The method of receiving phenylalkanoic and grease on their basis
Application: petrochemical industry. Essence: conduct the isomerization of paraffins, the subsequent dehydrogenation of isomerized paraffins and alkylation phenylpropanol the often weakly branched olefin. Effluent from the alkylation zone contains paraffins, which recycle the stage isomerization stage or dehydrogenation. Received phenylaline can be used as a lubricant. 2 C. and 7 C.p. f-crystals, 4 tab., 1 Il.
The technical field,
The present invention relates to a method for selective receipt of phenylalkanoic to phenylalkanoic compositions on their basis and application of such compositions.
More than thirty years ago, many detergents for home laundering were obtained on the basis of the branched alkylbenzenesulfonates (BABS). BABS made from a certain type of alkyl benzenes, called branched alkyl benzenes (WWA). The alkyl benzenes (phenylaline) belong to the General category of compounds containing alkyl group attached to the phenyl group and meet the General formula (mi-alkyli)i-n-phenyl-alkane. Aliphatic alkyl group consists of the aliphatic alkyl chain, referred to as “talkgroup, aliphatic alkyl chain represents the longest straight chain containing a carbon atom connected to the phenyl group. In addition, the aliphatic alkyl group may also contain one or more alkyl branches, each of which is connected with the aliphatic alkyl chain and marked as appropriate (mi-alkyl), formula (mialkyli)i-n-phenyl-alkane. Can be selected two or more chains of the same length as the aliphatic alkyl chain, with such a selection leads to a carbon chain with the maximum number of alkyl branches. In the above formula, the lower the symbol i is a value in the range from 1 to the number of alkyl branches, and each value of i corresponds to the alkyl branch attached to the carbon number mialiphatic alkyl chain. Phenyl group attached to the aliphatic alkyl group, particularly to a carbon atom number n aliphatic alkyl chain. Aliphatic alkyl chain is numbered from one end to the other, and the direction of numbering is chosen so that the position of the phenyl group had the lowest vozmojnym oligomerization of light olefins, particularly propylene, to obtain the branched olefin containing 10 to 14 carbon atoms with subsequent alkylation of benzene branched olefins in the presence of such a catalyst as HF. Although obtained in this way VAV contains a large number of alkyl-phenyl-alkanes, meet the General formula (mialkyli)-n-phenyl-alkane, to illustrate the three most important characteristics of the WWA is sufficient to consider only two examples VAV: m-alkyl-m-alkyl-n-phenylaline, in which mn, and m-alkyl-m-fenelonov, in which m2.
The most important characteristic of the VAV is the fact that for most VAV, aliphatic alkyl chain VAV usually attached at least one alkyl branch, as a rule, three or more alkyl branches. Consequently, VAV contains a relatively high number of primary carbon atoms per aliphatic alkyl group, as the number of primary carbon atoms per aliphatic alkyl group VAV, is equal to the number of alkyl branches plus one, in the case n=1, or plus two, in the case of n2, provided that the alkyl branches are nermal even greater number of primary carbon atoms. Thus, the aliphatic alkyl group in VAV usually contains three, four or more primary carbon atoms. As for the alkyl branches aliphatic alkyl groups in the WWA, each alkyl branch is typically a methyl branch, although there ethyl, sawn and higher alkyl branches.
Another characteristic of the WWA is the fact that the phenyl group VAV can be attached to any non-primary carbon atom aliphatic alkyl chain. This is typical VAV received standard petrochemical way. Except 1 fenelonov, the formation of which, as you know, is undesirable due to the relative instability of the primary carbenium ion and a negligibly small influence of branches in branched paraffins, stage oligomerization leads to the formation of carbon-carbon links, unordered distributed along the length of the aliphatic alkyl chain, and the stage alkylation occurs almost randomly attach alkyl groups to carbon atoms in the aliphatic alkyl chain. For example, in the case phenylaline with aliphatic alkyl chain, saduakasuly product will be almost random distribution of 2-, 3-, 4 - and 5-phenylalkanoic and selectivity of the process in such phenylaline as 2-phenylalkyl shall be 25% in a random distribution, but in practice this value is 10-40.
The third characteristic feature of the WWA is a relatively high probability that one of the carbon atoms of the aliphatic alkyl chain is a Quaternary carbon atom. As illustrated by the first example of the WWA, the Quaternary carbon atom can serve as a carbon atom in the aliphatic alkyl group and no carbon atom linked through carbon-carbon connection with the carbon atom of the phenyl group. However, as illustrated by the second example VAV, Quaternary carbon atom may also represent a carbon atom linked through carbon-carbon communications carbon of the phenyl group. In the case when the carbon atom of the alkyl side chain is associated not only with two different carbon alkyl side chain and the carbon atom alkyl branching, but also with the carbon atom of the phenyl group, the resulting alkyl-phenyl-alkane is called Quaternary alkyl-phenyl-alkanol, or reduced “Quat” ("quat"). Thus, Katy clues the second carbon atom from the end of the alkyl side chain, the resulting 2-alkyl-2-phenyl-alkane is called “limit katom”. If the Quaternary carbon atom is any other carbon atom of the alkyl side chain as it occurs in the second example, VAV, the resulting alkyl-phenyl-alkane is called “internal katom”. In the known methods of obtaining VAV relatively large number of VAV, usually more than 10 mol.%, are internal Katy.
About thirty years ago, it became clear that the detergent intended for household washing derived from WWA, gradually pollute rivers and lakes. Studies of such problems has led to the conclusion that BABS slowly undergo biodegradation. The solution of this problem has led to the creation of detergents on the basis of alkylbenzenesulfonates (LABS), which, as has been established, faster subjected to biodegradation than BABS. Currently, detergents based on LABS are used all over the world. LABS are made from a different type of alkyl benzenes, called linear alkyl benzenes (LAB). The standard process used in the petrochemical industry for the production of LAB, is the dehydrogenation of linear paraffins to linear olefins and subsequent alkylation of benzene is Oh phenylaline, comprising a linear aliphatic alkyl group and phenyl group, and meet the General formula n-phenyl-alkane. LAB does not have alkyl branches and, consequently, a linear aliphatic alkyl group typically contains two primary carbon atom (i.e., n2). Another characteristic feature of the LAB, obtained by standard methods, is the fact that the phenyl group in the LAB are typically connected with any secondary carbon atom of a linear aliphatic alkyl group. In the LAB, obtained using HF as catalyst, phenyl group, with a somewhat higher probability attached to a secondary carbon atom that is located closer to the center, not the end, as in the case of a linear aliphatic alkyl groups, while in the case of LAB obtained in the process Detalapproximately 25-35 mol.% n-phenylalkanoic are 2-phenylaline.
In the research of the last few years have identified some modified alkylbenzenesulfonate that in the text cited as MABS, and which differ in composition from alkylbenzenesulfonates used in industry at the present time, including BABS and LABS, as well as from all alkylated alkylation of aromatics using such catalysts as HF, aluminium chloride, aluminium silicate, fluorinated silicate, zeolites and fluorinated zeolite. In addition, MBAS differ from the considered alkylbenzenesulfonates improved characteristics regarding cleaning when washing, cleaning very dirty surfaces, and an excellent efficiency when washing in hard and/or cold water, with their ability to biodegradation compared with LABS.
MABS can be obtained by sulfonation of the third type of alkyl benzenes, called modified alkyl benzenes (MAV), and the desired characteristics of the MAV defined desirable solubility, surface-active properties and the ability of MABS to biodegradation. MAV is phenylalkyl, including legkomyslennuyu aliphatic group and phenyl group, and satisfies the General formula (mialkyli)i-n-phenyl-alkane. Typically, the MAV has only one alkyl branch and such alkyl branch is a metal group, preferably ethyl or various groups, resulting in the presence of only one alkyl branch and the implementation of the conditions n1, the aliphatic alkyl group in the MAV has three primary is a, if there is only one alkyl branch and n=1, or four primary carbon atoms, if there are two alkyl branches and n1. Thus, the first distinctive feature of the MAV is that aliphatic alkyl group MAV contains an intermediate number of primary carbon atoms compared to the VAV and LAB. Another distinctive feature of the MAV is that the object in question contains a large number of 2-phenylalkanoic, i.e., 40-100% phenyl groups selectively attached to the second carbon atom from the end of the alkyl side chain.
Finally, another feature of the alkylate MAV is that MAV contains a relatively low amount of internal cvetov. Some internal Katy, as, for example, 5-methyl-5-finlandian form MABS, demonstrating a slower biodegradation, while such end quaty as 2-methyl-2-penyuntikan form MABS with the ability to biodegradation similar ability LABS. For example, the biodegradation experiments have shown that when processing in the environment of activated sludge in porous vegetation vessel limit the degree of biodegradation was higher for 2-methyl-2-undecyl benzosulfimide alkylbenzene sulfonate in Environmental Science and Technology, so 31, №12, 3397-3404 (1997). A relatively low number, usually less than 10 mol.% from MAV, are internal Katy.
Because MABS have advantages over other alkylbenzenesulfonate conducted research on the development of catalysts and methods for selective receipt of the MAV. As suggested earlier, two of the main criteria of alkylation process in production MAV represent the selectivity for 2-phenylalkyl and selectivity for Quaternary phenylalkyl. Known methods of alkylation, used in the production LAB, using such catalysts as aluminum chloride or HF, is not able to provide MHA with the desired selectivity for 2-phenylalkyl and internal quatum. In this known methods, the reaction of slightly branched olefins (i.e., olefins with almost the same low degree of branching, as in the aliphatic alkyl group MAV) with benzene selectively formed Quaternary phenylaline. One of the mechanisms explaining such selectivity for Quaternary phenylalkyl, provides for the possibility of transforming delinearization in varying degrees of olefins in the intermediate primary, secondary and tertiary ion formation and subsequent reaction with benzene is most likely resulting in the formation of Quaternary phenylaline.
One of the suggested ways to get the MAV is divided into three stages. In the first stage, paraffin feedstock is fed to the isomerization zone to isomerization of paraffins and receiving stream isomerizing product containing often weakly branched paraffins (i.e., paraffins with the same small degree of branching, and aliphatic alkyl group MAV). Further, technological isomerate stream is fed to the dehydrogenation zone, which often weakly branched paraffins is subjected to dehydration with the formation of the product stream of the dehydrogenation, often weakly branched containing monoolefinic (i.e. monoolefinic with the same weak branching, and often weakly branched paraffins and, consequently, aliphatic akilina group MAV). Finally, a stream of the dehydrogenation product is fed to the alkylation zone in which the often weakly branched monoolefins in the product flow dehydrogenation react with benzene with the formation of the MAV.
