feed. In the dehydrogenation step, these non-linear paraffins sent for recycling may or may not be dehydrogenated to produce monoolefins. Already isomerized paraffins or already isomerized paraffins converted to olefins, then re-enter the stage of isomerization of olefins, where they can be subjected to additional isomerization. Thus, the isomerization product stream contains a mixture of non-linear paraffins and non-linear olefins, which can be obtained as a result of several paraffin passes through the stages of dehydrogenation, isomerization and alkylation.

Weakly branched monoolefins in the stream of isomerization products react with a phenyl compound. Alkylation takes place in an alkylation step consisting of a reaction zone and a separation zone. In this invention, it is possible to use any technological scheme of the alkylation step. The configuration of the alkylation step can be made essentially by the method described in US-A-6187981 B1. Any suitable alkylation catalyst may be used. Alkylation catalysts include zeolites having the structure of zeolite BEA, MOR, MTW and NES. Such zeolites include mordenite, ZSM-4, ZSM-12, ZSM-20, offretitis, gmelinite, beta, NU-87, and gottardiitis.

It is assumed that the alkylation conditions result in minimal isomerization of the skeleton of a weakly branched monoolefin or any other olefins and any paraffins in the isomerization product stream. Minimum skeleton isomerization corresponds to that less than 15% (mole), and more preferably less than 10% (mole) of olefin, aliphatic alkyl chain and any intermediate reaction product undergo isomerization of the skeleton. Thus, the alkylation preferably takes place essentially in the absence of isomerization of the skeleton of a weakly branched monoolefin, and the number of primary carbon atoms in the weakly branched monoolefin is the same as the number of primary carbon atoms per phenylalkane molecule. Any additional methyl branching group in the aliphatic alkyl chain of the phenylalkane product will lead to a slight increase in the number of primary carbon atoms in the phenylalkane product, due to the number of primary carbon atoms in the weakly branched monoolefin. In conclusion, we can say that, despite the fact that under the conditions of alkylation, the formation of 1-phenylalkane does not proceed on a significant scale, its production will lead to a slight decrease in the number of primary carbon atoms in the phenylalkane product.

Alkylation of the phenyl compound using weakly branched monoolefins results in (m _i -alkyl _i ) _i -n-phenylalkanes, where the aliphatic alkyl group contains two, three or four primary carbon atoms per phenylalkane molecule. An aliphatic alkyl group may contain three primary carbon atoms per phenylalkane molecule, more preferably when methyl groups are present at both ends of the chain. In this embodiment, the alkylation results in monomethylphenylalkanes. However, there is no need for all (m _i -alkyl _i ) _i -n-phenylalkanes obtained to have the same number of primary carbon atoms per phenylalkane molecule. From 0% (mol.) To 75% (mol.), And preferably from 0% (mol.) To 40% (mol.) Of the obtained (m _i -alkyl _i ) _i -n-phenylalkanes may contain 2 primary carbon atoms per phenylalkane molecule. As much as possible, and preferably from 25% (mol.) To 100% (mol.) Of the obtained (m _i -alkyl _i ) _i -n-phenylalkanes can contain 3 primary carbon atoms per phenylalkane molecule. In one embodiment, from 0% (mol.) To 40% (mol.) Of the obtained (m _i -alkyl _i ) _i -n-phenylalkanes may contain 4 primary carbon atoms. Thus, (m-alkyl) -n-phenylalkanes having only one methyl branching group are preferred, and are referred to herein as monomethylphenylalkanes. The number of primary, secondary and tertiary carbon atoms per molecule of the phenylalkane product can be determined using the high resolution multipulse nuclear magnetic resonance (NMR) spectra reading technique and the undistorted polarization transfer amplification (DEPT) method described in the brochure entitled "High Resolution Multipulse NMR Spectrum Editing and DEPT ”, distributed by Bruker Instruments, Inc., Manning Park, Billerick, Massachusetts, USA.

