Method of obtaining alkyl-aromatic compounds

FIELD: chemistry.

SUBSTANCE: invention relates to method of alkylating of aromatic compound to be alkylated with obtaining monoalkylated aromatic compound. method includes the following stages: A) supply of the first flow of raw material, including fresh aromatic compound to be alkylated, into the first reaction zone, which includes trans-alkylation catalyst; B) supply of the second flow of raw material, which includes polyalkylated aromatic compounds, into the first reaction zone; C) contact of said first and second flows of raw material with said trans-alkylation catalyst in said first reaction zone under conditions, suitable for realisation of reaction of trans-alkylation between said polyalkylated aromatic compounds and said aromatic compound to be alkylated, in fact, in liquid phase, with obtaining said monoalkylated aromatic compound; D) removal of the first output flow, which includes aromatic compound to be alkylated which did not react and said monoalkylated aromatic compound, from said first reaction zone; E) supply of said first output flow into fractioning system for division of said first output flow into the first light fraction, which includes said aromatic compound to be alkylated which did not react, and the first heavy fraction, including said monoalkylated aromatic compound; F) separation of monoalkylated aromatic compound from said first heavy fraction; G) supply of said first light fraction, which includes said aromatic compound to be alkylated, and third raw material flow, including alkylating agent, into the second reaction zone, which includes catalyst of alkylation; H) contact of said fist light fraction and the third flow of raw material with said catalyst of alkylation in said second reaction zone under conditions, suitable for alkylation of said aromatic compound to be alkylated by means of said alkylating agent, and obtaining the second output flow, which includes said monoalkylated aromatic compound, aromatic compounds to be alkylated which did not react and polyalkylated aromatic compounds; and I) separation of monoalkylated aromatic compound from said second output flow. In the first reaction zone, at least, part of one or more admixtures, contained in fresh flow of raw material, are removed.

EFFECT: obtaining monoalkylated aromatic compound.

15 cl, 2 dwg

 

Cross-reference to related applications

In this application claimed priority to provisional patent application US 61/104447, filed October 10, 2008, and European patent application 09150689.9, filed January 16, 2009, the contents of these applications are fully incorporated into the present description by reference.

The technical field to which the invention relates.

The present invention relates to a method for producing alkylaromatic compounds, specifically, ethylbenzene and cumene.

Background of invention

Ethylbenzene is a key raw material in the production of styrene, and it is obtained by the reaction of ethylene and benzene in the presence of an acid catalyst. Similarly, the cumene is an important precursor in the production of phenol, and it is produced by alkylation of benzene with propylene in the presence of an acid catalyst.

Traditionally ethylbenzene get in the headspace of the reactor systems, which carry out the reaction atilirovanie of benzene with ethylene at a temperature of approximately 380 to 420°C and a pressure of from 150 to 250 lb./square inch (Rel.), a few fixed layers of the zeolite catalyst. Ethylene becomes exothermic reaction with benzene to form ethylbenzene, although it can also occur undesirable chain and adverse reactions. The example is about 15% of the resulting ethylbenzene additionally reacts with ethylene to form isomers of diethylbenzene (DEB), isomers of triethylbenzene (TEB) and aromatic products with higher molecular weight. All these products are chain reactions usually called polietilenovoi benzenes (HSE). In addition to the reactions atilirovanie are adverse reactions, which are formed isomers of xylene in trace quantities. Such education xylene in the vapor-phase processes can lead to the end of ethylbenzene containing approximately from 0.05 to 0.20 wt%. xylenes. In subsequently produced styrene product xylenes are impurities that are typically considered desirable.

To reduce to a minimum the education, the FPU uses a stoichiometric excess of benzene, approximately from 400 to 2000% in one pass, depending on the optimization method. The exit stream of the reactor atilirovanie contains from about 70 to 85% of the mass. unreacted benzene, from about 12 to 20% of the mass. end of ethylbenzene and from about 3 to 4% of the mass. The HSE. In order to avoid reduction of output, HSE turn in ethylbenzene by TRANS-alkylation additional quantity of benzene, usually in a separate reactor, TRANS-alkylation.

Example vapor atilirovanie benzene over a crystalline aluminosilicate zeolite ZSM-5 is described in patents US 3751504 (Keown and others) 3751506 (Burress) and 3755483 (Burress).

In recent years in the industry) is there a trend away from the headspace of the reactors receiving ethylbenzene to liquid-phase reactors. Liquid-phase reactors operate at a temperature of from about 180 to 270°C, which is below the critical temperature of benzene (about 290°C). One of the advantages of liquid-phase reactor is very low formation of xylenes and other undesirable by-products. The reaction rate of atilirovanie usually reduced in comparison with a vapor-phase reactors, however, provided by the design of the lower temperature liquid-phase reactor is usually compensated for economic reasons, given the negative side associated with a large amount of catalyst. In addition, reduced temperature liquid-phase reactions can reduce the rate of chain reactions, in which are formed the FPU; namely, in liquid-phase reactions about 5 to 8% of the ethylbenzene is converted in the FPU, while in a vapor-phase reactions of this value is from 15 to 20%. Thus, a stoichiometric excess of benzene in the liquid-phase systems typically ranges from 150 to 400%, while in pulsed conditions, the excess is from 400 to 2000%.

The liquid-phase atilirovanie benzene using zeolite beta as catalyst described in patent US 4891458 and European patent publications 0432814 and 0629549. Later it was described that the MCM-22 and its structural analogues can be used in alkylation reactions/TRANS-Alki the financing, specifically, in order to obtain ethylbenzene and cumene. See, for example, US patents 4992606 (MCM-22), 5258565 (MCM-36), 5371310 (MCM-49), 5453554 (MCM-56), 5149894 (SSZ-25), 6077498 (ITQ-1) and 6231751 (ITQ-2).

Liquid-phase installation alkylation of aromatic compounds have significant advantages compared with vapor-phase processes, since the liquid-phase process is carried out at a lower temperature than the vapor. However, such liquid-phase installation, typically more sensitive to impurities in the raw materials, which act as catalytic poisons in relation to the zeolites, used as catalysts for alkylation and TRANS-alkylation. As a result, the majority of liquid-phase processes require the use of raw materials with high purity and/or provide pre-treatment of raw materials in order to remove such impurities, specifically, the basic nitrogen compounds.

One of the known configurations used in liquid-phase alkylation processes to remove impurities, is to set the reaction of the protective layer located upstream from the main alkylation reactor. The reaction protective layer includes one or more layers of catalyst, which are the same or different catalysts, and it can be withdrawn from use at any time to replace the catalyst, while the main set is the WHC alkylation continues to work. In the reaction protective layer alkilirutmi aromatic compound and the alkylating agent is introduced into contact in the presence of an alkylation catalyst, after which they proceed to the main alkylation reactor. The reaction protective layer serves not only to implement the desired alkylation reaction, but also removes from raw materials all reactive impurities, such as nitrogen compounds, which otherwise could deactivate the rest of the alkylation catalyst. Therefore, the catalysts in the composition of the reaction of the protective layer is subjected to more frequent regeneration and/or replacement, compared with the rest of the alkylation catalyst. In addition, the reaction protective layer, usually equipped with a bypass circuit, so that the raw materials of the process of alkylation can be made directly to the alkylation reactor, if the reaction protective layer does not work. One example of a system for the alkylation of aromatic compounds comprising the reaction protective layer described in patent US 6995295, the content of which is fully incorporated into the present description by reference.

Although liquid-phase alkylation processes formed significantly fewer polyallylamine connections than in vapor systems, based on economic considerations of the method there is a need for the fast installation of the reactor TRANS-alkylation, containing the catalyst TRANS-alkylation, in which polyallylamine compounds in the presence of benzene converted into an additional number monoalkylamines product. The benzene fed to the reactor TRANS-alkylation, is usually a part of the benzene coming from the benzene column, together with the additional make-up benzene, who also served in the column. The rest of the benzene coming from the benzene column is passed through the reaction protective layer and serves on the alkylation catalyst.