One of the problems of the proposed method is that in the traditional areas of the reactions of dehydrogenation to olefins becomes only about 10 wt.% submitted paraffins, resulting in approximately 90 wt.% the process stream from the zone degidio whom I served in the alkylation zone, all these waxes also come into the alkylation zone. Although it would be desirable to remove paraffins prior to submission to the alkylation zone, the difficulty in the separation of such paraffins and olefins with the same number of carbon atoms prevents this decision. Usually, in the alkylation zone more than 90 wt.% submitted monoolefins become phenylaline, while incoming paraffins are practically inert or directionspanel. Thus, the flow leaving the alkylation zone contains not only the desired MAV, but these paraffins. In the above studies to create ways to get the MAV with the efficient allocation and use of paraffins from the flow coming from the stage alkylation.
In accordance with one aspect, the present invention provides a method of obtaining fenelonov, especially modified alkyl benzenes (MAV), which includes stages isomerization of paraffin dehydrogenation of paraffins and alkylation of phenyl compounds, in which the paraffins contained in the stream from the stage alkylation, recycle on stage isomerization and/or stage of dehydrogenation. Subject recirculation PA is recycled paraffins can be converted into often weakly branched olefins in the present invention is the efficient allocation of paraffins from the stream from the stage alkylation and their use for the production of valuable phenylalkanoic products. Thus, in accordance with this aspect of the present invention is increasing the yield of valuable products in the calculation of the amount of paraffin feedstock introduced into the process, and this eliminates the difficult stage of separation of paraffins from monoolefins after the implementation phase dehydrogenation of paraffins and to conduct phase alkylation.
The aspect of the present invention relating to the production method, has several objectives. The main objective of the present invention consists in obtaining fenelonov, especially modified alkyl benzenes (MAV), in the isomerization of paraffins and their subsequent dehydrogenation to olefins, which carry out the alkylation of aromatic compounds. An additional objective of the present invention is to increase the output of phenylalkanoic in this process and, consequently, to reduce the amount of paraffin raw materials required for the implementation process. Another goal is to remove unreacted paraffins from phenylalkanoic product without the need for difficult and/or costly separation of paraffins from olefins after the stage of dehydrogenation and before stage alkylation.
In part, orauser continuously rising demand for selectivity for 2-phenylalkyl and selectivity to internal Quaternary phenylalkyl order to obtain modified alkyl benzenes (MAV). In turn, the MAV can be subjected to sulfonation with obtaining the modified linear alkylbenzenesulfonates (S), and improved cleaning performance in hard and/or cold water and retaining the ability to biodegradation, comparable to the ability of linear alkylbenzenesulfonates.
In accordance with another aspect, the present invention provides compositions on the basis of the MAV, obtained by the method of the present invention. It is assumed that the MAV obtained by the method of the present invention are not necessarily products that can be obtained by known methods which do not use the recirculation paraffins. Not limited to a particular theory, it is believed that in the dehydrogenation zone, the conversion of branched paraffins may exceed the degree of conversion of normal (linear) paraffins, and/or that the degree of conversion of heavy paraffins may be higher than the degree of conversion of light paraffins. In the considered cases, the concentration of linear paraffins and/or lighter paraffins in the recirculated stream of paraffins may increase. This, in turn, may lead to increased concentration and limit values converse linear and/or lighter paraffins in the dehydrogenation and subsequent alkylation become equal to the rate of introduction into the dehydrogenation zone under consideration paraffins from the isomerization zone. Accordingly, for a given value of the degree of conversion of olefins in the alkylation zone, aliphatic alkyl chain mAh-product of the present invention can be smaller and/or shorter than in the known methods. When the sulfonation of the resulting MABS can show a similar tendency to the formation of smaller and/or shorter aliphatic alkyl chain than in the known methods. Thus, for a given combination of raw materials, the method of the present invention can provide special MAV products with aliphatic alkyl chain with specially selected degree of branching, which is not necessarily similar to those that get in the known methods. According to another aspect, the present invention provides for the use of the MAV, obtained by the method of the invention as lubricating agents.
Disclosure of the invention
Paraffin feedstock, preferably, includes molecules unbranched (linear) or normal paraffins, typically containing 8-28, preferably 8 to 15, and more preferably 10-15 carbon atoms. Two carbon atoms in the molecule is an unbranched paraffin are the primary carbon is Kapinovo raw materials may also contain often weakly branched paraffin representing the paraffin with the total number of carbon atoms 8-28, three or four primary carbon atoms, and none of the remaining carbon atoms is a Quaternary carbon atom. Preferably, when often weakly branched paraffin contains 8-15, more preferably 10-15 carbon atoms. Often weakly branched paraffin typically includes aliphatic alkane, the General formula (Ri-alkyli)i-alkane and consists of the aliphatic alkyl chain and one or more alkyl branches. There is the possibility of selecting two or more chains of the same length as the aliphatic alkyl chain, with such a selection provides the chain with the highest number of alkyl branches. Subscript the symbol i is a value from 1 to the number of alkyl branches, and when each value of i corresponding alkyl branch is connected with the carbon number of the pialiphatic alkyl chain. Aliphatic alkyl chain is numbered from one end to the other, and the direction of numbering is chosen so that the carbon atoms having alkyl branches, had the lowest possible number.
The alkyl branch or branches are usually chosen from methyl, ethyl or profileration paraffin has only one alkyl branch, however, there may be two alkyl branches. Often weakly branched paraffins having two alkyl branches, or four primary carbon atoms, usually account for less than 40 mol.%, preferably, less than 25 mol.% from the total number of often weakly branched paraffins. Often weakly branched paraffins having one alkyl branch or three primary carbon atoms are preferably more than 70 mol.% from the total number of often weakly branched paraffins.
Paraffin feedstock may also contain more silkroadonline paraffins than the above often weakly branched paraffins. It is preferable to minimize the number of such highly branched paraffins introduced into the process. Wax molecules containing at least one Quaternary carbon atom, typically comprise less than 10 mol.%, preferably, less than 5 mol.%, more preferably less than 2 mol.% and most preferably less than 1 mol.% in the calculation of the amount of paraffin feedstock.
Usually paraffin feedstock is a mixture of linear and often weakly branched paraffins with different numbers of carbon atoms. Can be used in any suitable way to obtain this paraffin feedstock. Preferable from the cities of the oil fraction boiling within the kerosene. UOP Molexthe process is a proven, commercially viable method of liquid-phase adsorptive separation of normal paraffins, isotrate and cycloparaffins using separation technologies UOP Sorbex. Other suitable processes are the process UOP Kerosene Isosivand vapor adsorption process echop, in which as desorbent use ammonia. The flows of raw materials for such adsorption processes can be obtained by extraction or by suitable methods of oligomerization. For additional information concerning processes UOP Molexand Kerosene Isosivyou can refer to the book Handbook of Petroleum Refining Process. Robert A. Meyers, McGraw-Hill, New York, 1997.
The composition of the paraffin feedstock can be installed by gas chromatography in accordance with the work of N. Schuiz with al., Chromatographia 1, 1968, 315.
Phenyl raw materials includes capable of alkylation of phenyl compounds or any other substituted derivatives of higher molecular weight than benzene, including toluene, ethylbenzene, xylene, phenol, naphthalene, etc., Preferred phenyl compound is benzene.
For purposes of discussion, rasmar the AI isomerization, paraffin feedstock is fed to the area of skeletal isomerization, where there is a reduction in the number of linear molecules and increases the number of primary carbon atoms in the molecules of paraffin feedstock. The number of metal branches in the aliphatic alkyl chain preferably is increased by 2 or more, preferably 1. The total number of carbon atoms in the molecule paraffin remains unchanged.
In the process of isomerization of the material stream containing paraffins, combined with recycled hydrogen. As a result of this operation is formed thread isomerizing reagent, which is heated and passed through a layer of a suitable isomerization catalyst at an appropriate temperature, pressure, etc., the Stream exiting the catalytic layer, or stream, coming from the isomerization reactor, is cooled, partially condensed and fed into the separator system for vapor - liquid or product. The condensed material coming out of the separator of the product may be introduced into the desorption zone of separation, including the Stripping column, which removes all the components more volatile than most light aliphatic hydrocarbon, which it is desirable to apply section dehydrogenation rassmatrivaemaya without prior Stripping, together with the most volatile aliphatic hydrocarbons, and a stream of negidrirovannogo product is subjected to desorption, in order to remove all components that are more volatile than most light aliphatic hydrocarbon, which is advisable to apply section alkylation. Wax the thread supplied from the section isomerization section dehydrogenation is a flow isomerizing product.
Skeletal isomerization of paraffin feedstock may be carried out by any known method, or using any known catalyst. Suitable catalysts include metals of group VIII (IUPAC 8-10) of the Periodic system of elements and media. Suitable VIII group metals include platinum and palladium, each of which can be used separately or together. As the carrier can be used a material having an amorphous or crystalline structure. Suitable materials carriers include amorphous alumina, amorphous aluminosilicates, ferrierite, ALPO-31, SAPO-11, SAPO-31, SAPO-37, SAPO-41, SM-3 and MgAPSO-31, each of which can be used separately or in combination with other materials. ALPO-31 disclosed in U.S. patent US-A-4310440. SAPO-11, SAPO-31, SAPO-37, and SAPO-41 is described in US-A-4440871. SM-3 rectallycytotec molecular sieves, in which Me denotes magnesium (Mg). System type MeAPSO described in US-A-4793984, a MgAPSO described in US-A-4758419. MgAPSO-31 is the preferred representative systems MgAPSO, where numeral 31 denotes a MgAPSO with the structure 31. The isomerization catalyst may also contain a modifier selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, and mixtures thereof, in accordance with US-A-5716897 and US-A-5851949. It is assumed that other suitable materials carriers include ZSM-22, ZSM-23 and ZSM-35, which in dewaxing disclosed in US-A-5246566 in the article by S. J. Miller, published in Microporous Materials 2 (1994) 439-449.
Skeletal isomerization of paraffin feedstock can be carried out in the vapor phase, liquid phase and combination of these phases. Hydrocarbons, preferably, are in the liquid phase. The system may present an excess of hydrogen relative quantity, soluble in liquid hydrocarbons. Paraffin feedstock in the form of liquid is passed through the fixed bed of solid catalyst in the presence of vapors of hydrogen. Usually the temperature of the isomerization process is 122-752C. the Pressure of the isomerization process is usually in the range of from atmospheric to 13790 kPa (g), however, nie. The molar ratio of hydrogen : hydrocarbon typically has a value exceeding 0.01:1, but usually not more than 10:1.
Stream isomerizing product includes paraffins with a total number of carbon atoms per paraffin molecule, 8-28, preferably 8 to 15, and more preferably 10-15. Typically, the flow isomerizing product contains elevated concentrations often weakly branched paraffins in the calculation of the total paraffin content in the stream isomerizing product compared with concentrations often weakly branched paraffin in the paraffin feedstock, based on the total wax content in raw materials.