The alkylation selectivity parameters for the preparation of 2-phenylalkanes and internal quaternary phenylalkanes in the prior art were determined using two slightly different analytical and computational methods. US-A-6111158 and US-A-6187981 use methods that result in slightly different selectivities. Selectivities determined by the methods described in US-A-6111158 are hereinafter referred to as simplified selectivities, and selectivities determined by US-A-6187981 are referred to herein as selectivities (that is, without the adjective “simplified”). Alkylation of the phenyl compound using weakly branched monoolefins is characterized by selectivity for the production of 2-phenylalkanes in the range from 40 to 100, and preferably from 60 to 100 in another embodiment, and a selectivity for the production of internal quaternary phenylalkanes of less than 10 in one embodiment, and preferably less than 5.

Quaternary phenylalkanes can be obtained by alkylation of a phenyl compound using a weakly branched monoolefin containing at least one tertiary carbon atom. Depending on the location of the quaternary carbon atom with respect to the ends of the aliphatic alkyl chain, the quaternary phenylalkane may be either an internal or terminal quaternary compound.

At least a portion of the liquid distillate stream of the paraffin column in the separation zone during alkylation is recycled to the dehydrogenation step. The recycled portion of the liquid distillate stream may be an aliquot of the liquid distillate stream. The method may lead to the selective hydrogenation of any diolefins present in the dehydrogenation product stream.

A portion of the paraffin column liquid distillate stream can also be recycled to the isomerization step (section), since the paraffin column liquid distillate stream may contain monoolefins. However, the concentration of monoolefins in the liquid distillate stream of the paraffin column is generally less than 0.3% by weight.

The method may allow selective removal of any aromatic by-products present in the dehydrogenation product stream. Aromatic by-products can be selectively removed from the isomerization product stream, dehydrogenation product stream, paraffin column liquid distillate stream that is recycled to the dehydrogenation step, or diolefin selective hydrogenation product stream (if any).

In one embodiment, the implementation of the method leads to a composition of MAB containing phenylalkanes having one phenyl group and one aliphatic alkyl group, where phenylalkanes are characterized by:

(i) an average mass of aliphatic alkyl groups of phenylalkanes in the mass range from a C ₁₀ aliphatic alkyl group to a C ₁₃ aliphatic alkyl group;

(ii) a level of phenylalkanes having a phenyl group attached at position 2 and / or 3 of the aliphatic alkyl group in excess of 55% (wt.) phenylalkanes; and

(iii) an average branching level of aliphatic alkyl phenylalkane groups ranging from 0.25 to 1.4 alkyl branching groups per phenylalkane molecule if the sum of the levels of 2-phenylalkanes and 3-phenylalkanes is greater than 55% (wt.) and less than or equal to 85% (wt.) phenylalkanes, or an average level of branching of aliphatic alkyl phenylalkane groups in the range from 0.4 to 2.0 alkyl branching groups per phenylalkane molecule if the sum of the concentrations of 2-phenylalkanes and 3-phenylalkanes is led ichina, greater than 85% (wt.) phenylalkanes; and

(iv) where the aliphatic alkyl groups of the phenylalkanes mainly include linear aliphatic alkyl groups, one-branch aliphatic alkyl groups or two-branch aliphatic alkyl groups, and where the alkyl groups, if any, on the aliphatic alkyl chain of the aliphatic alkyl groups are mainly include small substituents such as methyl branching groups, ethyl branching groups or propyl branching groups, and where the alkyl groups are branched if present, are attached at any position on the aliphatic alkyl chain of aliphatic alkyl groups, provided that the phenylalkanes containing at least one quaternary carbon atom in the aliphatic alkyl group comprise less than 20% of the phenylalkanes.