In accordance with the present invention was developed improved method for the alkylation of aromatic compounds, in which the reactor TRANS-alkylation containing catalyst TRANS-alkylation, comes, essentially, the only fresh feed benzene, and only a small amount of light fractions of the column for the production of benzene. Supply only the make-up benzene in the reactor TRANS-alkylation allows you to apply the reactor TRANS-alkylation as the reaction of the protective layer to remove impurities from the benzene feedstock. In addition, it allows you to maintain in the reactor TRANS-alkylation much greater molar ratio of benzene to polyalkylthiophenes aromatic compounds. This leads to reduced formation of by-polyalkyl avannah aromatic compounds, to increase the degree of conversion polyallylamine aromatic compounds in a single pass and a higher thermodynamic output desired monoalkylamines product. At higher degrees of transformation polyallylamine aromatic compounds in a single pass flow rate of recirculating substances are reduced, also have fewer side polyallylamine aromaticheskikh compounds that should be the subject of distillation. In General, energy costs are also reduced. In addition, the reaction of TRANS-alkylation has zero thermal effect, which allows the operation of the entire plant at relatively low temperatures. The catalyst TRANS-alkylation reactor TRANS-alkylation is typically a zeolite with a high content of aluminum and increased pore size in comparison with the alkylation catalyst. This greatly increases the efficiency of the catalyst TRANS-alkylation in reducing the amount of impurities in the benzene raw material.

In the patent US 5902917 describes a method for alkylaromatic compounds, specifically, ethylbenzene and cumene, in which the raw material is first fed into the area of TRANS-alkylation, and all out of the zone of TRANS-alkylation stream is sent directly to the alkylation zone together with the olefin is lilirose agent, specifically, ethylene or propylene. However, fresh make-up benzene is fed directly into the alkylation zone, and use the alkylation zone as the reaction of the protective layer is not assumed.

In the improved method, the desired monoalkylamines product isolated from the out-flow reactors TRANS-alkylation and alkylation, and unreacted alkilirutmi aromatic compound is sent to the alkylation reactor. Thus it is possible to avoid loss monoalkylamines product, for example, an additional transformation polyallylamine connection in the alkylation reactor.

In the patent US 6096935 describes a method for alkylaromatic compounds using the reaction zone of the TRANS-alkylation reaction zone alkylation, and the output stream of the reaction zone of the TRANS-alkylation sent to the reaction zone alkylation, in which aromatic compounds in the composition of the exit stream of the reaction zone of the TRANS-alkylation alkylate with obtaining the desired alkylaromatic compounds, specifically, ethylbenzene and cumene. Similarly, the area of TRANS-alkylation as the reaction of the protective layer is not expected, and, although in the reaction zone of the TRANS-alkylation serves at least part of the fresh make-up Ben is Ola, the entire output stream zone of the TRANS-alkylation sent directly to the alkylation zone.

In patent application US 2007/0179329 described method of alkylation of aromatic compounds, in which alkiliruya aromatic compounds and, optionally, at least a portion of the alkylating agent in the presence of a certain quantity of water is passed through the reaction protective layer containing alkylation catalyst or TRANS-alkylation, and then introduced into the alkylation zone.

In the patent US 6894201 described method and device for removal of nitrogen compounds from the alkylation substrate, such as benzene. For the adsorption of basic organic nitrogen compounds used traditional layer of adsorbent containing clay or resin, while the hot layer of adsorbent comprising an acidic molecular sieve, used for adsorption of weakly basic nitrogen compounds, such as nitrites, usually in the presence of water. Hot layer of the adsorbent can be located in the reactor TRANS-alkylation upstream from the catalyst TRANS-alkylation (6), in the alkylation reactor upstream from the alkylation catalyst (7), or in both of these positions (Fig).

A brief description of the invention

In one aspect, the present invention relates to a method of alkylation alquiler is imago aromatic compounds with the aim of obtaining monoalkylamines aromatic compounds, includes the following stages:

A) the direction of the first flow of raw materials, including fresh alkilirutmi aromatic compound in a first reaction zone comprising catalyst TRANS-alkylation;

B) the direction of the second flow of raw materials, including polyalkylene aromatic compounds specified in the first reaction zone;

(B) contacting the above first and second flows of raw materials with the specified catalyst TRANS-alkylation specified in the first reaction zone under conditions suitable for the implementation of the reaction of TRANS-alkylation between these polyalkylbenzene aromatic compounds and specified alkilirutmi aromatic connection with obtaining the specified monoalkylamines aromatic compounds;

G) removing from the specified first reaction zone of the first effluent stream comprising unreacted alkilirutmi aromatic compound and a specified monoalkylamines aromatic compound;

D) the specified direction of the first exhaust system for fractionation to separate the specified first exit stream at the first light fraction comprising the specified unreacted alkilirutmi aromatic compound, and the first heavy fraction comprising the specified monoalkylamines aromatic soy is inania;

E) isolation monoalkylamines aromatic compounds from the specified first heavy fraction;

W) direction specified first light fraction comprising the specified alkilirutmi aromatic compound, and a third feedstock stream comprising an alkylating agent in the second reaction zone, comprising the alkylation catalyst;

C) contacting the specified first light fraction and a third flow of raw materials with the specified alkylation catalyst specified in the second reaction zone under conditions suitable for the alkylation specified alkilirutego aromatic compounds using the alkylating agent, and receiving the second output stream comprising the specified monoalkylamines aromatic compound; and

And the selection monoalkylamines aromatic compounds from the specified second output stream.

In some preferred embodiments, the first flow of raw materials includes one or more impurities. At least part of these impurities are removed in the first reaction zone at a stage of contacting (C).

In some preferred embodiments, the impurities in the composition of the first stream of raw materials include at least 0,02 frequent./million, preferably at least 0.05 to frequent./million by weight calculated on the first flow of raw materials. Such impurities wybir the t group, including compounds containing one or more of the following elements: the Halogens, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and metals of groups 1 to 12. Typically, these impurities include reactive nitrogen compounds other than molecular nitrogen. The catalyst TRANS-alkylation acts as a protective layer, removing at least 10% of the mass. these reactive nitrogen compounds in the composition of the specified first stream of raw materials.

Conveniently, the method further includes the following stage:

To) the specified direction of the second effluent stream in a fractionation system to separate the specified second exit stream at the second light fraction comprising unreacted alkilirutmi aromatic compound, and a second heavy fraction comprising the specified monoalkylamines aromatic compound and polyalkylene aromatic compounds, and specified monoalkylamines aromatic compound can be distinguished in stage (C) from the specified second heavy fraction.

Conveniently, the second light fraction comprising unreacted alkilirutmi aromatic compound, is sent to the specified second reaction zone.

In one of the preferred options the first output and the second output stream is directed to the bottom of the fractionation system.

Conveniently, the method further includes the following stages:

L) the direction of the first and second heavy fractions, at least one additional system fractionation to isolate specified monoalkylamines aromatic compounds of these United fractions, and allocating a third faction that includes the specified polyalkylene aromatic compounds; and

M) returning at least part of this third fraction specified in the first reaction zone.

In one of the preferred options the way sometimes additionally includes the following stages:

H) stopping delivery of these first and second flows of raw materials in the first reaction zone;

A) the direction of the first and second flows of raw materials in the third reaction zone comprising catalyst TRANS-alkylation;

H) contacting the above first and second flows of raw materials with the specified catalyst TRANS-alkylation specified in the third reaction zone under conditions that allow to remove at least a portion of these impurities in a specified first flow of raw materials, and TRANS-alkylation above polyalkylene aromatic compounds specified alkilirutmi aromatic compound in order to obtain the specified monoalkylamines aromatic connection is to be placed; and

R) the replacement or regeneration of the catalyst TRANS-alkylation in the first reaction zone.

Conveniently, the catalyst TRANS-alkylation and catalyst alkylation include aluminosilicate molecular sieves, and the molar ratio of silicon oxide to aluminum oxide in the catalyst TRANS-alkylation is less than the alkylation catalyst.