Often weakly branched paraffins containing two alkyl branches, or four primary carbon atom, preferably less than 40 mol.%, more preferably less than 30 mol.% from the total number of often weakly branched paraffins in the stream isomerizing product. Often weakly branched paraffins containing one alkyl branch or three primary carbon atom, preferably constitute more than 70 mol.% from the total number of often weakly branched paraffins in the stream isomerizing product. Often weakly branched paraffins containing 3 or 4 primary carbon atoms and not containing czetwertynska flow isomerizing product. Preferred often weakly branched paraffin contained in the stream isomerizing product are monomethylamine. In a joint presence in the stream isomerizing product with often weakly branched paraffin content of linear paraffins can reach 75 mol.%, but, as a rule, it is less than 40 mol.% from the total amount of paraffins in the stream isomerizing product. The amount of paraffin molecules containing at least one Quaternary carbon atom, usually less than 10 mol.%, preferably, less than 5 mol.%, more preferably less than 2 mol.%, and most preferably less than 1 mol.% the number of stream isomerizing product.
In section dehydrogenation, a stream containing paraffins, combined with recycled hydrogen with the formation of flow negidrirovannogo reagent, which is heated and brought into contact with the dehydrogenation catalyst in the form of a fixed layer, under appropriate conditions of dehydrogenation. The flow of exhaust with a fixed catalyst layer, and the stream leaving the dehydrogenation reactor, is cooled, partially condensed and fed into vapor-liquid separator. In the vapor-liquid separator is formed in the vapor phase from the separator, served in the Stripping column, which removed all compounds more volatile than most light hydrocarbons, which are preferably submitted in section alkylation. Then registergui stream is served from section dehydrogenation section alkylation and this thread is a product of dehydrogenation. For additional information about LAB processes in General and the processes of dehydrogenation of paraffins, in particular, mention may be made of pages 153-166 and 511-519 above cited books Meyers, referred to in the present description,
The dehydrogenation catalyst can be used in the form of a moving layer or fluidized bed. The dehydrogenation zone may include one or more reaction zones containing a catalyst with heat exchangers which will maintain the desired reaction temperature at the entrance to each reaction zone. Hot flow of gas enriched with hydrogen, can be introduced into the space between the reaction zones with the purpose of the heated flow between the reaction zones. For more information on this issue, you can refer to US-A-5491275 and US-A-5689029. Each reaction zone can operate in continuous or batch modes. Each reaction zonecom layer as they move up, down or radius, or the specified operation can be carried out in the heat exchange reactor. For more information regarding heat exchange reactors, you can refer to the contents of the patents US-A-5405586 and US-A-5525311 referenced in this description.
The dehydrogenation catalysts known from the prior art, examples of which can serve US-A-3274387; US-A-3315007; US-A-3315008; US-A-3745112; US-A-4430517; US-A-4716143; US-A-4762960; US-A-4786625, and US-A-4827072. However, the preferred catalyst is a layered composition comprising an inner core and an outer layer that is associated with the inner core and the outer layer contains a refractory inorganic oxide, in which is uniformly dispersed, at least one metal of the platinum group (group VIII (IUPAC 8-10) and at least one metal promoter, and catalyst composition dispersed in at least one modifying metal. Preferably, the outer layer was associated with the inner core to such an extent that losses abrasion does not exceed 10 wt.% based on the weight of the outer layer. For more information on layering catalytic compositions can be mentioned in the application for U.S. patent No. 09/185189 from 3 Nov the zoom, to reduce cracking, isomerization and formation of polyolefin products. The hydrocarbon may be in the liquid phase or mixed vapor-liquid phase, but preferably in the vapor phase. The dehydrogenation conditions include a temperature usually in the range of 400-900With, preferably, 400-525With pressure in the range 1-1013 kPa (g) and LHSV in the range of 0.1 to 100 h-1. The pressure is maintained at as low as possible value, it typically has a value less than 345 kPa (g), in compliance with the technical limitations of technological equipment, to maximize the favorable shift of chemical equilibrium.
Stream of the isomerization product may be mixed with the same diluent as the hydrogen before, during, or after the filing in the dehydrogenation zone at a molar ratio of hydrogen : hydrocarbon in the range of 0.1:1 to 40:1, preferably 1:1-10:1. The flow of dilution of the hydrogen supplied to the dehydrogenation zone, is usually a recirculating the hydrogen separated from the flow of exhaust from the dehydrogenation zone.
Water or material decaying in the dehydrogenation conditions with formation of water, such as alcohol, aldehyde, ether or ketone, may continuously or the weight.h./million from a stream of hydrocarbons. Adding water in the amount of 1-10000 weight.h./million provides the best results in the case when daydreamy paraffins contain 2-30 or more carbon atoms.
Stream of the dehydrogenation product containing monoolefinic, from the process of dehydrogenation of paraffins, typically, is a mixture of unreacted paraffins, linear (unbranched) olefins and branched monoolefins, including the often weakly branched monoolefins. Usually, 25-75 vol.% olefins in minoritenstrasse the flow of the process of dehydrogenation of paraffin are linear (unbranched) olefins.
Stream of the dehydrogenation product may contain the highly branched monoolefins or linear (unbranched) olefin, however, it is preferable that monoolefins represented the often weakly branched monoolefins. Often weakly branched monoolefins is monoolefins with the total number of carbon atoms 8-28, three or four primary carbon atoms, among the remaining carbon atoms and no Quaternary carbon atoms. Preferably, the often weakly branched monoolefins contains 8-15, more preferably 10-15 carbon atoms.
Often weakly branched monoolefins usually includes alifan has aliphatic alkenylphenol chain, representing the longest straight chain containing carbon-carbon double bond often weakly branched of monoolefins, and one or more alkyl branches, each of which are attached to aliphatic alkenylphenol chain. If there is the possibility of selecting two or more chains of the same length as aliphatic alkenylphenol chain, this selection will provide the chain with the highest number of alkyl branches. Thus, the subscript character i is a value from 1 to the number of alkyl branches, and for each value of i there is a corresponding alkyl branch attached to a carbon atom number Rialiphatic alkenylphenol chain. The double bond located between carbon number q and the carbon number (q+1) aliphatic alkenylphenol chain. Aliphatic Alchemilla the chain is numbered in the direction from one end to the other, and the direction of numbering is chosen so that the carbon atoms bearing the double bond, had the smallest possible number.
Often weakly branched monoolefins can be an alpha monoolefins or vinylidene monoolefins, but, preferably, it is venotrain, having the chemical formula R-CH=CH-R; tizanidine internal olefins have the formula R-C(R)=CH-R; a Tetra-substituted olefins have the formula R-C(R)=C(R)-R. Disubstituted internal olefins include beta internal olefins, corresponding to the chemical formula R-CH=CH-(CH3). In each of the described in this paragraph, chemical formulas, R represents an alkyl group, which may be identical or different alkyl groups, if they are present in each of the above formulas.
In the case of the often weakly branched monoolefins other than vinylidene olefins, alkyl branch or branches often weakly branched of monoolefins usually choose from metal, ethyl and various groups, with short and normal branches are preferred. In contrast, in the case of the often weakly branched monoolefins vinylidene type alkyl branch attached to a carbon atom number 2 aliphatic alkenylphenol chain can be selected not only from metal, ethyl and various groups, but also from alkyl groups of up to tetradecyl (C14) groups, although any other alkyl branches vinylidenes of olefin is usually chosen from the YMI. For all the often weakly branched monoolefins preferred monoolefins this type contains only one alkyl branch, although it is also possible the presence of two alkyl branches. Often weakly branched monoolefins containing two alkyl branches, or four primary carbon atom, typically account for less than 40 mol.%, and preferably less than 30 mol.% from the total number of often weakly branched of monoolefins, and often weakly branched remaining monoolefinic have one alkyl branch. Often weakly branched monoolefins having one alkyl branch or three primary carbon atom, preferably constitute more than 70 mol.% from the total number of often weakly branched of monoolefins. Monomethylamine are often weakly branched preferred monoolefins contained in the product flow dehydrogenation.
Vinylidene monoolefins are typically impurity component and are usually present in concentrations of less than 0.5 mol.% and, typically, less than 0.1 mol.% from the amount of olefins in the product stream of the dehydrogenation. Therefore, all subsequent references to the often weakly branched monoolefins and product flow dehydrogenation assume no vinylidene monopole is accordance with the methods previously mentioned article Schuiz and others using the injector, equipped with generator plug-in tube for hydrogenation of monoolefins in paraffin.
In addition to the often weakly branched monoolefins stream of the dehydrogenation product may contain other acyclic compounds. One of the advantages of the present invention is the fact that the stream of the dehydrogenation product may directly be submitted to the section for the reaction of alkylation, despite the fact that the thread also contains paraffins with the same number of carbon atoms, and the often weakly branched monoolefins. Thus, the present invention makes optional the separation of paraffins from monoolefins before filing section alkylation. Other acyclic compounds include unbranched (linear) olefins and monoolefins. Unbranched (linear) olefins, which can be loaded into the reactor, usually have the total number of carbon atoms per paraffin molecule in the range of 8-28, preferably 8 to 15 and more preferably 10-14 carbon atoms. Two carbon atoms per molecule unbranched olefins are primary carbon atoms, and the remaining carbon atoms are secondary carbon atoms. Non-branched olefin can transform linear olefins can reach 75 mol.%, but usually it is less than 40 mol.% of the total number of monoolefins in the stream of the dehydrogenation product.
Stream of the dehydrogenation product may contain, on average, about 3, or of 2.25-4, or 3-4 primary carbon atoms per molecule monoolefins in the stream of the dehydrogenation product.
Linear and/or nonlinear paraffins in the product flow dehydrogenation typically have a total content of carbon atoms per paraffin molecule in the range of 8-28, preferably 8 to 15 and more preferably 10-14 carbon atoms. Nonlinear paraffins in the product flow dehydrogenation may contain often weakly branched paraffins and waxes containing at least one Quaternary carbon atom. It is expected that the linear and nonlinear paraffins will serve as diluent under alkylation and will not hamper the implementation phase alkylation. However, the presence of such diluents in the alkylation reactor tends to increase the volumetric velocity of flow.
It is preferable to minimize the flow of product dehydrogenation number of monoolefins, which are more highly branched than the often weakly branched monoolefins. Molecules monopole the equipment is less than 5 mol.%, more preferably less than 2 mol.% and most preferably less than 1 mol.% from the product stream of the dehydrogenation.