One way to obtain this MAB composition involves first dehydrogenating paraffins to produce the corresponding monoolefins. The method includes the isomerization of monoolefins having an average weight in the mass range from C ₁₀ paraffin to C ₁₃ paraffin, to produce isomerized monoolefins having an average branching level in the range of 0.25 to 1.4 or from 0.4 to 2.0 alkyl groups branching per olefin molecule. These isomerized monoolefins mainly include linear monoolefins, single-branching monoolefins or two-branching monoolefins, and alkyl branching groups, if any, on the aliphatic alkyl chain of the isomerized monoolefins mainly include small substituents, such as methyl branching groups, these branching groups or propyl branching groups. The alkyl branching groups of the isomerized monoolefins can be attached at any position on the aliphatic alkyl chain of the olefin, subject to certain restrictions that depend on the desired characteristics of the resulting phenylalkanes. The isomerized monoolefins provide alkylation of the phenyl compound to produce phenylalkanes. The resulting phenylalkanes have the characteristics that phenylalkanes having a phenyl group attached at position 2 and / or 3 of the aliphatic alkyl group comprise more than 55% (wt.) Of phenylalkanes, and phenylalkanes containing at least one the quaternary carbon atom in the aliphatic alkyl group, make up less than 20% of phenylalkanes.

Sulfonation of the phenylalkanes obtained by the methods of this invention and the neutralization of the sulfonated product can be carried out by the methods described in US-A-6187981.

In other aspects of the present invention, the present invention is a MAB composition and MABS composition obtained by the methods described in this application. MAB compositions obtained by the methods of this invention may contain lubricants, and lubricating additives may be contained in MABS compositions obtained by the methods of this invention.

The drawing shows the layout for the integrated dehydrogenation-isomerization-alkylation scheme of the present invention. The drawing shows a paraffin feedstock containing C ₁₀ -C ₁₃ normal paraffins entering the process through line 10. The paraffin feedstock is combined with a paraffin stream sent for recycling containing C ₁₀ -C ₁₃ normal paraffins and coming in line 46, s obtaining a combined feed stream flowing through line 12, which leads to a dehydrogenation section 14 for dehydrogenation of paraffins to olefins. Line 16 pits hydrogen, releasing it from the process. The dehydrogenation product stream in line 18 contains C ₁₀ -C ₁₃ normal paraffins, C ₁₀ -C ₁₃ normal monoolefins, C ₁₀ -C ₁₃ normal diolefins and aromatic by-products. The selective hydrogenation section 20 receives hydrogen feed via line 22 to selectively hydrogenate the diolefins in the dehydrogenation product stream to produce monoolefins and thereby remove the C ₁₀ -C ₁₃ normal diolefins. The stream of selective hydrogenation products passes through line 24 to the olefin isomerization section 26, where normal monoolefins are isomerized to produce weakly branched monoolefins. The stream of isomerization products in line 28 contains C ₁₀ -C ₁₃ weakly branched monoolefins, C ₁₀ -C ₁₃ normal paraffins and aromatic by-products. In the aromatics removal section 30, aromatic by-products are removed and eliminated from the process via line 32. The product flow of the aromatics removal section passes through line 34 to the alkylation section 52, which includes a reaction zone for alkylation 36 and a separation zone for alkylation 40. As a stream aromatics removal section product, and the recycle phenyl benzene stream in line 44 is charged to the alkylation reaction zone 36, where C ₁₀ -C ₁₃ slightly branched monoolefins alkylated b nzol to produce MAB. The product stream from the alkylation reaction zone contains benzene, C ₁₀ -C ₁₃ normal paraffin, MAB and heavy alkyl benzenes such as by-products of polyalkyl benzenes. This product stream passes through line 38 to the separation zone during alkylation 40. The phenyl feedstock containing benzene enters the separation zone 40 via line 42. In the separation zone during alkylation 40, the phenyl stream sent for recycling is recovered and fed to line 44 sent for recycling the paraffin stream with the supply to line 46, heavy alkylbenzenes excluded from the process through line 50, and the product stream containing MAB entering line 48.

All references herein to the groups of elements belong to the Periodic Table of the Elements, " CRC Handbook of Chemistry and Physics", CRC Press, Boca Raton, Florida, 80 ^th Edition, 1999-2000.