Conveniently, the catalyst TRANS-alkylation and the alkylation catalyst includes a variety of aluminosilicate molecular sieves, and the catalyst TRANS-alkylation has a larger pore size compared with the alkylation catalyst.

Conveniently, the catalyst transalkylating includes a molecular sieve having the index of difficulty, which is less than 2. Typically, the catalyst TRANS-alkylation comprises a molecular sieve selected from the group comprising zeolite beta, zeolite Y, ultrastable (with respect zeolite Y (USY), dealuminated zeolite Y (Deal. Y), rare earth zeolite Y (RSU), mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, and mixtures of the foregoing.

Conveniently, the specified catalyst TRANS-alkylation and/or specified alkylation catalyst comprises a molecular sieve selected from the group comprising zeolite beta molecular sieve, the index of difficulty is from about 2 to about 12, and molecular sieves is a family of MCM-22. Typically, the alkylation catalyst comprises a molecular sieve of the MCM family-22, selected from the group comprising MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, ITQ-30, MCM-36, MCM-49, MCM-56, UZM-8, and mixtures of the foregoing.

In one of the preferred options of the conditions specified in the first reaction zone during the specified contact (stage b) such that allow you to maintain your desired polyalkylene aromatic compound and a specified alkilirutmi aromatic compound, essentially in the liquid phase, and appropriately these conditions include temperature, comprising from about 50 to about 300°C and a pressure of from about 170 to about 10,000 KPa.

In one of the preferred options of the conditions specified in the second reaction zone during the specified contact (stage C) such that allow you to maintain your desired alkilirutmi aromatic compound, essentially in the liquid phase, and appropriately these conditions include temperature, comprising from about 50 to about 270°C and a pressure of from about 1000 to about 10000 KPa.

In one preferred options alkilirutmi aromatic compound includes benzene or naphthalene, and the alkylating agent includes at least one of the following substances: ethylene, propylene, 1-butene, 2-butene and isobutene.

Brief description the drawings

Figure 1 presents a simplified process flow scheme of the process of obtaining monoalkylamines compounds, such as ethylbenzene, in accordance with one of the preferred variants of the present invention.

Figure 2 is a flow diagram previously known in the art method of producing ethylbenzene.

A detailed description of the preferred options

In the present description provides a method of obtaining monoalkylamines compounds by alkylation alkilirutego aromatic compounds alkylating agent in the presence of the alkylation catalyst with subsequent TRANS-alkylation all polyallylamine aromatic compounds, formed during the alkylation, with additional alkilirutego aromatic compounds with additional monoalkylation product. Stage TRANS-alkylation is carried out in the presence of certain catalyst TRANS-alkylation, and in the method according to the present invention, first carry out the contacting of fresh raw materials containing alkilirutmi aromatic compound with a catalyst TRANS-alkylation, so that it serves not only for the TRANS-alkylation polyallylamine aromatic compounds with the aim of obtaining additional manual euronations product, but also acts as the reaction of the protective layer to remove impurities, for example, reactive nitrogen compounds contained in alkiliruya aromatic raw material. As a catalyst for TRANS-alkylation can be chosen so that it had more pentecosta acid sites per unit mass and a larger pore size than the alkylation catalyst, it is more suitable for use as a protective layer to remove poisons in comparison with the alkylation catalyst.

In addition, the supply of fresh aromatic feedstock to the catalyst, TRANS-alkylation allows you to maintain a much higher molar ratio of aromatic substrate and polyallylamine aromatic compounds at the stage of the TRANS-alkylation. This helps reduce the formation of by-products, to increase the degree of conversion in a single pass and to achieve higher thermodynamic output desired monoalkylamines product. In turn, increased the degree of conversion polyallylamine aromatic compounds in one pass reduces as speed recirculatory and quantity of by-products that require distillation, thus, decrease energy costs. In addition, the reaction of TRANS-alkylation has zero thermal effect that is allows to carry out the entire installation at relatively low temperatures.

In the present description, the term "reactive nitrogen compounds" is understood nitrogen compounds other than molecular nitrogen, which in the conditions used in the method according to the present invention, is relatively inert.

Raw materials

Raw materials used in the method according to the present invention, includes alkilirutmi aromatic compound and an alkylating agent.

The expression "aromatic" in relation alkilirutmi compounds suitable for use in the present invention, should be understood in accordance with the value adopted in this technical field, it includes both mono-and polynuclear aromatic hydrocarbons. It is also possible to use aromatic compounds containing heteroatom, provided that they do not act as catalytic poisons under the selected reaction conditions.

Suitable aromatic hydrocarbons include benzene, naphthalene, anthracene, Naftalan, fixed, crown and phenanthrene, and benzene is preferred.

As a rule, fresh aromatic raw materials used in the method according to the present invention, will contain impurities, and, if not removed, they can destructively affect the alkylation catalyst and/or TRANS-alkylation. Examples of such impurities include reactive nitrogen compounds, halog the us and/or compounds includes one or more of the following elements: oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and metals, including metals of groups 1 to 12 of the Periodic table of elements. Typically, these impurities present in the raw materials available from commercial sources, in such quantities that they are impossible to detect by traditional analytical tools. In such cases, about the destruction of not detectable impurities from raw materials is evidenced by the recovery of the catalyst and the degree of conversion of the product after processing.

In some preferred embodiments, the impurities present in the raw materials from such sources in the quantity constituting at least 0,02 frequent./million (mass.), often, at least from 1 to 5 ppm million (mass.), or even 5 ppm million (mass.) or more. In addition, most commercially available aromatic raw materials in the form in which it is put, saturated with water, that is the raw material contains at least 50 ppm million (mass.) water, typically at least 200 ppm million (mass.) water. The method according to the present invention provides an advantageous method of decreasing the quantity of these impurities in the raw materials available from commercial sources aromatic raw materials to an acceptable level.

Alkylating agents that can be used in the method according to the present invention, typically include l the specific organic compounds, containing at least one available alkylating group that can react with alkilirutmi aromatic compound and an alkylating group typically contains from 1 to 5 carbon atoms. Examples of suitable alkylating agents are olefins such as ethylene, propylene, butenes and pentene, alcohols (including monosperma, diatomic alcohols, triatomic alcohols, etc.), for example, methanol, ethanol, propanol, butanol and pentanol, aldehydes, e.g. formaldehyde, acetaldehyde, Propionaldehyde, Butyraldehyde and n-valeric aldehyde, and alkylhalogenide, for example, methyl chloride, ethylchloride, propylchloride, butylchloride, pantellaria and so on.

Preferably the raw material used in the method according to the present invention, represents a benzene and ethylene, and the target reaction product is ethylbenzene.

The alkylation reaction

The main stage alkylation reaction involves contacting alkilirutego aromatic compound with an alkylating agent in the presence of an alkylation catalyst under such conditions that the alkylating agent reacts with alkilirutmi aromatic compound for selective formation of the desired monoalkylation connection. Although the alkylation reaction may occur in the vapor phase, it is often desirable reg is its alkylation conditions so to support alkilirutmi aromatic compound, essentially in the liquid phase. For example, if alkilirutmi aromatic compound includes benzene, alkene includes ethylene, and alkylaromatic compound comprises ethylbenzene, the alkylation conditions, as appropriate, include temperature, comprising from about 50 to about 270°C and a pressure of from about 1000 to about 10000 KPa.

In one of the preferred options the alkylation catalyst includes at least one molecular sieve with an average pore size, metric difficulties which ranges from 2 to 12 (as defined in the patent US 4016218). Suitable molecular sieve with an average pore size include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48. Molecular sieve ZSM-5 is described in detail in the patents US 3702886 and Re. 29948. Molecular sieve ZSM-11 is described in the patent US 3709979. Molecular sieve ZSM-12 is described in the patent US 3832449. Molecular sieve ZSM-22 is described in the patent US 4556477. Molecular sieve ZSM-23 described in the patent US 4076842. Molecular sieve ZSM-35 described in the patent US 4016245. Molecular sieve ZSM-48 is more specifically described in the patent US 4234231.