Often weakly branched monoolefins react with phenyl compound. In General, the often weakly branched monoolefins can react with other phenyl compounds in addition to benzene, for example, alkylated or otherwise substituted derivatives of benzene, including toluene and ethylbenzene, however, benzene is a preferred phenyl connection. Although the stoichiometry alkylation reaction consumes 1 mole of phenyl compounds per mole of monoolefins, using a molar ratio of 1:1 leads to excessive polymerization of the olefin and polyallylamine. On the other hand, it is desirable to use a molar ratio of phenyl connection : monoolefins as possible close to 1:1 in order to increase the utilization of phenyl compounds and to reduce the number or recirculating unreacted phenyl compounds. Used the molar ratio of phenyl compound and the total number of monoolefins will have an important effect on conversion and selectivity of the alkylation reaction. The total molar ratio of phenyl phenyl derivative and often weakly branched by monoolefins spend alkylation conditions in the presence of a solid alkylation catalyst. The said alkylation conditions include a temperature in the range of 80-200With, usually no more than 175C. Since the alkylation is conducted at least partially in the liquid phase, and preferably in completely liquid phase or at supercritical conditions, should be used under sufficient pressure to maintain the reactants in liquid phase. Pressure necessarily depends on the nature of the olefin, phenyl derivative and temperature, but it usually takes 1379-6895 kPa (g), most preferably, 2069-3448 kPa (g).
Although alkylation conditions sufficient for the alkylation of phenyl derivative often weakly branched by monoolefins, it is assumed that in the conditions of alkylation skeletal isomerization often weakly branched of monoolefins is realized only to a small extent. Under skeletal isomerization of the olefin at alkylation conditions implied isomerization occurring during alkylation and changing the number of carbon atoms in the aliphatic alkenylphenol chain olefins, aliphatic alkyl chain phenylalkanoic product or any reaction intermediate product that is formed, or is derived laboratorial less than 10 mol.% the olefin, aliphatic alkyl chain and any reaction intermediate product is subjected to skeletal isomerization. It is also considered that any other olefins contained in the olefinic feedstock subjected to skeletal isomerization only to the minimum extent. Thus, the alkylation, preferably, occurs without significant skeletal isomerization often weakly branched of monoolefins and the degree of branching often weakly branched of monoolefins identical to the weak degree of branching in the aliphatic alkyl chain of the molecule phenylalkanoic product. Accordingly, the number of primary carbon atoms in the often weakly branched monoolefins, preferably, is equal to the number of primary carbon atoms in the molecule phenylaline. However, the number of primary carbon atoms in fenilalanina product may slightly exceed or be slightly smaller number of primary carbon atoms in the often weakly branched monoolefins.
Alkylation of phenyl compounds often weakly branched by monoolefins leads to the formation of mialkyli)i-n-phenylalkanoic, aliphatic alkyl group which contains two, three or four primary carbon atoms per molecule phenylalkylamine and more preferably, when one of the three primary carbon atoms is a metal band on one end of the aliphatic alkyl chain of the second primary carbon atom is a metal group at the other end of the chain, and the third primary carbon atom is an insulated metal branch, United with the chain. Usually, 0-75 mol.% and preferably 0-40 mol.% received (mialkyli)i-n-phenylalkanoic can contain 3 primary carbon atoms per molecule phenylaline. Usually, as much as possible the number of received (mialkyli)i-n-phenylalkanoic typically 25-100 mol.% may contain 3 primary carbon atoms per molecule phenylaline. Usually, 0-40 mol.% received (mialkyli)i-n-phenylalkanoic may contain 4 primary carbon atom. Preferred substances are monomethylaniline. The number of primary, secondary and tertiary carbon atoms per molecule obtained phenylaline can be defined on the spectrum of multipulse nuclear magnetic resonance (NMR) and undistorted amplification as a result of polarization transfer (DEPT). For more information on this issue can>alkilirovanie phenyl derivative often weakly branched olefins usually occurs with selectivity for 2-phenylalkyl 40-100, and preferably 60-100%, whereas the selectivity for internal Quaternary phenylalkyl usually less than 10%, preferably less than 5%. Quaternary phenylaline can be formed in the alkylation of phenyl derivative often weakly branched by monoolefins containing at least one tertiary carbon atom. The resulting phenylalkyl can be an internal hydrocarbon or quit.
Alkylation of the phenyl derivative often weakly branched by monoolefins may be periodic manner, or, preferably, in a continuous way. The alkylation catalyst may be used in the form of a stationary layer or fluidized bed. Olefinic feedstock can be fed into the reaction zone from the bottom up, or top-down, or even horizontally, as it takes place in the reactor with radial catalyst bed. A mixture of benzene and olefin feedstock containing the often weakly branched monoolefins injected into the reactor at a total molar ratio of phenyl derivative : monoolefins in the range of 2.5:1-50:1, although, as pravil such areas, the molar ratio of phenyl derivative : monoolefins may be higher than 50:1, although the overall ratio of benzene : olefin remains within the above interval. The total feed mixture, i.e., phenyl derivative plus olefinic feedstock containing the often weakly branched monoolefins, is fed through a dense layer of catalyst with time volumetric rate of liquid raw materials (LHSV) in the range of 0.3 to 6 h-1depending on the temperature of the alkylation, the duration of use of the catalyst, etc.,
Lower values of LHSV within the above intervals are preferred. The temperature in the reaction zone is maintained in the range of 80-200And pressure can usually vary in the range 1379-6895 kPa (g) to ensure liquid phase or create supercritical conditions. After passing phenyl derivative and olefinic raw materials through the reaction zone effluent is collected and separated into unreacted phenyl derivative, which recycle to the feed point in the reaction zone, paraffin, which recycle in the installation dehydrogenation and phenylaline. Usually, phenylaline additionally divided into monoalkylbenzenes used in subsequent sulfonation with the formation of alkylbenzenesulfonates, and oligomers plus polyalkylene is regulated in only a small number of monoolefins.
In the present invention can use any suitable alkylation catalyst, provided that he satisfies the requirements for conversion, selectivity and activity. The preferred alkylation catalysts include zeolites with structure type selected from the BEA, MOR, MTW and NES. Such zeolites include mordenite, ZSM-4, ZSM-12, ZSM-20, offretite, gmelinite, beta, NU-87 and Gottardi. Such terms relating to the structure of zeolites type a zeolite structure” and “structure izotopicheskoj grid” used in the text in accordance with their definition and use of the W. M. Meier with TCS. in Atlas of Zeolite Structure Types published by the Structure Commission of the International Zeolite Association by Elsevier, Boston, Massachusetts, USA, fourth revised edition, 1996. Alkylation reaction using NU-87, NU-85, representing germinated forms of zeolites EU-1 and NU-87, described in U.S. patent 5041402 and 5446234, respectively. Gottardi having the structure izotopicheskoj lattice structure type NES zeolite, revealed in the works of A. Alberti with al., in Eur.J. Mineral., 8, 69-75 (1996) and E. Galli with al., in Eur.J. Mineral., 8, 687-693 (1996). The preferred alkylation catalyst is a mordenite.
Zeolites suitable for use as rolled and from the ions of alkali or alkaline earth metals. Other ions include, but are not limited to, hydrogen, ammonium, ions of rare earth elements, zinc, copper and aluminum. Especially preferred group of elements of this type include ammonium, hydrogen, rare earth elements, or combinations thereof. In accordance with a preferred embodiment of the present invention, these zeolites are mainly transferred to the hydrogen form, usually as a result of replacement of the original alkali metal ion or another precursor ion of the hydrogen ion, such as ammonium ions, which in the firing transferred to the hydrogen form. Specified currency conveniently be accomplished by interaction of the zeolite with a solution of ammonium salts, for example ammonium chloride, using well-known ion exchange techniques. According to some technical solutions make use of this degree of substitution, to obtain a zeolite material, in which at least 50 percent cationic centers are occupied by hydrogen ions.
The zeolites may be subjected to various chemical treatments, including extraction of aluminium (dealumination) and combination with one or more metallic components, for example IIIB metals (IUPAC 3), IVB (IUPAC 4), VIB (IUPAC 6), VIIB (IUPAC 7), VIII (IUPAC or firing in the air, in the environment of hydrogen or inert gas such as nitrogen or helium. Suitable processing Stripping involves contacting the zeolite with an atmosphere containing 5-100% steam at a temperature of 250-1000C. Steaming can be done within 0.25 to 100 hours at a pressure in the range of from subatmospheric to several hundred atmospheres.
In accordance with the present invention, it is useful to introduce the used zeolite in another material, for example material is a matrix or binder, which are resistant to the temperature and other conditions used in the process. Suitable matrix materials include synthetic substances, substances of natural origin, and such inorganic materials as clay, silica and/or metal oxides. Matrix materials can be used in the form of gels including mixtures of silica and metal oxides.
Gel a mixture of silicon oxide and metal oxide can have a natural origin or applied in the form of gels or gel precipitation. Clay natural origin, which can connect to the zeolites used in the present invention include clay from the family of montmorillonite, kaolin Florida and others, the main mineral component of which may be halloysite, kaolinite, Dixit, nacrite or anoxic. These clays can be used as matrix material in the form of newly produced material, or may be subjected to calcination, acid treatment or chemical modification to their use as matrix materials.
In addition to these materials, the zeolites used in the present invention, can connect with porous matrix materials, such as aluminum oxide, a mixed oxide of silicon and aluminum mixed oxide of silicon and magnesium mixed oxide of silicon and zirconium mixed oxide of silicon and thorium mixed oxide of silicon and beryllium, a mixed oxide of silicon and titanium and aluminum phosphate, as well as the triple combination as a mixture of oxides of silicon, aluminum and thorium oxides of silicon, aluminum and zirconium, oxides of silicon, aluminum and magnesium, oxides of silicon, magnesium and zirconium. The specified matrix material may be in the form of joint gel. The ratio between the zeolite and the matrix material can vary widely, with the zeolite is usually 1-99 wt.%, usually 5-80 wt.% and preferably 30-80 wt.% from the total mass is the ratio of the lattice of silicon oxide and aluminum oxide in the range of 5:1-100:1. In that case, when the zeolite of the alkylation catalyst is a mordenite, its lattice molar ratio of silica : alumina is 12:1-90:1, preferably 12:1-25:1. The term "lattice molar ratio of silica: alumina" refers to the molar ratio between silicon oxide and aluminum oxide, representing the molar ratio of SiO2/Al2O3in the lattice of the zeolite.
In the case where the zeolite is prepared in the presence of organic cations, they may not be catalytically active for conducting the alkylation reaction. Not limited to a particular theory, it is possible to assume that the lack of catalytic activity is the result of organic cations from the forming solution, which occupy the intracrystalline free space. Such catalysts can be activated, for example, by heating in an inert atmosphere at 540C for one hour, carrying out ion-exchange reaction with ammonium salts and firing in air at 540C. the Presence of organic cations in the forming solution may be a significant factor for the contraction in the PA using different activation methods and other methods of processing, for example, ion-exchange, steaming, removal of aluminum, and firing. In the case where the zeolite is synthesized in the form, based on the alkali metal, it is easily converted into the hydrogen form, generally by intermediate formation of the ammonium form as a result of ion exchange for ammonium and firing ammonium form with the formation of the hydrogen form. Although the hydrogen form of the zeolite successfully catalyze a reaction, the zeolite may also partially be in the form containing alkali metal.