EXAMPLE 1

100 cubic meters was placed in a reactor tube having an inner diameter of 2.22 cm (7/8 inch). cm sample of catalyst containing 50% (wt.) MgAPSO-31 associated with gamma alumina. A feedstock consisting of a mixture containing 1-dodecene was passed over the catalyst at a fluid hourly space velocity of 5 h ^-1 . The temperature of the catalyst was first set to 250 ° C. (482 ° F.), and then adjusted to maintain the desired degree of conversion of linear olefins.

The product was analyzed using a Hewlett Packard (HP) HP5890 gas chromatograph equipped with a slit / slitless device for introducing a sample, and a flame ionization detector (PID) was used. In the sample injection device, the gas chromatograph was equipped with a plug-in hydrogenator tube. The column was a 50-meter Hewlett Packard HP PONA column having an inner diameter of 0.2 mm. A Restek red lite 11 mm membrane and an HP O-ring were used as gasket material at the inlet. Gas chromatography parameters included: a gaseous hydrogen carrier; Column head pressure 138 kPa (g.) (20 lb / in ² (g).); flow rate in the column 1 ml / min; retention of 250 ml / min; washing the membrane 4 ml / min; sample volume 0.2 microliters; the temperature in the device for entering the sample 175 ° C (367 ° F); detector temperature 275 ° C (527 ° F); and a program for setting the temperature in the furnace, consisting of holding at 50 ° C (122 ° F) for 5 minutes, ramping at 3 ° C / min (5 ° P / min) to 175 ° C (347 ° F) and linear changes at 10 ° C / min (18 ° F / min) to 270 ° C (518 ° F). The sample was prepared for injection by weighing 4-5 mg of the sample into a container of a 2 ml gas chromatograph automatic sampler. A catalyst for the hydrogenator was prepared by preparing a solution of 20 g of nickel nitrate hexahydrate and 40 ml of methanol. The nickel nitrate solution was slowly poured into an evaporation cup on 20 g of Chromosorb P material, which was a calcined diatomite obtained from crushed refractory brick. To evaporate methanol, the mixture in the evaporation cup was heated on a heating plate with constant stirring to 65 ° C (149 ° F) until the mixture began to look dry. 3 g of the mixture was placed in the tube of the plug-in hydrogenator and kept here, placing glass wool on each end. To activate the catalyst, a hydrogen carrier gas was passed through the catalyst at 60 ml / min, and the temperature was increased to 350 ° C (662 ° F) and the catalyst was treated under these conditions for 3 hours. The standards required for this method were n-decane, n-undecane, n-dodecane, n-tridecane and n-tetradecane. The relative positions of monomethyl isomers are presented in the previously mentioned article by H. Schultz et al.

The products were summarized, sorted into five categories as follows, while the contents of each category were indicated as shown in parentheses: light products characterized by carbon atoms of 11 or less, [C ₁₁ -], linear olefins [linear], olefins with monomethyl branching [mono], olefins with dimethyl and ethyl branches [di] and heavy products characterized by carbon atoms corresponding to C ₁₃ or more [C ₁₃₊ ]. In addition, the following performance criteria were calculated:

The degree of conversion = 100 · (1 - ([linear] _product / [linear] _feedstock ))

Monomethyl = 100 · ([mono] / ([mono] + [di]))

Lungs = 100 · ([C _11- ] / ([C _11- ] + [linear] + [mono] + [di] + [C ₁₃₊ ]))

Heavy = 100 · ([C ₁₃₊ ] / ([C _11- ] + [linear] + [mono] + [yes] + [C ₁₃₊ ]))

The results are shown in table 1:

Table 1
results Degree of conversion Monomethyl Lungs Heavy 69.9 86.8 0.64 3.53

EXAMPLE 2

Example 1 was repeated except that the feedstock consisted of a mixture of C ₁₁ , C ₁₂ and C ₁₃ linear olefins. The feedstock contained 28.7% (mol.) C ₁₁ , 39.6% (mol.) C ₁₂ and 31.7% (mol.) C ₁₃ . The product contained monomethyl branched olefins. The distribution of monomethyl branched olefins in the product was 30.9% (mol.) C ₁₁ , 42.4% (mol.) C ₁₂ and 26.7% (mol.) C ₁₃ . This example demonstrates that, without recycling, the distribution by the number of carbon atoms in the monomethyl branching olefin product is different from the distribution of carbon atoms in the feed.