In another preferred embodiment, the alkylation catalyst comprises at least one molecular sieve of the MCM family-22. In the present description, the expression "molecular sieve of the MCM family-22" (or "the material with which the family MCM-22", or "zeolite family of MCM-22") includes one or more of the following substances:

molecular sieves consisting of standard structural elements of the first degree, which represents the crystalline structural unit corresponding to the structural topology MWW. (Structural cell represents the spatial arrangement of the atoms, and it being surrounded by similar structural cells in three-dimensional space that describes the structure of the crystal. These crystal structures are described in the book Atlas of Zeolite Framework Types, fifth edition, 2001, the contents of which are fully incorporated into the present description by reference.);

molecular sieves consisting of standard crystalline structural elements of the second degree, representing a two-dimensional configuration of said structural cells MWW topology, forming a monolayer thickness of one structural cell, preferably, a thickness in a single structural-cell;

molecular sieves consisting of standard structural elements of the second degree, representing layers of thickness in one or more of the structural cell, and the layer thickness of more than one structural cell obtained by folding, sealing or binding at least two monolayers thick one structural cell. The folding of such structural cell battery (included) is tov second-degree can have a regular order, uneven order, random order, or any combination thereof; and

molecular sieves consisting of any regular or random two-dimensional or three-dimensional combination of structural cells corresponding structural topology MWW.

Molecular sieves of the MCM family-22 include molecular sieves, x-ray diffraction pattern which comprises peaks interplanar distances components 12,4±0,25, 6,9±0,15, 3,57±0,07 and of 3.42±0.07 Angstrom. X-ray diffraction data used to describe the material, get any of the standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation detector and connected to it by computer, intended for data collection.

Materials collection MCM-22 include MCM-22 (described in patent US 4954325), PSH-3 (described in patent US 4439409), SSZ-25 (described in patent US 4826667), ERB-1 (described in European patent 0293032), ITQ-1 (described in US 6077498), ITQ-2 (described in international patent publication WO 97/17290), MCM-36 (described in patent US 5250277), MCM-49 (described in patent US 5236575), MCM-56 (described in the patent US 5362697), UZM-8 (described in patent US 6756030) and mixtures of the above.

In an additional preferred embodiment, the alkylation catalyst comprises one or more porous molecular sieve, the indicator is Otradnensky which is less than 2. Suitable porous molecular sieves include zeolite beta, zeolite Y, ultrastable (with respect zeolite Y (USY), dealuminated zeolite Y (Deal. Y), mordenite, ZSM-3, ZSM-4, ZSM-18 and ZSM-20. Zeolite ZSM-14 described in the patent US 3923636. Zeolite ZSM-20 described in the patent US 3972983. Zeolite beta is described in the patent US 3308069 and Re. 28341. Ultrastable (with respect molecular sieve Y (USY) with low sodium described in patents US 3293192 and 3449070. Dealuminated zeolite Y (Deal. Y) can be obtained by the method described in patent US 3442795. Zeolite UHP-Y described in the patent US 4401556. Mordenite is a natural material, but it is also available in synthetic forms, such as tea-mordenite (i.e. synthetic mordenite obtained from the reaction mixture, including tetraethylammonium as a template). The tea-mordenite is described in patents US 3766093 and 3894104.

Preferred molecular sieves for the alkylation reaction include zeolite beta, ZSM-5 molecular sieves family MCM-22.

The above molecular sieves can be used as catalysts for the alkylation without any binder or matrix, i.e. in the so-called samosatenus form. Alternatively, the molecular sieve can be combined with another material resistant to the temperatures and other conditions employed in the alkylation reaction. Such materials include active and inactive mother of the crystals and synthetic or natural zeolites, as well as inorganic materials such as clay and/or oxides, such as alumina, silica, silica - alumina, zirconium oxide, titanium oxide, magnesium oxide or mixtures of these and other oxides. The latter may be natural or may be in the form of a gel-like precipitation or gels including mixtures of silica and metal oxides. Clay can also be used in conjunction with a binder oxide type in order to modify the mechanical properties of the catalyst or to facilitate its production. Use in conjunction with the molecular sieve material, that is connected to it or present during synthesis of the material, which itself has catalytic activity, can change the degree of conversion and/or selectivity of the catalyst. Inactive materials suitably serve as diluents to control the degree of conversion so that products can be obtained economically and in the correct order, without the use of other methods of speed control of the reaction. Such materials can be entered in natural clays, such as bentonite and kaolin, to improve the crushing strength of the catalyst when working in an industrial environment, and they serve as a binder or matrix of the catalyst. The relative ratio of the molecular sieve with the inorganic oxide matrix vary widely, in this case, the contents of the sieve is from about 1 to about 90 wt. -%, usually, specifically if the composite is obtained in the form of beads, from about 2 to about 80% of the mass. based on the weight of the composite.

The alkylation catalyst may be a single layer of catalyst, usually, a fixed layer, located in the alkylation reactor. However, to improve the selectivity of the reaction in relation to mono-alkylated product, the alkylation catalyst is usually divided into several layers connected in series catalyst, and, essentially, all alkilirutmi aromatic compound fed to the first catalyst layer, and an alkylating agent are served separately between layers.

Reaction of TRANS-alkylation

Output stream alkylation reaction, in addition to the desired monoalkylamines product and unreacted alkilirutego aromatic compounds, will inevitably contain a certain amount polyallylamine aromatic compounds. Thus, the output stream alkylation reaction are referred to the Department of product, typically a sequence of distillation columns, which serves not only to remove unreacted alkylated aromatic compounds and target monoalkylamines product, but it was the same separates polyallylamine connection. On the main stages of the reaction of TRANS-alkylation polyallylamine substance is then applied to the reactor TRANS-alkylation, installed separately from the alkylation reactor, which receive monoalkylamines product by the reaction between polyalkylene connections and an additional amount of aromatic compounds in the presence of a catalyst TRANS-alkylation. Typically, the reactor TRANS-alkylation works under such conditions that polyallylamine aromatic compounds and alkilirutmi aromatic compound, at least, mainly located in the liquid phase.

For example, suitable conditions for the implementation of liquid-phase TRANS-alkylation of benzene with positivesale may include temperature, comprising from about 150 to about 260°C, a pressure of 7000 KPa or less, MCOS based on the weight of the whole liquid raw materials into the reaction zone comprising from about 0.5 to about 100 h-1, and the molar ratio of benzene to polietileno constituting from about 1:1 to about 30:1.

The catalyst TRANS-alkylation may include one or more molecular sieves described above in relation to the alkylation catalyst, such as material collection MCM-22, and it can be used with a binder or matrix, or without such. However, usually, although as kata is isator TRANS-alkylation, and the alkylation catalyst include aluminosilicate molecular sieves, the molar ratio of silicon oxide to aluminum oxide in the catalyst TRANS-alkylation is less than the alkylation catalyst. In addition, the catalyst TRANS-alkylation usually contains a molecular sieve, the pore size than the pore size of the alkylation catalyst.

Typically, the catalyst TRANS-alkylation includes molecular sieve, the index of difficulty is less than 2, specifically, molecular sieve selected from the group comprising zeolite beta, zeolite Y, ultrastable (with respect zeolite Y (USY), dealumination molecular sieve Y (Deal. Y), rare earth zeolite Y (REY), mordenite, ZSM-3, ZSM-4, ZSM-5, ZSM-11, ZSM-18, ZSM-20, and mixtures of the foregoing.

Processing raw materials

As described above, fresh alkilirutmi aromatic raw materials used in the method according to the present invention usually contains substantial amounts of catalyst poisons, specifically, reactive nitrogen compounds, and preaction-able nitrogen compounds, and water. Therefore, usually aromatic feedstock is subjected to a pretreatment in order to reduce the water content and the removal of at least some catalytic poisons. Such pre-processing typically involves the transmission alkilirutego aroma is practical raw material through a zone of dehydration, for example, the installation for the removal of volatile substances, installed before or after the layer of adsorbent such as clay, resin or molecular sieve, usually at or at about the environmental conditions such as temperature, ranging from about 25 to about 250°C, preferably from about 25 to about 150°C and a pressure of from about 50 to about 10000 KPa.