In the zone selective alkylation is formed corresponding effluent flowing into the separation device for the regeneration of the reaction products and recycled raw components. The flow of exhaust from the zone selective alkylation, enters the column, irrigated benzene, which is formed extending from the top stream containing benzene, and the bottom stream containing alkylate. Bottom flows into the paraffin column, in which is formed the upper liquid stream containing unreacted paraffins and a bottom stream containing alkylate and high molecular weight side of the hydrocarbons formed in the zone selective alkylation. Consider the bottom stream of the paraffin column Moreta, containing surface-active alkylate, and the flow coming from the bottom of the column secondary distillation, contains polymerized olefins and polyallylamine benzenes (heavy alkylate). On the other hand, if the content of heavy alkylate in the bottom stream of the paraffin column slightly, the need for secondary column distillation disappears and the bottom stream of the paraffin column may be emitted, in the form of a target process flow of surface-active alkylate.
In accordance with the present invention, at least part of the liquid stream of the paraffin column recycle zone isomerization, dehydrogenation zone or both zones. Preferably, the portion of the liquid stream of the paraffin column recycle to the isomerization zone or zone dehydrogenation, was an aliquot of the head of fluid flow. Aliquot portion of the fluid flow is a part of the flow, which has almost the same composition as that of the parent fluid flow. The head stream of the paraffin column includes paraffins with a total number of carbon atoms per paraffin molecule, usually comprising 8-28, preferably 8-15 and more preteenboy columns recycle only in the dehydrogenation zone. Typically, 50-100 wt.% head of fluid flow from the paraffin column recycle to the isomerization zone and/or a dehydrogenation zone and, preferably, the entire head fluid flow from paraffin recycle column only in the dehydrogenation zone.
Regardless of whether the recirculation zone isomerization or dehydrogenation zone, the head stream of the paraffin column may contain unbranched (linear) paraffins, and often weakly branched paraffins, even when processing received only non-branched paraffins. This is due to the fact that approximately 60-80 wt.% unbranched paraffins introduced into the area of skeletal isomerization, turn into often weakly branched paraffins, dehydrogenation zone 10-15 wt.% input paraffins, typically turn into olefins and a fraction of olefins in the product stream of the dehydrogenation, representing often weakly branched olefins, approximately corresponds to the amount of paraffins in the stream isomerizing product, representing often weakly branched paraffins. Because the conversion of olefins in the alkylation zone is typically greater than 90 wt.% from the supplied volume of olefins, typically more than 98 wt.%, and since converse razvetvlennye paraffins.
To illustrate this in practice, it is useful to consider the initial stage of the process, when the isomerization zone are only linear paraffins and this zone is the transformation of x wt.% supplied to the processing of unbranched paraffins in the often weakly branched paraffins. Often weakly branched paraffins begin to form in the head stream of the paraffin column. As recycling often weakly branched paraffins to the isomerization zone, the mixture of paraffins filed in the isomerization zone, will gradually change from a mixture containing only non-branched paraffins, to a mixture containing unbranched and often weakly branched parafine. Accordingly, hereinafter, the isomerization zone can operate in conditions where the nonlinear conversion of paraffins has a value less than x wt.%. Over time, the conversion rate of isomerization may undergo further adjustment until establishment of the stationary state at which the rate of conversion of non-branched paraffins in the often weakly branched paraffins to the isomerization zone, expressed in moles per unit time becomes approximately equal to the lowest value of the speed at which MAV phenylaline eliminated from the process.
Konz is ephiny, contained in the main fluid flow, of the paraffin column can be recycled to the isomerization zone and/or the dehydrogenation zone. The concentration of paraffins in the liquid stream of the paraffin column containing at least one Quaternary carbon atom, preferably, has a minimum value of.
One of the variants of the method of the present invention includes the selective hydrogenation of diolefins contained in the product flow dehydrogenation, because diolefin can be formed during the catalytic dehydrogenation of paraffins. In the selective hydrogenation of diolefin turn in monoolefinic and form a product flow selective hydrogenation of olefins having a lower concentration of diolefins than the stream of the dehydrogenation product.
Another variant of the method of the present invention includes the selective removal of aromatic by-products contained in the product flow dehydrogenation. Aromatic by-products may be formed during the catalytic dehydrogenation of paraffins and such by-products can have a number of undesirable effects on the process. Suitable areas removal of aromatics include sorption zone of separation, sod the s extraction system fluid the fluid. Aromatic by-products may be selectively removed from the product stream of the dehydrogenation, but also, or instead, from the product stream of the isomerization and/or downstream of the fluid flow from the paraffin column, which recycle to the isomerization zone or zone dehydrogenation. In the case where the process includes the zone selective hydrogenation of diolefins, aromatic by-products may be selectively removed from the product stream by selective hydrogenation of diolefins. Although selective removal of these aromatic by-products preferably takes place continuously, this selective removal may be performed alternately or periodically. Detailed information concerning the selective removal of aromatic by-products from the manufacturing process LAB described in patent US-A-5276231, referred to in the present description, may be considered as additional information. It is assumed that the specialist in the art will be able to adapt these patent US-A-5276231 relating to the removal of aromatic by-products, for the successful removal of aromatic by-products from the production process MAV.
Other ascolano another aspect of the present invention, provides for the application composition based MAV obtained in the described manner, as a residue. I believe that phenylaline possess such properties related to the viscosity dependence of viscosity on temperature and density, which make them attractive materials for use as an oil residue. The use of phenylalkanoic as lubricants are described, for example, in the article by E. R. Booser in Kirk-Othmer Encyclopedia of Chemical Technology, fourth edition, T. 15. John Wiley and Sons, New York, USA, 1995, pp. 463-517, the contents of which can be referred to as material depicting specified lubricants and their application.
The above drawing shows the preferred generalized diagram of a method of the present invention, including stage isomerization - dehydrogenation - alkylation.
Paraffin feedstock comprising a mixture of normal paraffins C10-C13loaded into the system through line 12. Normal paraffins in line 12 is mixed with hydrogen-rich recycle stream from line 22 and the mixture is fed through line 16. A mixture of paraffins and hydrogen supplied through line 16, is first heated in the indirect heat exchanger 18 and then fed through line 24 into the furnace 20. On the other hand, instead of shown on the drawing option, to the ICA 18 and heater 20, the stream in line 22 can be mixed with normal paraffins at a point between the heat exchanger 18 and heater 20, or between the heater 20 and the reactor 30. The resulting mixture of hydrogen and liquid paraffin are served by the line 26 in the isomerization reactor 30. In the reactor 30 paraffins in the presence of isomerization catalyst are given in such a state that provides the conversion of a significant part of normal paraffins in the often weakly branched paraffins. The result is the waste stream from the isomerization reactor, the exhaust line 28, which contains a mixture of hydrogen, normal paraffins and often weakly branched paraffins. Effluent from the isomerization reactor is first cooled in the indirect heat exchange in heat exchanger 18 and then, after a feed line 32, is subjected to further cooling in an indirect heat exchanger 34. Provides sufficient cooling to condense all With10+hydrocarbons with the formation of flow of the liquid phase and separation of the stream from the remaining vapor is enriched in hydrogen. Then the stream effluent of the isomerization reactor is served by line 36 into the vessel 38 to separate system vapor - liquid, in which the flow is divided into the turn 50. Vapor stream is divided into a cleansing stream, designed for removal of light hydrocarbons, C1-C7on line 42, the flow of hydrogen recycle line 44. The flow of hydrogen from line 44 combined with a stream of hydrogen supplied through line 46. The combination of the flux of hydrogen from line 44 with a fresh stream in line 46 provides the creation of a re-circulating stream supplied through line 22.
Stream of the isomerization product withdrawn from the bottom of the separation vessel 38, contains normal paraffins, often weakly branched paraffins and some dissolved hydrogen. Then the stream of the isomerization product, represents a part of the liquid phase effluent from the separation vessel 38 serves on line 50 and unite recirculating paraffins in line 48. The combined stream of paraffins is supplied via line 54 and is mixed with recycle hydrogen from line 82 with the formation of a mixture of paraffins and hydrogen, which is supplied via line 56. A mixture of paraffins and hydrogen supplied through line 56, is first heated in the indirect heat exchanger 58 and then fed through line 62 into the furnace 60. A two-phase mixture of hydrogen and liquid paraffins, coming out of the oven 60, is supplied via line 64 to the dehydrogenation reactor 70. In the reactor dehydroretinol amount of paraffins to the corresponding olefins. This results in the flow effluent from the dehydrogenation reactor, supplied through line 66, which contains a mixture of hydrogen, paraffins, monoolefins, including the often weakly branched monoolefins, diolefins, hydrocarbons to C9and aromatic hydrocarbons. Such stream of exhaust from the dehydrogenation reactor, the first cooled by indirect heat exchange in heat exchanger 58, serves on line 68 and then again cooled in indirect heat exchanger 72. This cooling is sufficient to condense practically all hydrocarbons10+in the flow of the liquid phase and separating the flow of the liquid phase from the remaining vapor is enriched in hydrogen. Effluent from the dehydrogenation reactor is supplied via line 74 into the vessel for the separation system vapor - liquid 80. In the separating vessel 80 stream effluent from the dehydrogenation reactor is divided into a flow of vapor phase enriched in hydrogen exhaust line 76, and the dehydrogenation product stream withdrawn through line 84. The flow of the vapor phase is divided into a flow of pure hydrogen exhaust line 78 and the hydrogen-containing stream, recirculating through line 82.
The dehydrogenation product stream withdrawn from the bottom of the separation vessel 80, contains paraffins, labor the olefins, aromatic by-products and some dissolved hydrogen. The dehydrogenation product stream representing the effluent liquid phase from the separation vessel 80, served by line 84 to the selective hydrogenation reactor 86. In the selective hydrogenation reactor 86 the dehydrogenation product stream is brought into contact with a catalyst for selective hydrogenation under conditions that provide for the conversion of a significant part of diolefins in the appropriate monoolefinic. This conversion by hydrogenation can be carried out using hydrogen dissolved in the product stream of the dehydrogenation and/or additional fresh hydrogen (not shown) fed to the reactor for selective hydrogenation. The result is a stream effluent from the selective hydrogenation reactor, supplied to the line 88, containing a mixture of hydrogen, normal paraffins, often weakly branched paraffins, normal monoolefins, often weakly branched of monoolefins, hydrocarbons to C9and aromatic by-products. Then the effluent from the selective hydrogenation reactor serves on line 88 to the Stripping column 90. In this column steaming hydrocarbons to C9formed in sub> hydrocarbons are concentrated in the main stream which is withdrawn from the process through line 94.