EXAMPLE 3

The method was implemented as shown in the drawing, with the exception of the absence of a paraffin stream sent for recycling to line 46. Paraffin feed was supplied to the process through line 10, and the MAB was extracted in line 48 and the method was implemented under stationary conditions. The stream entering line 24 was characterized by the composition of the feedstock from Example 2, and the stream entering line 28 was characterized by the composition of the product from Example 2. After that, the paraffin stream sent for recycling to line 46 was started. Once stationary conditions were re-established, the distribution by the number of carbon atoms in the aliphatic alkyl groups of the MAB product shifted to smaller numbers of carbon atoms in comparison with what was obtained when the method was implemented in the absence of etsikl paraffins stream.

EXAMPLE 4

The method was implemented as shown in the drawing. The paraffin feedstock entered the process through line 10, and the MAB was extracted in line 48 and the method was implemented under stationary conditions. The flow entering line 28 was characterized by the composition shown in table 1.

EXAMPLE 5

The starting compound 1-dodecene was isomerized and an isomerized product stream was obtained containing a mixture of C ₁₂ monomethyl olefins and characterized by the composition shown in Table 2.

table 2
The composition of the flow of isomerization products Olefin component Content (% (wt.)) Lungs ¹ 0.64 Linear olefins ² 30.11 6-methylundecene 7.66 5-methylundecene 15.33 4-methylundecene 11.82 3-methylundecene 12.95 2-methylundecene 8.87 Other alkyl olefins ³ 9.05 Heavy ⁴ 3.53 Total 99.96 ¹ Lungs include olefins containing less than 12 carbon atoms.
² Linear olefins include linear C ₁₂ olefins.
³ Other alkyl olefins include dimethyl, trimethyl and other C ₁₂ olefins.
⁴ Heavy include dimers and trimers of C ₁₂ olefins.

The isomerization product stream was mixed with benzene to obtain a combined feedstock consisting of 93.3% (wt.) Benzene and 6.7% (wt.) Isomerization product stream, which corresponded to a 30: 1 molar ratio between benzene and olefin. In a cylindrical reactor, which had an internal diameter of 0.875 inches (22.2 mm), 75 cubic meters was charged. cm (53.0 g) of the extrudate obtained in Example 1 of US-A-6111158.

The combined feedstock is transferred to a reactor and contacted the extrudate at a LHSV of 2.0 hr ^-1, a total pressure of 500 lb / ⁱⁿ² (g.) (3447 kPa (g.)) And temperature at the reactor inlet of 125 ° C (257 ° F). Under these conditions, the reactor was preliminarily operated for a period of 24 hours, and then the first liquid product was collected over a subsequent period of 6 hours.

Upon completion of the collection of the first liquid product over a period of 6 hours and at entry to the reactor of the combined feedstock at a LHSV of 2.0 hr ^-1 and a total pressure of 500 lb / ⁱⁿ² (g.) (3447 kPa (g. )) the temperature at the inlet to the reactor was increased from 125 ° C (257 ° F) to 150 ° C (302 ° F). The reactor was pre-worked for 12 hours at admission to the reactor of the combined feedstock and its coming into contact with the extrudate at a LHSV of 2.0 hr ^-1, a total pressure of 500 lb / ⁱⁿ² (g.) (3447 kPa (g. )) and the temperature at the inlet of the reactor 150 ° C (302 ° F). Under these conditions, a second liquid product was collected over a subsequent period of time of 6 hours. The results for the second liquid product are shown in table 3.