Next alkilirutmi aromatic feedstock is passed through the column fractionation, with the aim of separating the aqueous phase and the hydrocarbon phase in the composition of the stream of light fractions. Dry aromatic raw materials emit in a stream of heavy fractions, containing not more than 100 ppm million of water. It was found that some catalyst poisons are removed from the system together with the aqueous phase.

However, while the adsorption pre-treatment and fractionation are effective ways of removing many harmful impurities found in alkiliruya aromatic raw materials, it was found that even after such pre-processing the content of impurities, specifically, reactive nitrogen compounds is quite high, although in some cases impossible to detect them, which leads to a significant reduction of the service life of the catalyst, specifically, the alkylation catalyst, permitting the contacting aromatic with the earth with the total amount with the catalyst without additional processing. Thus, in the method according to the present invention, all fresh aromatic raw materials after adsorption pre-treatment or without such, serves on the catalyst TRANS-alkylation, so that the latter serves not only to increase the degree of conversion polyallylamine aromatic by-products in additional monoalkylamines product, but also as the reaction of the protective layer to further reduce the content of impurities in the raw materials, usually at least 10%, for example at least 20%, such as at least 30%.

Catalysts TRANS-alkylation as the reaction of the protective layer necessarily leads to some poisoning of the catalyst TRANS-alkylation, but as a catalyst for TRANS-alkylation can be chosen in such a way that it had a low molar ratio of silicon oxide to aluminum oxide and a larger pore size compared to the alkylation catalyst, it is usually more effective as a protective layer, for example, than known configurations in which the applied layer of the alkylation catalyst as a protective layer. Moreover, the supply of fresh feed benzene to the catalyst TRANS-alkylation allows you to maintain in installing the TRANS-alkylation mountain is to a higher molar ratio of benzene to polyalkylthiophenes aromatic compounds. This allows a reduced formation of by-products, increased the degree of conversion in a single pass and a higher thermodynamic yield of the target monoalkylamines product. With an increased degree of conversion polyallylamine aromatic compounds in a single pass, speed recirculatory decrease as the number of products requiring distillation. In General, therefore, also reduces energy costs. Typically, in the method according to the present invention, the molar ratio of benzene to polyalkylthiophenes aromatic compounds fed to the reactor TRANS-alkylation is at least 1:1, for example, from about 1:1 to about 30:1 from 1:1 to 15:1, and from 1:1 to 10:1.

In one of the preferred options in method apply two separate coats of catalyst TRANS-alkylation, which can alternately switch between an operating mode in which the catalyst bed operates as a TRANS-alkylating layer and the reaction of the protective layer, and a non-working mode, in which the catalyst regenerate or replace. Thus, one of the layers will always be in operation, at a time when the second layer is not working. In addition, these layers can operate in serial or parallel mode.

One of the preferred variants of the method according to N. the present invention, in which alkilirutmi aromatic compound is a benzene and the alkylating agent is a dilute stream of ethylene is shown in figure 1.

As shown in figure 1, the fresh benzene raw material containing impurities, for example, nitrogen impurities, served by lines 11 and sent to the adsorption unit 12, including the adsorbents on the basis of molecular sieves and/or other materials for processing, including, for example, clay and/or resin designed to remove at least part of the impurities from raw materials. Processed fresh benzene feedstock is sent to the reactor TRANS-alkylation 13, which also receives polietileno (HSE) as a stream of light fractions 14 from the column 15 for distillation, the FPU. The reactor TRANS-alkylation 13 contains one or more layers of catalyst TRANS-alkylation, such as zeolite beta, zeolite Y, ultrastable (with respect zeolite Y (USY), dealumination molecular sieve Y (Deal. Y), rare earth zeolite Y (REY), mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, and mixtures of the above, and the reactor 13 works under such conditions that the benzene and the HSE are mainly in the liquid phase and react with each other to form ethylbenzene. The reactor TRANS-alkylation 13 also serves as a protective layer to remove at least part of the reactive nitrogen and other impurities in the Yessei, contained in fresh benzene raw material.

The exit stream of the reactor TRANS-alkylation 13 consists mainly of unreacted benzene, containing a reduced amount of impurities, etilbenzene product, HSE and heavy compounds coming from the reactor 13 through line 16. The exit stream in line 16, is fed into the column 17 distillation of benzene, in which the unreacted benzene is separated from the exit stream as stream 18 light fractions. Then the stream 18 of benzene serves in conjunction with the thread 19 of the ethylene feedstock to the alkylation reactor 21, containing several consecutive layers of alkylation catalyst, such as zeolite family of MCM-22. The reactor alkylation is carried out at such conditions that the benzene is mainly in the liquid phase and reacts with the ethylene raw material with the formation of ethylbenzene in conjunction with a number of HSE.

The output stream of the alkylation reactor 21 is composed mainly of unreacted benzene, the end of ethylbenzene and a quantity of the FPU. Output stream alkylation reaction out of the reactor 21 through line 22 and enters the column 17 distillation of benzene. In column 17 of unreacted benzene is removed from the exit stream of the alkylation and sent as part of the stream 18 lung fractionate in the reactor 21, and the thread 23 heavy fractions consisting mainly of the end of ethylbenzene and HSE leave. The flow of heavy fractions refer to the column 24 ethylbenzene distillation, in which the final ethylbenzene allocate as stream 25 light fractions, while the thread 26 of heavy fractions refer to the column 15 of the distillation, the FPU. In column 15 of the distillation, the FPU, the FPU is separated from the heavy fraction as stream 14 light fraction and the heavy fraction is discharged as stream 27 waste.

In contrast, the previously described conventional process of obtaining ethylbenzene shown in figure 2, and to specify the shared components apply the same numerical designation as in figure 1. Thus, figure 2 fresh thread 11 of benzene after passing through the adsorption installation 12, together with the raw output stream 16 installation TRANS-alkylation, served in column 17 of the distillation of benzene. Part of the flow 18 easy benzene fraction still containing impurities contained in raw materials (i.e. reactive nitrogen compounds and other impurities), sent to the reaction protective layer 31 containing alkylation catalyst. The rest of the thread easy benzene fraction, coming from the column 17 distillation of the benzene, serves as a small stream 32 into the reactor TRANS-alkylation 13.

Although the present invention would be what about the described and shown with reference to specific preferred options, persons skilled in the art will appreciate that the present invention includes variations not necessarily illustrated in the present description. For this reason, in order to determine the true scope of the present invention, reference should be made only on the enclosed claims.

1. The way alkylation alkilirutego aromatic compounds with getting monoalkylamines aromatic compounds, comprising the following stages:
A) the direction of the first flow of raw materials, including fresh alkilirutmi aromatic compound in a first reaction zone comprising catalyst TRANS-alkylation;
B) the direction of the second flow of raw materials, including polyalkylene aromatic compounds specified in the first reaction zone;
(B) contacting the above first and second flows of raw materials with the specified catalyst TRANS-alkylation specified in the first reaction zone under conditions suitable for the implementation of the reaction of TRANS-alkylation between these polyalkylbenzene aromatic compounds and specified alkilirutmi aromatic compound, essentially in the liquid phase, with obtaining the specified monoalkylamines aromatic compounds;
G) removing from the specified first reaction zone of the first output stream comprising the non-is reacted alkilirutmi aromatic compound and a specified monoalkylamines aromatic compound;
D) the specified direction of the first exhaust system for fractionation to separate the specified first exit stream at the first light fraction comprising the specified unreacted alkilirutmi aromatic compound, and the first heavy fraction comprising the specified monoalkylamines aromatic compound;
E) isolation monoalkylamines aromatic compounds from the specified first heavy fraction;
W) direction specified first light fraction comprising the specified alkilirutmi aromatic compound, and a third feedstock stream comprising an alkylating agent in the second reaction zone, comprising the alkylation catalyst;
C) contacting the specified first light fraction and a third flow of raw materials with the specified alkylation catalyst specified in the second reaction zone under conditions suitable for the alkylation specified alkilirutego aromatic compounds using the alkylating agent, and receiving the second output stream comprising the specified monoalkylamines aromatic compound, unreacted alkiliruya aromatic compounds and polyalkylene aromatic compounds; and
And the selection monoalkylamines aromatic compounds from the specified second outgoing flux is A.