The rest of hydrocarbons filed in the Stripping column 90, concentrated in the stream effluent from the stage steam discharged through line 96. Then the stream effluent from the stage of the steam fed to the zone of removal of aromatics 100. In this zone the flow effluent from the stage steam in contact with the adsorbent under conditions that promote removal of aromatic by-products. Effluent from the zone of removal of aromatics 100 serves to line 98. This thread contains a mixture of normal paraffins, often weakly branched paraffins, normal monoolefins and often weakly branched of monoolefins and significantly lower concentration of aromatic by-products than the flow effluent stage with steam. The resulting mixture was combined with benzene from line 112 and line 102 serves in the alkylation reactor 104. In the alkylation reactor, benzene and monoolefinic brought into contact with an alkylation catalyst under conditions conducive to reaction of alkylation, with the formation of phenylalkanoic.
Stream effluent from the alkylation reactor serves on line 106 column fractionation of benzene 110. The feed stream contains a mixture of benzo portion and one aliphatic alkyl portion, containing 1 or 2 primary carbon atom, and phenylalkanoic molecules containing one aliphatic alkyl portion and the phenyl part, and an aliphatic alkyl part has 2, 3 or 4 primary carbon atoms and contains no Quaternary carbon atoms except for the Quaternary carbon atom bound to the phenyl fragment.
In other words, the stream contains a mixture of benzene, normal paraffins, often weakly branched paraffins, LAB, and MAV. This thread share in the benzene fractionation column 110 at the bottom of the stream head and stream containing benzene and light gaseous products. Head flow away along the line 107 and combine with fresh benzene supplied on line 109. The combined stream is available on line 108 in the separation drum 120, which nscontainerframe light gases, if any, output line 114, and the condensed liquid is discharged through line 116 to provide phlegmy for column 110 through line 118 and benzene for recycle through line 112. On line 122 residual flow effluent from the stage of alkylation of the columns 110 is served in the paraffin column 124, from which the bottom stream containing phenylaline and heavy by-products of Ala is 130 on the bottom stream 132, containing heavy alkylate, and head alkylation product stream 128 that contains phenylalkanoic derivatives. The head stream of the paraffin column 124 is a recirculating stream that contains a mixture of paraffins, which recycle to the dehydrogenation zone through line 48. Although it is not shown in the drawing, some portion of the flow of their paraffin column 124 may be submitted to the dehydrogenation zone and the isomerization zone.
As an alternative process scheme shown in the drawing, the head stream from line 48 may be introduced into the dehydrogenation zone at other points, such as line 62, line 64, or through the reactor 70. In the case when the input is the dehydrogenation reactor 70, the head stream may be injected at a point between the inlet 64 and the outlet line 66, resulting in the parent thread may come in contact with only part of the catalyst in the reactor 70. Another way of contacting the downstream flow only part of the dehydrogenation catalyst is ensured by the separation of the dehydrogenation reactor 70 for two or more intermediate reactor containing the catalyst, series-connected with each other by one or more lines, and wego input into the dehydrogenation reactor 70 will be determined by factors including olefins in the main stream and the required reaction conditions dehydrogenation, including conversion. Similarly, in the technical solution, which enter the head of the stream to the isomerization zone along the line 48, the insertion point may be located above the input line 26 to the isomerization reactor 30, resulting in the parent thread needs to be in contact with the entire amount of catalyst in the isomerization reactor 30. However, depending on the conversion isomerization reactions, the degree of branching of the head of the stream in line 48 and other factors, the insertion point may occupy an intermediate position between input 26 and output line 28, in consequence of which will be provided by the parent stream is in contact only with a part of the catalyst in the isomerization reactor 30. The isomerization reactor 30 can be divided into two or more smaller sequential reactor, resulting in the parent thread may be imposed in such a way that it will not pass through all of the isomerization reactor. As a result of composition analysis of the product of isomerization, dehydrogenation product and product streams alkylation is the preferred point of entry recirculating the downstream flow in the process will not work the products of alkylation 128 may be implemented as described above with obtaining phenylalkanoic sulphonic acids, which may be subjected to neutralization in accordance with the above described methods.
Examples are presented to illustrate the beneficial properties and advantages of the present invention.
Examples 1 and 2 illustrate the application of the preferred isomerization catalyst of the present invention. In both examples, we used the following methodology. Sample isomerization catalyst with a volume of 20 cm3was placed in a tubular reactor with an inner diameter of 1.27 see the isomerization Catalyst was subjected to preliminary restoration by contact with a 0.27 nm3/h of hydrogen at a pressure of 69 kPa (g), while the temperature of the catalyst was maintained equal to 110C for 1 hour, increased from 110 to 400C for 3 hours and then kept at the value 400C for 2 hours. After this preliminary reduction of the isomerization catalyst was cooled to 150C.
Thereafter, the catalyst was tested for activity in isomerization reactions using as raw material a mixture of normal paraffins With10-C14. The original reaction mixture (“raw”) was passed over the catalyst isome the tour of the catalyst is regulated so in order to achieve the desired conversion of linear paraffins. The flow of exhaust from the tubular reactor was applied to the separator system gas - liquid and collecting the liquid phase (the“product”). The obtained product was analyzed by gas chromatography in accordance with the above.
In examples 1 and 2, the individual components of the raw product, determined by gas chromatography, were grouped in five classifications: light products containing 9 and less carbon atoms (C9-); linear paraffins containing 10 to 14 carbon atoms (“linear”); monomethylaniline paraffins containing 10 to 14 carbon atoms in the product (“mono”); dimethylethylene paraffins and etilatsetatnyj paraffins containing 10 to 14 carbon atoms in the product (“di”); and heavy products containing 15 or more carbon atoms (C15+). Based on these five groups was calculated with the following operational characteristics:
Conversion = 100[1-(number linear in the product) /(the number of linear raw materials)].
ii. Selectivity for monomethylmercury:
Selectivity for monomethylmercury: 100x[mono/mono+di)]
iii. The yield of light products:
The yield of light products: 100The yield of heavy products = 100[C15+/(C9-+(linear in the number of product) +
MONO + DI + C15+)].
The catalyst of example 1 was prepared by joint extrusion of 0.39 wt.% Pt on the media, including the extrudate from 60 wt.% SAPO-11 and 40 wt.% aluminum oxide. During isomerization conversion was 73,4 mol.%, selectivity for monometallism of 55.5 mol.%, the yield of light products to 7.9 mol.% and quit heavy products of 0.01 mol.%.
The catalyst of example 2 were prepared by impregnation of a mixture of 50 wt.% MgAPSO-31 and 50 wt.% aluminum oxide 0.26 wt.% Pt. In the isomerization conversion was $ 73.3 mol.%, selectivity for monometallism 69,6 mol.%, the yield of light products amounted to 13.5 mol.%, and the output of heavy products less than 0.01 mol.%.
The data given in examples 1 and 2 demonstrate good value conversion and high selectivity for monomethylaniline, which can be achieved with the use of isomerization catalysts comprising SAPO-11 and MgAPSO-31.
Example 3 illustrates the preferred dehydrogenation catalyst designed for use in the present invention, and the method of preparation of such a catalyst. Spheres of aluminum oxide was prepared by a well-known method is uchet forming a Hydrosol of aluminum by dissolving aluminum in hydrochloric acid. Hexamethylenetetramine was added to solo for solidification of the latter, with the formation of spheres in the dispersion in the form of droplets in an oil bath at a temperature of 93C. Drops left in the oil bath to their deposition and the formation of spheres from the hydrogel. After removing these areas from the hot oil they were subjected to aging under pressure at 135C and washed with dilute ammonium hydroxide solution, dried at 110S and annealed at 650C for 2 hours with the formation of spheres of gamma-aluminum. The calcined alumina was ground into a fine powder with a particle size less than 200 microns (0.2 mm).
After that was preparing a slurry by mixing 258 g of aluminum Sol (20 wt.% Al2O3) and 6.5 g of a 50% aqueous solution of tin chloride and 464 g of deionized water and mixing until a homogeneous distribution of chloride of tin. To the resulting mixture were added 272 g prepared above powder of aluminum oxide and the suspension was stirred for 2 hours in a ball mill, reducing the maximum particle size to a value less than 40 micron (0.04 mm). The resulting suspension (1000 g) for 17 minutes sprayed using ostreicole of 1.05 mm, with the formation of the outer layer thickness of about 74 microns (0,074 mm). After completion of the process remained 463 g of the suspension, the engine which had no coverage. Spherical carrier coated layer was dried at 150C for 2 hours and then subjected to firing at 615C for 4 hours with the aim of turning pseudoboehmite in the outer layer of gamma-alumina and transformation of tin chloride to tin oxide.
The calcined carrier with a layer (1150 g) was impregnable lithium using a rotary impregnator, as a result of contacting the substrate with an aqueous solution (volume ratio of solution : native 1:1) containing lithium nitrate and 2 wt.% nitric acid based on the weight of the carrier. The impregnated catalyst was heated using a rotary impregnator before full removal solution, dried and again progulivali for 2 hours at 540C.
The composite containing lithium and tin, was impregnated with platinum as the result of contacting the composite with an aqueous solution (volume ratio of solution : native 1:1) containing chloroplatinic acid and 1.2 wt.% hydrochloric acid (calculated on the weight of the carrier). The impregnated composite was heated with the img src="https://img.russianpatents.com/chr/176.gif">With and restored in hydrogen at 500C for 2 hours. According to the elemental analysis of the resulting catalyst contained 0,093 wt.% platinum 0,063 wt.% tin and 0.23 wt.% lithium calculated on the total weight of the catalyst. Distribution of platinum was determined by microanalytical analysis with an electronic probe (EPMA) using scanning electron microscopy, the results of which showed that platinum is uniformly distributed only in the outer layer.
The catalyst of example 3 was tested for activity against dehydrogenation. In a reactor with a diameter of 1.27 cm was placed 10 cm3catalyst and hydrocarbon feedstock containing 8.8 wt.% n-C10, 40.0 wt.% n-C11, and 38.6 wt.% n-C12, 10.8 wt.% n-C13, 0.8 wt.% H-C14and 1% vol. nonlinear hydrocarbons was passed over the catalyst at a pressure of 138 kPa (g), a molar ratio of hydrogen : hydrocarbon of 6:1 and a LHSV 20 h-1.Injected water with a concentration of 2000 ppm based on the weight of the hydrocarbon. In the temperature control of the reactor, the total concentration of normal olefins in the product (%TNO) was maintained at a value of 15 wt.%.
In the test the following results were obtained. Selectivity,6 wt.%. The concentration of the non-linear olefin, which was calculated as 100% TNO amounted to 5.4 wt.%.
The results show that the used in the present invention is applied, the catalyst has a low rate of deactivation and high selectivity for normal olefins. Because hydrocarbons in this example, mainly consisted of normal paraffins, high selectivity by TNO indicates relatively low skeletal isomerization of hydrocarbons during dehydrogenation.