Upon completion of the collection of the second liquid product during 6 hours the combined feedstock supply to the reactor was kept at a liquid hourly space velocity of 2.0 hr ^-1, and the total pressure was maintained at 500 lb / ⁱⁿ² (g.) (3447 kPa (g. )). Under these conditions, the temperature at the inlet to the reactor was increased from 150 ° C (302 ° F) to 175 ° C (347 ° F). The reactor was pre-worked over a period of 12 hours at admission to the reactor of the combined feedstock and its coming into contact with the extrudate at a LHSV of 2.0 hr ^-1, a total pressure of 500 lb / ⁱⁿ² (g.) (3447 kPa (g.)) and a reactor inlet temperature of 175 ° C (347 ° F). Under these conditions, a third liquid product was collected over a subsequent period of time of 6 hours. The third liquid product was analyzed by ¹³ C NMR as previously described. Table 3 shows the simplified selectivity for the production of 2-phenylalkanes and the simplified selectivity for the production of internal quaternary phenylalkanes for the third liquid product. Selectivities for the production of terminal quaternary phenylalkanes were determined using the analytical and computational methods proposed in US-A-6187981.

Table 3
Liquid Product Analysis Reactor inlet temperature, ° C (° F) Simplified selectivity for 2-phenylalkanes Simplified selectivity for the production of internal quaternary phenylalkanes 150 (302) 66,4 4.6 175 (347) 77.7 2.9

Thus, the alkylation in the example was characterized by selectivity for the production of 2-phenylalkanes in the range from 40 to 100 and selectivity for the production of internal quaternary phenylalkanes of less than 10. Despite the fact that recycling of paraffins was not used in this example, it seems that if, in accordance with the present invention, the recycling of paraffins was used, then the selectivity for the production of 2-phenylalkanes would fall in the range from 40 to 100, and the selectivity for internal quaternary phenylalkanes teachings would constitute a value smaller than 10.

Claims (15)