2. The method according to claim 1, wherein said first flow of raw materials includes one or more impurities, and at least some of these impurities are removed in the specified first reaction zone under contact ().

3. The method according to claim 2, in which these impurities in the composition of the first stream of raw materials include at least 0,02 frequent./million based on the weight of the specified first stream of raw materials.

4. The method according to claim 2, in which these impurities in the composition of the specified first flow of raw materials selected from the group including compounds containing one or more of the following elements: the Halogens, oxygen, sulfur, arsenic, selenium, tellurium, phosphorus, and metals of groups 1 to 12.

5. The method according to claim 2, in which these impurities in the composition of the specified first flow of raw materials include reactive nitrogen compounds.

6. The method according to claim 5, in which remove at least 10% of the mass. these reactive nitrogen compounds.

7. The method according to claim 1, additionally comprising the following stage:
To) the specified direction of the second effluent stream in a fractionation system to separate the specified second exit stream at the second light fraction comprising unreacted alkilirutmi aromatic compound, and a second heavy fraction comprising the specified monoalkylamines aromatic compound and polyalkylene aroma is practical connection moreover, the specified monoalkylamines aromatic compound can be distinguished in stage (C) from the specified second heavy fraction.

8. The method according to claim 7, in which the specified second light fraction comprising unreacted alkilirutmi aromatic compound is directed to the second reaction zone.

9. The method according to claim 1, sometimes additionally comprising the following stages:
H) stopping delivery of these first and second flows of raw materials in the first reaction zone;
A) the direction of the first and second flows of raw materials in the third reaction zone comprising catalyst TRANS-alkylation;
H) contacting the above first and second flows of raw materials with the specified catalyst TRANS-alkylation specified in the third reaction zone under conditions that allow to remove at least a portion of these impurities in a specified first flow of raw materials, and TRANS-alkylation above polyalkylene aromatic compounds specified alkilirutmi aromatic compound in order to obtain the specified monoalkylamines aromatic compounds; and
R) the replacement or regeneration of the catalyst TRANS-alkylation specified in the first reaction zone.

10. The method according to claim 1, wherein said catalyst TRANS-alkylation comprises a molecular sieve selected from the group comprising zeoli the beta, zeolite Y, ultrastable (with respect zeolite Y (USY), dealumination molecular sieve Y (Deal. Y), mordenite, ZSM-3, ZSM-4, ZSM-18 and ZSM-20.

11. The method according to claim 1, wherein said alkylation catalyst comprises a molecular sieve selected from the group comprising zeolite beta molecular sieve, the index of difficulty is from about 2 to about 12, and a molecular sieve of the MCM family-22.

12. The method according to claim 11, wherein said alkylation catalyst comprises a molecular sieve of the MCM family-22, selected from the group comprising MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, ITQ-30, MCM-36, MCM-49, MCM-56, UZM-8, and mixtures of the foregoing.

13. The method according to claim 1, in which the conditions specified in the first reaction zone during the specified contact (stage b) such that allow you to maintain your desired polyalkylene aromatic compound and a specified alkilirutmi aromatic compound, essentially in the liquid phase, or the conditions specified in the second reaction zone during the stage of contacting (C) such that allow you to maintain your desired alkilirutmi aromatic compound, essentially in the liquid phase.

14. The method according to claim 2, in which the specified alkilirutmi aromatic compound includes benzene or naphthalene.

15. The method according to claim 1, wherein said alkylating agent comprises at least one of the following is exist: ethylene, propylene, 1-butene, 2-butene and isobutene.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method for transalkylation of a crude stream containing C7, C9, C10 and C11+ aromatic hydrocarbons to obtain a transalkylation product stream with high concentration of C8 aromatic compounds compared to concentration thereof in the crude stream. The method involves bringing a crude stream, in transalkylation conditions, into contact with a catalyst containing aggregated material UZM-14, which contains globular aggregates of crystallites, having a mordenite-type skeleton with channels of 12-member rings, mesopore volume of at least 0.10 cm3/g and average length of crystallites parallel to the direction of channels of 12-member rings equal to or less than 60 nm.

EFFECT: disclosed method enables to obtain xylenes with high output, wherein the catalyst is active and stable during the transalkylation process.

10 cl, 6 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for transalkylation of benzene with polyalkyl benzenes on a zeolite-containing catalyst to obtain ethylbenzene or isopropylbenzene. The method is characterised by that the polyalkyl benzenes used are diethyl benzenes or diisopropyl benzenes; the process is carried out in a section reactor. The main benzene stream is fed into the first section of the reactor with the ratio of benzene to diethyl benzene in the first section of the reactor equal to 9:1 or 10.5:1, or 15:1 or 16.5:1 or 18:1 or the ratio of benzene to diisopropyl benzene in the first section of the reactor equal to 7.2:1 or 9.6:1. Polyalkyl benzenes are fed into each section of the reactor having a zeolite catalyst bed, and an amount of benzene, which is such that the total weight ratio of benzene to polyalkyl benzene in the reactor is equal to 1:1-6:1, is fed into each section of the reactor having a zeolite catalyst bed, except the first section.

EFFECT: use of the present invention prolongs catalyst life, increases conversion of polyalkyl benzene and selectivity with respect to the end product.

4 cl, 14 ex, 2 tbl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to transalkylation catalysts. Described is a catalyst for transalkylation of benzene with diethylbenzenes in form of cylindrical granules with a regular shape, which contains zeolite Y in an acidic H+ form, which contains 100 wt % zeolite with degree of substitution of Na+ ions with H+ ions of not less than 0.95 and more than 80% of volume of the transported pores of the granules is made up of pores with diameter larger than 100 nm. Described is a method of producing said catalyst, which involves preparation of cylindrical granules with a regular shape, involving drying and calcination of the granules, wherein to obtain the catalyst, zeolite NaY, which is granulated with binding material and has high phase purity, wherein more than 80% of the volume of the transported pores is made up of pores with a diameter larger than 100 nm, is successively treated with aqueous solutions of ammonium salts with concentration of 20-25 g/dm3 (with respect to NH4+) with the ratio of mass of granules to volume of the solution of (1:6)-(1:7) and temperature of 80-90°C for 1.0-1.5 hours, alternating three or four steps of said treatment with two or three intermediate calcinations, respectively, at temperature of 540-600°C for 3-4 hours, drying at temperature of 120-150°C for 3-4 hours and calcining for 3-4 hours at temperature of 540-600°C. Described is a method for transalkylation of benzene with diethylbenzenes, involving reaction of benzene with diethylbenzenes in liquid phase at high temperature and pressure using said catalyst, wherein content of water in the material is less than 200 ppm.

EFFECT: high conversion of diethylbenzenes.