Example 5 illustrates the alkylation catalyst designed for use in the present invention, which is prepared in the usual way, used for the preparation of catalysts for the alkylation. As source material used hydrogen form of mordenite with a ratio of SiO2/Al2About3about 18, which is hereinafter referred to as the original mordenite. 90 mass parts of the original mordenite was mixed with 10 weight parts of alumina powder. To the mixture was added to an acidified solution for peptization. Then the mixture was extrudible using known devices. After completion of the extrusion process the resulting extrudate was dried and ProCal the l for 2 hours at 66With a volume ratio solution : the extrudate, is equal to 6:1. After washing the extrudate within 1 hour, washed with water at a volume ratio solution : the extrudate equal to 5:1, and then dried.
Example 6 illustrates the use of the alkylation catalyst obtained in example 5.
Used olefinic feedstock comprising a mixture of monomethyl-olefins With12and having the composition shown in table 1.
Olefinic feedstock was mixed with benzene to obtain the combined raw materials containing 93,3 wt.% benzene, 6.7 wt.% olefinic feedstock, which corresponds to a molar ratio of benzene : olefin of about 30:1. In a cylindrical reactor with an inner diameter of 22.2 mm downloaded 75 cm3(53,0 g) of the extrudate obtained in example 5.
United raw material fed into the reactor and brought into contact with the extrudate at LHSV of 2.0 h-1total pressure of 3447 kPa (g) and the temperature at the inlet of the reactor 125C. under these conditions, the reactor was futurevalue within 24 hours and then spent the next 6 hours collecting liquid product.
The liquid product of selective reactions were analyzed by the method of13Nuclear magnetic resonance (NMR) to determine the selectivity of 2-brezec phenylaline in the amount of 0.5 g was diluted to 1.5 g anhydrous deuterated chloroform. An aliquot volume of 0.3 ml of diluted phenylalkanoic mixture was mixed with 0.3 ml of 0.1 M solution of chromium acetylacetonate (III) in deuterated chloroform at 5 mm vials for NMR. To the mixture was added a small amount of tetramethylsilane (TMS) as a reference for the chemical shift at 0,0 h/million Range were recorded on a spectrometer Bruker ACP-300 FT-NMR obtained from Bruker Instruments, Inc., Billerica, Massachusetts, USA. The carbon spectrum was recorded at field strength 22727 Tesla or frequency 75,469 MHz in 5 mm QNP probe with a width deviation 22727 Hz (301,1 h/m), recording with about 65000 experimental data. Quantitative carbon spectrum was obtained using the process strobing1H cleavage (splitting with a back-gate). Quantitative13With a range of recorded pulses 7,99 microseconds (90), when the process time 1,442 second, 5-second delay between pulses, when the power splitting, using a mixed pulse splitting (CPD) order N when pulse width 105 microseconds (90and the number of scans at least 2880. Used number of scans depends on the implementation of the Stripping of benzene from the liquid product before selecting the above-mentioned sample quantity the company Bruker Instruments, Inc. During data processing used an extension of the data at 1 Hz. Specific peaks were integrated in the field of 152 hours/million and 142 hours/million Identification chemical shifts in the peaks of the13With NMR, related to the benzyl carbon of isomeric fenelonov presented in table 2. Used in the text the term “benzyl carbon” refers to carbon atom in the phenyl ring, associated with the aliphatic alkyl group.
Peak at 148,3 hours/million identified as 4-methyl-2-phenylalkanoic and m-methyl-m-phenylaline (m>3). However, in the presence of m-methyl-m-phenylaline (m>3) more than 1% of these substances give a distinct peak, shifted by 0.03 hours/million relative to peak 4-methyl-2-phenylalkanoic. Peak 147,8 hours/million, according to table 2, identified as relating to the 2-phenylalkyl, with possible interference from 3-methyl-3-phenylalkanoic.
The selectivity limit phenylalkyl was calculated by dividing the integral of the peak with 149,6 hours/million by the sum of the integrals of all the peaks listed in table 2, multiplied by 100. The selectivity for 2-phenylalkyl can be determined if the contribution from the number of internal Quaternary of phenylalkanoic in spades with 148,3 h/m and 147,8 hours/million status the ranks approximation this condition is satisfied in the case when the sum of the integrals of the peaks corresponding to 4-phenylamino and 3-phenylamino, 146,2-146,3 h/m and 145,9-146,2 h/m (respectively) is small relative to the sum of the integrals of all the peaks from 145,9 PM/149,6 million to h/m, and the selectivity limit Quaternary phenylalkyl less than 10%. In this case, the selectivity for 2-phenylalkyl is calculated by dividing the sum of the integrals of the peaks from 149,6 to 146,6 hours/million by the sum of the integrals of all the peaks listed in table 2, multiplied by 100.
The liquid product of selective reactions were also analyzed by gas chromatography-mass spectrometry to determine the selectivity to internal Quaternary phenylalkyl. The analytical method is gas chromatography-mass spectrometry consists in the following. The liquid product was analyzed on a gas chromatograph (GC) HP 5890 series II, equipped with an automatic device for applying samples HP 7673 and mass spectrometric (MS) detector HP 5972. To control the characteristics of the process and the resulting data used HP Chemstation. HP 5890 series II HP 7673, HP 5972 and HP Chemstation, or any other hardware and software supplied by Hewlett-Packard Company, Palo Alto, California, USA. GC equipped with a column DB1HT (df=0,l μm) size 30m0.25 mm or is arranged helium at a constant pressure of 103 kPa (g) and a temperature of 70C. the temperature of the evaporator was maintained equal to 275C. the temperature of the feed line and the MS source was maintained at a value of 250C. we Used the following temperature program: 70C for 1 minute, then heated to 180With speeds of 1With in a minute, then heated to 275With a speed of 10With in a minute and subsequent aging at 275C for 5 minutes. MS was tuned using HP Chemstation, the program of which was regulated using standard spectral auto-tuning. Start scan MS was 50-550 Da threshold =50. The concentration of internal Quaternary of phenylalkanoic in the liquid product was determined (i.e., the selective liquid product was subjected to quantitative determination) using the method of adding standard. Basic information on how to add standard set forth in Chapter 7 of the book, called Samples and Standards. B. W. Woodget with al., published ACOL, London by John Wily and Sons, New York, 1987.
First I prepared the original internal solution of Quaternary phenylalkanoic and determined its composition. Benzene alkilirovanie monomial is its alkylation contains a mixture of internal Quaternary of phenylalkanoic and is considered as the basic internal solution of Quaternary fenelonov. Using the GC method identified the highest peaks, corresponding to internal Quaternary phenylalkyl in the base solution, and determined their concentrations (i.e., conducted quantitative determination of the components of the basic solution) using a flame ionization detector (FID). The concentration of each internal Quaternary phenylaline was calculated by dividing the peak area of the considered internal phenylaline to the sum of the areas of all peaks.
Then cooked reference (spiking) solution of internal Quaternary of phenylalkanoic. An aliquot of the original solution was diluted with dichloromethane (methylene chloride) to obtain the nominal concentration of the specific internal Quaternary phenylaline (for example, 3-methyl-3-phenyldecane) 100 wt.h./million resulting solution was designated as the reference internal solution of Quaternary fenelonov. The concentration of any other internal Quaternary phenylaline in the reference solution may be higher or lower than 100 wt.h./million, depending on the concentration of this Quaternary phenylaline in the original rastburg capacity of 10 ml Then the contents of the flask was diluted with dichloromethane, adding it to the mark corresponding to a volume of 10 ml. of the resulting contents of the volumetric flask was defined as the sample solution.
Finally, preparing the resulting solution. 0.05 g aliquots of the selective liquid product was placed in a volumetric flask with a capacity of 10 ml and Then the contents of the flask was diluted to the mark corresponding to a volume of 10 ml of reference solution. The resulting contents of the flask were identified as resulting solution.
The sample solution and the resulting solution was analyzed by method GC/MS using the conditions above. Table 3 lists the ions extracted from the full scan MS spectrum, and data for these ions were subjected to the processing and integration using software HP Chemstation. These software HP Chemstation was used to determine peak areas related to individual ions, corresponding to internal quatum listed in table 3.
The concentration of each internal Quaternary phenylaline listed in table 3 was calculated by the following equation:
in which C - conc the CSOs phenylaline in the reference solution, wt.%;
A1the peak area of the internal Quaternary phenylaline in the sample solution, the unit area;
And2the peak area of the internal Quaternary phenylaline in the resulting solution, the unit area.
Concentrations of C and S have the same dimension, provided that the area of A1and a2also have the same dimension. After that, the concentration of each internal Quaternary phenylaline in the selective liquid product was calculated from the concentration of this Quaternary phenylaline in the sample solution, taking into account the effect of dilution of the sample solution with dichloromethane. Similarly calculates the concentration of each of the inner Quaternary of phenylalkanoic listed in table 3. The total concentration of internal Quaternary of phenylalkanoic in the selective liquid product, CIQPAwas calculated by summing the individual concentrations of each are listed in table 3 internal Quaternary of phenylalkanoic.
It should be noted that the selective liquid product may contain internal Quaternary phenylaline other than those listed in table 3, for example, m-methyl-m-phenylaline, where m>5, depending on the number of carbon is renovage raw materials and conditions described in example 6, the concentration of such other internal Quaternary of phenylalkanoic are relatively small compared to the internal content of Quaternary fenelonov listed in table 3. In this regard, in example 6 the total concentration of internal Quaternary of phenylalkanoic in the selective liquid product, CIQPAwas calculated by summing only those individual concentrations of each of the inner Quaternary of phenylalkanoic that are listed in table 3. However, when the olefin feedstock contains olefins with the number of carbon atoms, for example, to 28, the total concentration of internal Quaternary of phenylalkanoic in the selective liquid product, WithIPQAshould be calculated by summing the individual concentrations of m-methyl-m-fenelonov, where m has a value in the range of 3-13. In General, if the olefinic feedstock contains olefins with the number of carbon atoms of x, then the total concentration of internal Quaternary of phenylalkanoic in the selective liquid product, WithIPQAcalculate the sum of the individual concentrations of m-methyl-m-fenelonov, where m has a value in the interval 3 - x/2. Can be identified, at least one peak with respect to mass-to-charge (m/z) of the sample is and the concentration of each of the inner Quaternary of phenylalkanoic and subsequent summation can be obtained the value ofIPQA.
Selectivity for internal Quaternary phenylalkyl in the selective liquid product can be calculated by the following formula:
in which Q is the selectivity for internal Quaternary phenylalkyl;
WithIPQAthe concentration of internal Quaternary of phenylalkanoic in the selective liquid product, wt.%;
WithMAVthe concentration of modified alkyl benzenes in the selective liquid product, wt.%.
The concentration of modified alkyl benzenes,MAVin the selective liquid product was determined by the following method. Firstly, by gas chromatography was determined by the impurity concentration in the selective liquid product. In the context of relating to the definition of CMAVthe term “impurity” refers to the components of the selective liquid product, the retention times which are outside a specified interval used in gas chromatography method. Such “impurities” usually include benzene, some dialkylphenol, olefins, paraffins, etc.