1. A method of producing phenylalkanes, comprising the steps of:
a) dehydrogenating a feedstock containing C ₈ -C ₂₈ paraffins in a dehydrogenation section operating under dehydrogenation conditions sufficient to dehydrogenate paraffins, and recovering from the dehydrogenation section a stream of dehydrogenation products containing monoolefins and paraffins;
b) passing at least a portion of the dehydrogenation product stream to the isomerization section operating under isomerization conditions sufficient to isomerization of olefins and recovering from the isomerization section a stream of isomerization products containing monoolefins and paraffins, where the monoolefins in the isomerization product stream contain from 8 to 28 carbon atoms, and where at least a portion of the monoolefins in the dehydrogenation product stream contains 3 or 4 primary carbon atoms and does not contain quaternary carbon atoms;
c) passing the phenyl compound and at least part of the flow of isomerization products containing monoolefins to the alkylation section, operating the alkylation section under alkylation conditions sufficient to alkylate the phenyl compound using monoolefins in the presence of an alkylation catalyst to produce phenylalkanes containing molecules including one phenyl moiety and one aliphatic alkyl moiety containing from 8 to 28 carbon atoms; where at least a portion of the phenylalkanes formed in the alkylation section contains 2, 3 or 4 primary carbon atoms and does not contain quaternary carbon atoms with the exception of any quaternary carbon atom bonded by the carbon-carbon bond to the carbon atom of the phenyl moiety; and where the alkylation is characterized by a selectivity for the production of 2-phenylalkanes in the range from 40 to 100 and a selectivity for the production of internal quaternary phenylalkanes of less than 10;
d) recovering from the alkylation section a stream of alkylation products containing phenylalkanes and containing a paraffin stream for recycling; and
e) passing at least a portion of the stream sent for recycling to the dehydrogenation section. 2. The method according to claim 1, in which at least one stream selected from at least a portion of the dehydrogenation product stream and at least a portion of the isomerization product stream contains weakly branched monoolefins, and preferably at least at least a part of the isomerization product stream is characterized by a concentration of weakly branched monoolefins in excess of 25 mol.% when calculating at least a part of the isomerization product stream. 3. The method according to claim 2, in which at least a portion of the monoolefins in at least one stream selected from at least a portion of the isomerization product stream and at least a portion of the dehydrogenation product stream contains linear monoolefins and preferably at least a portion of the isomerization product stream is characterized by a concentration of linear monoolefins of less than or equal to 75 mol%. 4. The method according to claim 2, in which at least a portion of the monoolefins in at least one stream selected from at least a portion of the stream of dehydrogenation products and at least a portion of the stream of isomerization products contains at least one quaternary carbon atom, and preferably at least part of the isomerization product stream is characterized by a concentration of olefins containing at least one quaternary carbon atom of less than 10 mol%. 5. The method according to claim 1, in which phenylalkanes are characterized by an average weight of aliphatic alkyl groups of phenylalkanes in the mass range from a C 10 aliphatic alkyl group to a C 13 aliphatic alkyl group; the level of phenylalkanes having a phenyl group attached at position 2 and / or 3 of the aliphatic alkyl group is greater than 55% by weight of phenylalkanes; the average level of branching of aliphatic alkyl groups of phenylalkanes in the range from 0.25 to 1.4 of the alkyl group of branching per molecule of phenylalkane, if the sum of the levels of 2-phenylalkanes and 3-phenylalkanes is greater than 55 wt.% and less than or equal to 85 wt.% phenylalkanes, or an average level of branching of aliphatic alkyl groups of phenylalkanes in the range from 0.4 to 2.0 alkyl branching groups per phenylalkane molecule, if the sum of the concentrations of 2-phenylalkanes and 3-phenylalkanes exceeds 85 wt.% phen ilalkans; aliphatic alkyl groups of phenylalkanes include linear aliphatic alkyl groups, single-branch aliphatic alkyl groups or two-branch aliphatic alkyl groups; alkyl branching groups, if any, on the aliphatic alkyl chain of aliphatic alkyl groups include methyl branching groups, ethyl branching groups or propyl branching groups; and the branching alkyl groups, if any, are attached at any position on the aliphatic alkyl chain of the aliphatic alkyl groups, provided that the phenylalkanes containing at least one quaternary carbon atom in the aliphatic alkyl group comprise less than 20% of the phenylalkanes. 6. The method according to claim 1, in which the dehydrogenation section includes a dehydrogenation catalyst containing at least one Group VIII metal (IUPAC 8-10) and a promoter metal dispersed on the outer layer of an inorganic oxide that is bonded to a heat-resistant inorganic oxide, which makes up the inner core, and the metal modifier is further dispersed on the dehydrogenation catalyst. 7. The method according to claim 1, in which the isomerization section includes an isomerization catalyst containing a carrier material selected from the group consisting of ferrierite, SAPO-11 and MgAPSO-31. 8. The method according to claim 1, in which the isomerization section includes an isomerization catalyst containing a metal of group VIII (IUPAC 8-10), and the isomerization section is operated under isomerization conditions, including a molar ratio between hydrogen and hydrocarbon greater than 0.01: 1, and a temperature in the range of 50 to 400 ° C. 9. The method according to claim 1, in which the alkylation catalyst comprises a zeolite having a zeolite structure of the type selected from the group consisting of BEA, MOR, MTW and NES. 10. The method according to claim 1, in which the monoolefins include monomethylalkene, and phenylalkanes include monomethylphenylalkanes. 11. The method according to claim 1, in which at least part of the stream sent for recycling, characterized by a concentration of monoolefins, less than 0.3 wt.%. 12. A composition for producing a detergent containing mainly modified phenylalkane obtained by the method according to any one of claims 1 to 11. 13. The composition according to item 12, further comprising a lubricant or lubricating additive. 14. A method of obtaining a product stream containing phenylalkanesulfonates, in which at least a portion of the alkylation product stream obtained by the method according to claim 1 is contacted with a sulfonating agent under sulfonation conditions sufficient to sulfonate the phenylalkanes and to obtain a sulfonation product stream, containing phenylalkanesulfonic acids, and at least a portion of the sulfonation product stream is contacted with a neutralizing agent under neutralization conditions sufficient to neutralize phenyl kansulfonovyh acid neutralization and to obtain a product stream comprising fenilalkansulfonaty. 15. A detergent composition containing a modified phenylalkanesulfonate obtained by the method of claim 14.