3 cl, 2 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: method involves: a. continuously feeding benzene and a mixture containing paraffin and olefin into at least one alkylation zone under alkylation conditions, involving presence of an amount of an alkylation catalyst sufficient for catalysis, to obtain an alkylation product containing alkyl benzene, dialkyl benzenes and unreacted benzene; the alkylation catalyst is selected from a group consisting of zeolites, acidified refractory oxides and mixtures thereof. Then b. separating benzene from the alkylation product to obtain a fraction rich in benzene, at least a portion of which is taken for recycling at step (a) and a fraction containing alkyl benzene, paraffin and dialkyl benzene, and essentially not containing benzene. Further c. separating paraffin from said fraction essentially not containing benzene to obtain a fraction rich in paraffin and a fraction containing alkyl benzene and dialkyl benzene and essentially not containing paraffin. Further d. separating alkyl benzene from said fraction not containing paraffin to obtain an alkyl benzene fraction and a fraction of heavy hydrocarbons containing dialkyl benzenes. Then e. feeding benzene and at least a portion of the fraction of heavy hydrocarbons into at least one transalkylation zone, where molar ratio of benzene and dialkyl benzene is at least equal to 20:1, preferably from 30:1 to 60:1. Further f. keeping said at least one transalkylation zone under transalkylation conditions, involving an amount of a solid transalkylation catalyst efficient for catalysis, for obtaining a transalkylation product in which at least 20 mol % dialkyl benzene in the portion of material fed into said reaction zone is converted to alkyl benzene. Further g. fractionation of at least a portion of the transalkylation product to obtain a low-boiling point fraction rich in benzene, and a high-boiling point fraction containing alkyl-substituted benzene. Then h. feeding at least a portion of the fraction rich in benzene into at least one transalkylation zone as at least a portion of benzene for said reaction zone; and i. feeding at least a portion of the high-boiling point fraction from step (g) to step (b).

EFFECT: use of the present method enables to efficiently maintain high molar ratio of benzene and dialkyl benzene in order to increase catalyst stability.

10 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: xylene isomer process involves (versions): (a) contacting the raw stock containing aromatic compounds C9 with the catalyst containing unsulphurised mordenite impregnated with metal oxide of group VIB to produce the intermediate flow containing xylene isomers; (b) separating, at least, parts of xylene isomers from the intermediate flow and (c) delivering the intermediate flow back to the raw stock from the stage (a) that have been impoverished with xylene isomers prepared at the stage (b). There is also disclosed invention concerning versions of xylene isomerisation process for the raw stock containing aromatic compounds C9.

EFFECT: application of specified process ensures high conversion of aromatic compounds C9 and methylethylbenzol, and also to high ratios of xylene isomers to ethylbenzol, xylene isomers to aromatic compounds C9, xylene isomers to aromatic compounds C10, trimethylbenzol to methylethylbenzol, benzol to ethylbenzol in conversion products.

15 cl, 3 dwg, 6 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to catalyst compositions containing zeolite and inorganic binding agent with particular mechanical characteristics porosity and characteristics, and available as a catalysts in industrial fixed-bed catalytic reactors. There is disclosed composition containing zeolite and inorganic binding agent, where zeolite has crystal structure with holes formed by 12 tetrahedrons, while binding agent is aluminium γ-oxide. Herewith the composition described above is characterised by pore space derived from summing up mesoporous and macroporous components found in the specified catalyst composition, exceeding or equal 0.7 cm3/g, and at least 30% of said pore space volume consist of pores of diameter exceeding 100 nanometres. Additionally there are disclosed method of preparing catalyst composition specified above, method of aromatic hydrocarbon transalkylation involving aromatic hydrocarbon contacting to one or more polyalkylated aromatic hydrocarbon with the said catalyst composition added. Besides, there is disclosed method of preparing monoalkylated aromatic hydrocarbons involving: a) aromatic hydrocarbon contacting to C2-C4- olefin with acid catalyst added in such alkylation conditions, that reaction is enabled, at least partially in liquid phase, b) product separation to fraction containing aromatic hydrocarbon, fraction containing monoalkylated aromatic hydrocarbon, fraction containing polyalkylated aromatic hydrocarbons, and fraction containing heavy aromatic hydrocarbons, c) fraction containing polyalkylated aromatic hydrocarbons contacting to aromatic hydrocarbon with the said catalyst added, in such transalkylation conditions, that reaction is enabled, at least partially in liquid phase.

EFFECT: improved catalyst performance, both concerning its durability and productivity, improved mechanical characteristics of the catalyst, such as crushing strength and abrasion resistance, ensured high yield and high efficiency of transalkylation.

40 cl, 1 tbl, 6 dwg, 4 ex

The invention relates to a method for conversion of heavy aromatic hydrocarbons to lighter aromatic compounds such as benzene, by contacting the fraction WITH9+ aromatic hydrocarbons and toluene above the first catalyst containing a zeolite having an index of permeability of 0.5 - 3, and a hydrogenation component and a second catalyst composition comprising a zeolite with an average size of pores having an index of permeability 3 - 12, the ratio of silica to alumina of at least 5, this reduces the number or preventing the formation of jointly boiling compounds

The invention relates to an improved method for the disproportionation of toluene comprising processing the catalyst is a molecular sieve selected from the group comprising ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, preferably ZSM-5, selectivities on paraxylene organosilicon agent and contacting a reaction stream containing toluene, with the specified catalyst at a temperature 350-540oWith the pressure 100-35000 KPa, space velocity of the raw material is 0.1-20 h-1and the molar ratio of hydrogen to hydrocarbon of 0.1-2.0, characterized in that as selectivities on paraxylene organosilicon agent use volatile organosilicon compound selected from the class of siloxanes, silanes or disilanes, and handling of the catalyst specified selectivities agent is carried out by feeding selectivities agent, taken in an amount of 0.1-50 wt.% by weight of toluene, simultaneously with the filing of the reaction stream containing toluene, for up to 300 h to obtain in a single pass product containing at least 90% of paraxylene by weight of the component WITH8when the conversion of toluene at least 15 wt

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining engine fuel in interval of petrol boiling by benzole alkylation. Invention deals with method of obtaining hydrocarbon product in interval of petrol boiling, which has concentration of benzole not more than 1 vol.% and regulated temperature of evaporation, from raw material, which consists of reforming product, with concentration of benzole at least 20 wt %, which includes reforming product alkylation in reactor of alkylation in presence of zeolite catalyst MWW at least in two immobile catalytic layers in mode of single passing in liquid phase by alkylation agent.

EFFECT: high level of benzole and olefin conversion.

10 cl, 10 dwg, 15 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining monoalkylated aromatic compound, in which: aromatic raw material and olefin compound are passed into reactor of alkylation, with reactor of alkylation including catalyst, which contains zeolite with molar ratio of silicon dioxide to aluminium oxide being less than 8, and rare earth element, embedded into zeolite lattice; amount of rare earth element constitutes more than 16.5 wt % in terms of zeolite, the remaining part includes cations of alkali, alkali earth elements, nitrogen compounds or their mixtures, rare earth elements are involved into exchange to such a degree that molar ratio of rare earth element to aluminium is within the range 0.51-1.2; the remaining cation-exchange ions are represented by cations, selected from group, consisting of alkali, alkali earth elements, nitrogen compounds or their mixture, thus forming output flow. Output flow is directed to operation of separation, thus forming flow of aromatic compounds, flow of products, containing monoalkylated aromatic compound, and flow of non-productive alkylated aromatic compounds.

EFFECT: method makes it possible to increase quality of alkylbenzene by increase of alkylbenzene linearity.

9 cl, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: disclosed is a method of producing a monoalkyl aromatic compound which involves contacting, in alkylation reaction conditions, material which contains an alkylatable aromatic compound and an alkylating agent. Contacting is carried out in the presence of a catalyst. The catalyst is an EMM-13 type molecular sieve The EMM-13 catalyst used in the method is a molecular sieve having a frame structure of tetrahedral atoms linked by bridges of oxygen atoms, wherein a tetrahedral atomic frame is defined by a structural unit, having specific atomic coordinates given in the claim.

EFFECT: high output of the end product while reducing formation of by-products.

16 cl, 6 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: method includes supplying diluted flow of ethylene, which contains between 5 and 50 wt % of ethylene; supplying benzol flow, containing,at least 3 wt % of toluol and, at least, 20 wt % of paraffins; interaction of diluted ethylene flow and benzol flow with catalyst of alkylation, which contains UZM-8; and conversion of, at least, 20% of benzol in raw material flow into alkylbenzol. Invention also relates to device for alkylation of benzol with ethylene.

EFFECT: application of claimed invention makes it possible to eliminate application of reformate by fractionation column, which leads to essential exploitation and financial savings.