To determine the number of considered impurities in the selective liquid product has used the following gas chromatographic method. For determination of impurities in the selective liquid product can iatry GC, different from those specified below, provided that they provide results equivalent to the following.
- Gas chromatograph Hewlett Packard HP 5890 series II, equipped with a metering device with a flow divider or without it and a flame ionization detector (FID);
- J&W research capillary column DB-1HT, length 30 m, internal diameter 0.25 mm, film thickness of 0.1 mcm;
11 mm wall Restek Corporation (USA) Red lite Septa;
- 4 mm S-shaped inlet hose from upeslacis company Restek;
- O-shaped ring gasket for the inlet line of Hewlett Packard;
- methylene chloride or its equivalent purity HPLC from J. T. Baker Company (USA);
- 2 ml ampoules for chromatographic automatic device for applying samples with curved edges, or their equivalents.
- Sample of 4-5 mg was weighed in a vial GC auto sampler.
In the GC vial was added 1 ml of methylene chloride; the ampoule was closed corrugated, Teflon lined septum (cap); and the contents of the ampoule were intensively mixed.
The GC parameters:
- Carrier gas: hydrogen
- Pressure in the head of the chromatographic column: 62 kPa
- Flow: the flow of gas through the column, 1 ml/min; separation inteprets 10 μl; the volume of injected sample 1 μl.
The injector temperature: 350
The detector temperature: 400
- Temprogressive: initial exposure at 70C for 1 minute; heating at a rate of 1C/min; final extract for 10 minutes at 180C.
Used gas chromatographic method requires the use of two standards that are carefully distilled to a purity higher than 98 mol.%. Typically, each standard is a 2-phenylalkyl. One of the 2-phenylalkanoic standards, which is hereinafter referred to as ' light standard, contains aliphatic alkyl group the number of carbon atoms of which at least one carbon atom less than the olefin in the olefinic feedstock fed to the alkylation zone, with a minimum number of carbon atoms. Another 2-phenylalkanoic standard referenced as heavy standard, contains aliphatic alkyl group, at least one carbon atom more than the olefin in the olefinic feedstock fed to the alkylation zone, with the largest number of carbon atoms. For example, if the olefins in the olefinic feedstock fed to trilochan, and suitable heavy standard - 2-phenylpentane. Each of the standards is passed through the chromatographic column in the above conditions for determining retention time and two obtained values of retention time was determined by the total interval of the retention times of the components of the mixture. Then in the same conditions hold for the gas chromatographic analysis of the aliquot of sample selective liquid product. If more than 90% of the GC peak areas fall within the specified range of the retention time, it is considered that the amount of impurities in the selective liquid product does not exceed 10 wt.% the number of selective liquid product, and solely in order to simplify the calculation, the selectivity for internal Quaternary phenylalkyl,MAV, was taken equal to 100 wt.%.
If the total interest amount of surface area of the chromatographic peaks within the specified interval retention time is less 90%, it is considered that the amount of impurities in the selective liquid product exceeds 10 wt.% from the mass selective liquid product. In this case, to determine the CMAVimpurities are removed from the selective liquid product, which uses the following method of distillation. To remove primepay and the equivalent conditions of distillation, other than described below, but provide equivalent results.
For the distillation process is designed to remove impurities from the selective liquid product, use a 5-liter, 3-necked round bottom flask with a magnetic stir bar and a small amount of cepelak. The Central throat hole flask was placed a Vigreux condenser length 24,1 see from the Top of the Vigreux condenser attached water-cooled refrigerator, equipped with a control thermometer. By the end of the refrigerator attach the vacuum receiver. One of the outlets 5-liter distillation flask closed by a glass tube, and a thermometer placed on the other allotment of the flask. The flask and condenser Vigreux wrapped with aluminum foil. A 5-liter flask is charged with 2200-2300 g aliquot part of the selective liquid product, containing about 10 wt.% impurities in accordance with the data of chromatographic analysis. To the vacuum receiver attach the line from the vacuum pump. Selective liquid product in a 5-liter flask is stirred and vacuum system. After reaching the maximum value of the vacuum (residual pressure of at least 25.4 mm Hg or less) selective liquid product is heated using electoral next mark, as fraction A, is selected in the temperature interval from 25C to the boiling point of a light standard. The other faction, the faction selected in the temperature range from the boiling point of easy standard to the boiling point of the heavy standard. Easy boiling fraction and a low-boiling residues cast. Fraction b contains a modified alkyl benzenes and weighed. The described method can optionally be scaled. Vapour pressure of phenylalkanoic at different temperatures can be taken from an article in Industrial and Engineering Chemistry, T. 38, 194, starting on page 320.
Then an aliquot of the sample fractions analyzed by gas chromatography in the above conditions. If more than 90% of the total number of chromatographic peaks in the faction to fall Within the interval of retention time, the amount of impurities in the faction believe In not more than 10 wt.% from the selective liquid product, and solely for purposes of calculating the selectivity to internal Quaternary phenylalkyl,MAVcalculated as quotient of the weight fractions In the weight of the aliquot part of the selective liquid product, is loaded into a 5-liter flask in the above-described method of distillation. If the total percentage of chromatogr what about the impurities in the faction To consider greater than 10 wt.% from the mass fraction Century In this case, the impurities contained in the faction, again removed using the above method distillerie. Accordingly, the low-boiling fraction (denoted as fraction C) and high-boiling distillation residues drop, fraction (denoted as fraction (D) containing modified alkyl benzenes, isolated and weighed, and an aliquot of the sample fractions analyzed by gas chromatography. If more than 90% of the total number of chromatographic peaks in fraction D fall within the corresponding interval of retention time, solely for purposes of calculating the selectivity to internal Quaternary phenylalkyl valueMAVcalculated as quotient of the weight fractions of D on the weight of the aliquot part of the selective liquid product, initially loaded into a 5-liter flask. Otherwise, the distillation fractions D and its gas chromatographic analysis of the repeat.
The above-described methods of distillation and gas chromatography analysis can be repeated to obtain fractions containing modified alkyl benzenes and less than 10 wt.% impurities, provided that after each stage distillation remains sufficient material for subsequent tests indicated metabyte calculated by the above formulas. The results of the analysis are presented in table 4:
In the absence of size selectivity, as in the case of using such catalysts as aluminum chloride or HF, it can be expected that a large part of the 2-methylundecane converted into 2-methyl-2-finlandese (i.e., the end Quat). Similarly, it can be expected that a large part of the 6-methylundecane, 5-methylundecane, 4-methylundecane and 3-methylundecane turns into internal Katy. As expected, linear olefins give the statistical distribution of 2-phenyldecane, 3-vinyltoluene, 4-phenyldecane, 5-phenyldecane and 6-phenyldecane.
Thus, if excluded from the calculation of light, heavy and other alkylamine listed in table 1, the selectivity for 2-phenylalkyl will not exceed 17 and selectivity for internal Quaternary phenylalkyl will reach 55. The data presented in table 4 show that the selectivity for 2-phenylalkyl significantly higher than might be expected in the absence of size selectivity, and selectivity for internal Quaternary alkyl benzenes obtained by using a catalyst based on mordenite, much less than the value m is 1. The method of receiving fenelonov, especially modified alkyl benzenes, comprising the following stages: a) passing a stream of material containing paraffins C8-C28in the isomerization zone, the zone isomerization conditions sufficient for the isomerization of paraffins, and the allocation of zone isomerization stream isomerizing product containing paraffins; (b) passing at least part of the flow isomerizing product in the dehydrogenation zone, the zone dehydrogenation dehydrogenation conditions sufficient for the dehydrogenation of paraffins, and regeneration of the dehydrogenation zone flow dehydrogenation product containing monoolefinic and waxes, monoolefinic in the dehydrogenation product stream containing 8-28 carbon atoms and at least part of monoolefins in the stream of the dehydrogenation product contains 3 or 4 primary carbon atoms and contains no Quaternary carbon atoms; (c) the filing of a phenyl derivative and at least part of the dehydrogenation product stream containing monoolefinic zone alkylation zone alkylation conditions sufficient for the alkylation of phenyl derivative with monoolefins in the presence of a catalyst and efficiency alkyl part, containing 8-28 carbon atoms; and at least a portion of phenylalkanoic formed in the alkylation zone contains 2, 3 or 4 primary carbon atoms and contains no Quaternary carbon atoms except for any Quaternary carbon atom connected through a carbon-carbon link carbon atom of the phenyl portion of the molecule; and the selectivity of the alkylation of 2-phenylalkyl is 40-100, and selectivity for internal Quaternary phenylalkyl has a value less than 10; (d) regeneration of the area alkylation alkylate stream containing phenylaline and re-circulating stream containing paraffins; and (e) feeding at least part of the recirculating flow in the area isomerization or dehydrogenation zone.
2. The method according to p. 1, characterized in that at least part of the stream of the isomerization product has a concentration of paraffins containing 3 or 4 primary carbon atoms and containing no Quaternary carbon atoms, more than 25 mol.%, from at least part of the stream of the isomerization product.
3. The method according to p. 1, characterized in that at least part of the stream of the isomerization product has a concentration of paraffins containing a secondary carbon atoms and 2 primary operon is m, the alkylation catalyst includes a zeolite with structural type selected from the group consisting of BEA, MOR, MTW and NES.
5. The method according to p. 1, characterized in that the phenyl derivative includes a compound selected from the group consisting of benzene, toluene and ethylbenzene.
6. The method according to p. 1, characterized in that phenylaline include monomethylaniline.
7. The method according to p. 1, characterized in that at least part of the recycle stream is fed to the isomerization zone, and additionally characterized in that the isomerization zone contains the first catalytic layer comprising an isomerization catalyst and a second catalyst layer comprising a catalyst for isomerization, and the material flow is served on the first catalytic layer, under conditions favoring the isomerization of paraffins, the flow of exhaust from the first catalytic layer containing waxes, derived from the first layer, at least a portion of effluent of the first layer and at least a portion of the recirculating stream is served on the second catalytic layer, in terms of providing the isomerization of paraffins, and product flow isomerization away from the second catalytic layer.
8. The method according to p. 1, characterized in that CR is naliticheskie layers, comprising a dehydrogenation catalyst, and at least a portion of the product stream isomerization served on the first catalytic layer, under conditions conducive to the dehydrogenation of paraffins, and the flow of exhaust from the first catalytic layer containing waxes, derived from the first layer, at least a portion of effluent of the first layer and at least a portion of the recirculating stream is served on the second catalytic layer, under conditions which ensure the dehydrogenation of paraffins, and product flow dehydrogenation away from the second catalytic layer.
9. Grease on the basis of modified alkyl benzenes obtained by the method according to p. 1.