10 cl, 3 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to catalytic processes for producing cumene. Described is a method of prolonging stable operation of a catalyst, which contains a hydrogenating component and an alkylating component, in a reaction for producing cumene by hydroalkylation of benzene with acetone, involving layer by layer arrangement of the hydrogenating and alkylating components in the catalyst, wherein the hydrogenating component is placed first on the path for feeding material, the hydrogenating component being copper chromite and/or copper oxide, which is promoted by metals selected from: manganese, gallium, chromium, rare-earth metals, with weight ratio of copper to promoter metals equal to (4.0-6.0):1; the alkylating component is placed second on the path for feeding material, the alkylating agent being micro-mesoporous dealuminated MOR or BEA or FAU, wherein the amount of the hydrogenating component in the catalyst is equal to 15-35 wt % of the total amount of the catalyst. Described is a method of producing cumene by hydroalkylation of benzene with acetone, which is characterised by that hydroalkylation is carried out in a flow reactor with a fixed catalyst bed at 150-250°C, mass flow rate of feeding material of 0.3-7 h-1, molar ratio of benzene to acetone of 4:1-9:1, molar ratio of hydrogen to acetone of 1:1-10:1, and pressure of 0.1-3 MPa, using the catalyst described above.

EFFECT: longer time for stable operation of the catalyst.

5 cl, 1 tbl, 19 ex

FIELD: chemistry.

SUBSTANCE: invention relates to transalkylation catalysts. Described is a catalyst for transalkylation of benzene with diethylbenzenes in form of cylindrical granules with a regular shape, which contains zeolite Y in an acidic H+ form, which contains 100 wt % zeolite with degree of substitution of Na+ ions with H+ ions of not less than 0.95 and more than 80% of volume of the transported pores of the granules is made up of pores with diameter larger than 100 nm. Described is a method of producing said catalyst, which involves preparation of cylindrical granules with a regular shape, involving drying and calcination of the granules, wherein to obtain the catalyst, zeolite NaY, which is granulated with binding material and has high phase purity, wherein more than 80% of the volume of the transported pores is made up of pores with a diameter larger than 100 nm, is successively treated with aqueous solutions of ammonium salts with concentration of 20-25 g/dm3 (with respect to NH4+) with the ratio of mass of granules to volume of the solution of (1:6)-(1:7) and temperature of 80-90°C for 1.0-1.5 hours, alternating three or four steps of said treatment with two or three intermediate calcinations, respectively, at temperature of 540-600°C for 3-4 hours, drying at temperature of 120-150°C for 3-4 hours and calcining for 3-4 hours at temperature of 540-600°C. Described is a method for transalkylation of benzene with diethylbenzenes, involving reaction of benzene with diethylbenzenes in liquid phase at high temperature and pressure using said catalyst, wherein content of water in the material is less than 200 ppm.

EFFECT: high conversion of diethylbenzenes.

3 cl, 2 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a product containing alkyl aryl sulphonate, involving the following steps: (a) contacting an alkyl aromatic hydrocarbon with sulphur trioxide at 25-120°C and pressure of up to 50 kPa to obtain a first liquid product containing alkyl aryl sulphonic acid and a gaseous effluent stream containing sulphur oxides, sulphuric acid and alkyl aryl sulphonic acid; (b) separating the first liquid product from the gaseous effluent stream; (c) purifying the gaseous effluent stream to obtain a cleaned gaseous stream and a second liquid product; (d) returning the second liquid product to the first liquid product obtained after the separation step (b) to obtain a third liquid product containing alkyl aryl sulphonic acid, followed by neutralisation thereof; wherein the alkyl aromatic hydrocarbon is obtained by contacting an aromatic hydrocarbon with an olefin under alkylating conditions, and said olefin is obtained by dehydrogenation of a Fischer-Tropsch derived paraffin material.

EFFECT: efficient and environmentally acceptable method of obtaining a product containing alkyl aryl sulphonic acids, which does not have significant negative effect on properties of the end alkyl aryl sulphonates.

7 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: system comprises a first a first reactor (14) an inlet, an outlet and a reaction zone, where the first reactor is capable of receiving a stream (12) of material containing oxygenates and hydrocarbons, converting a portion of the oxygenates to light olefins and alkylating aromatic compounds. The light olefins and the alkyl aromatic compounds are included in a first effluent stream (15). A separator system (18) in fluid connection with the outlet of the first reactor (14) for obtaining the first effluent stream (15) of the first reactor (14) and for forming a first product stream (20) containing a C3 olefin, a second stream (24) containing C7 aromatic compounds and a third stream (26) containing C8 aromatic compounds. The system further includes a first line connecting the separator (18) to the inlet of the first reactor (14) for conveying the second stream (24) to the first reactor (14). The system includes a second line in fluid connection with the separator system (18) for conveying the C3 olefin to a propylene recovery unit (56). The system includes a third line in fluid connection with the separator system (18) for conveying the C8 aromatic compounds to a xylene separating unit (30) and a second reactor (40) for obtaining a stream (28 and 29) of material containing C6+ aromatic hydrocarbons form the separator system (18) and subjecting the streams (28, 29) of material to conditions for transalkylating the C6+ aromatic hydrocarbons to form an effluent stream (46) rich in C8 hydrocarbons.

EFFECT: use of the present method enables to obtain xylenes together with propylene from methanol.

7 cl, 2 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a linear monoalkylaromatic compound with controlled concentration of 2-phenyl isomers and very low colour index after sulphonation, involving use of a catalyst system based on highly stable solid catalysts. The alkylation process is carried out with a catalyst which enables to obtain a linear alkylaromatic compound with minimum content of 2-phenyl isomers, which constitutes 20 wt %, contains MOR type zeolite, from 0.01 to 0.20 wt % of at least one metal selected from a group consisting of Li, Na, K, Mg or Ca, with maximum Na content of 0.01%, and from 0 to 0.5 wt % of at least one metal selected from a group consisting of Ti, Zr and Hf, wherein the catalyst, which enables to obtain at most 20 wt % 2-phenyl isomers, also contains FAU type zeolite, from 0.5 to 2 wt % of at least one metal selected from a group consisting of Li, Na, K, Mg or Ca, and rare-earth metals in amount of: from 4.5 to 10 wt % La, from 1.2 to 4 wt % Ce, from 0.5 to 1.5 wt % Pr and from 2 to 3 wt % Nd.

EFFECT: high activity and high selectivity with respect to linear monoalkylated compounds.

19 cl, 8 ex, 28 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: described is a continuous method for monoalkylation of an aromatic compound of an aliphatic raw material containing an aliphatic olefin with 8-18 carbon atoms per molecule, to obtain a linear arylalkane without excess skeletal isomerisation of the alkane group of the arylalkane, which is carried out using at least 3 reaction zones connected in series, each containing a solid alkylation catalyst, cooling the output stream between the reaction zones, each of said reaction zones being provided with a portion of fresh aliphatic raw material such that the Reaction Zone Delta T in each reaction zone is less than 15°C. Molar ratio of the total amount of the aromatic compound to the olefin is less than 20:1.

EFFECT: alkylation product has the desirable linearity and low amount of dimmers, dealkylated compounds and diaryl compounds even when low molar ratio of aromatic compound to olefin is used.

10 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing alkylbenzenes of general formula , where R1=H: R2=Et, i-Pr or R1R2=-CH2-CH2-CH2-. The method involves hydrogenating styrene with hydrogen gas in the presence of a catalyst, followed by separation of end products, and is characterised by that styrene or derivatives thereof selected from α-methyl styrene or indene is subjected to hydrogenation, and the catalyst used is nickel nanoparticles obtained by reducing nickel (II) chloride with sodium borohydride in situ and the process is carried out at atmospheric pressure of hydrogen in a medium of isopropanol at temperature of 55-65°C for 4-6 hours.

EFFECT: use of the present method simplifies production of compounds of the disclosed structural formula.

1 cl, 3 ex

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