A method of producing benzene, toluene, ortho - and paraxylene

 

(57) Abstract:

Usage: petrochemistry. The inventive products: benzene BF C6H6the output of 14.2 and 14.6%; toluene BF C7H8the output of 22.2 - 23.3% of o - and p-xylenes BF C8H10the output of 6.0 - 8.9 per cent. Reagent: C3-C4-alkanes. Catalyst: Zn or Ga-containing zeolite ZSM-8. Process conditions: reactor unit consisting of a cascade of series-connected 3 - 4 reactor; 400 - 600°C. recycling the products isolated from contact m-xylene fraction in the latter in the course of the reaction the reactor, the time of contact in the last reactor 0,3 - 1,8 C. 1 C.p. f-crystals, 2 ill., 8 table.

The invention relates to the field of petrochemical synthesis, more specifically to the production of benzene, toluene, o - and p-xylenes.

The main method for industrial preparation of these hydrocarbons is currently the catalytic reforming of gasoline. The process is carried out at a temperature of 480-520aboutC, hydrogen pressure, 7-25 at. In this process, m-, o - and p-xylenes is obtained in equilibrium. To obtain the o - and p-xylenes uses a process of isomerization of m-xylene fraction on platinumiridium catalyst. Disadvantages of the process are definiteley aromatic hydrocarbons due to the presence of paraffin hydrocarbons with similar boiling points, the use of different catalysts in catalytic reforming and isomerization of m-xylene fraction.

An alternative method for obtaining aromatic hydrocarbons may be getting from gaseous hydrocarbons3-C4where resources are great and the use of insufficiently qualified.

The known method of synthesis of benzene, toluene, o - and p-xylene from a hydrocarbon WITH3-C4when the temperature 482-537aboutWith a minimum working pressure of 9105PA and space velocity 2H-1(probe 5) using as catalysts for various high-silica zeolites of type ZSM promoted various metals (zinc, gallium). The process is carried out in a cascade of series-connected reactors heated reaction products between the reactor with continuous catalyst regeneration. The main disadvantage of this method is relatively low, the outputs of benzene, toluene, o - and p-xylenes due to the formation of m-xylene, ethyl benzene and aromatics WITH9+.

The closest in technical essence is an improved method of producing aromatics from hydrocarbons WITH3- aboutAnd pressure of 5-7 at. The total residence time of the raw material mixture in the reaction zone 6-7 C. In the reaction of dehydrocyclization is obtained a mixture of products and unreacted propane (stream 7) which, passing through the condenser 8 and the separator 9, is divided. light gases and H2in accordance with the balance returned to recycling (stream 4), and the liquid phase separated in a system of fractional columns according to Fig.1. Part of the separated benzene or toluene (up to 8 mol.% for hydrocarbons) is returned in recycling. The conversion of propane to aromatics in the recycling 6 wt.% benzene was 66%. Without recycle benzene conversion of propane was 60%. Because ER N 0230655 not presents the material balance for the products, the authors have reproduced this patent in the reaction of dehydrocyclization propane high purity recycle 6 mol.% toluene catalyst ZSM-5 module 60 and applied Ga in the amount of 3% at 560aboutAnd the total residence time in the reaction zone 6-7 C. When this monostatic way - low yield of o - and p-xylenes.

The aim of the present invention is to increase the yield of o - and p-xylenes.

This goal is achieved by an improved method for obtaining aromatic hydrocarbons from hydrocarbon WITH3-C4using as catalyst Zn or GA-containing high-silica zeolite catalyst of the ZSM-5 reactor unit consisting of a cascade of series-connected reactors at 400-600aboutC. the resulting reaction products are separated on a recycle fraction of the original alkanes, benzene, toluene, xylene fraction and a fraction WITH9+-aromatics. Dedicated xylene fraction is subjected to separation methods of rectification and adsorption or by using cryogenic techniques. Selected m-xylene fraction (all or part of it) is sent to the recycling in the past during a reactor unit at the time of contact of the stream containing metaxylene fraction with a catalyst 0,3-1,8 C.

The proposed process can be carried out in the reactor block with a fixed catalyst bed, or moving bed of catalyst and with continuous regeneration.

The process of aromatization of hydrocarbonsthe 3-4 consecutive reactors, serves a mixture of hydrocarbons WITH3-C4(thread 1) in the first as the reactor. Hydrocarbons WITH3-C4with products consistently come in second 3 third 4 fourth 5 reactors. The process is carried out on silica zeolite ZSM-5 modified with gallium or zinc, with 400-600aboutAnd the total time of contact 5-7 C. the Catalyst reactors distributed in such a way (with a fixed bed of catalyst), the time of contact in the last reactor of the reactor block was varied in the range of 0.3 to 1.8 C. In the reactor unit with a moving bed of catalyst required contact time stream containing m-xylene fraction is achieved by changing the location of the input m-xylene fraction. m-Xylene fraction resulting from the separation of the xylene fraction in the separation unit xylenes 24 methods of distillation, extraction or cryogenic method, heated and served in the last reactor of the reactor block (stream 6). The reaction products and unreacted3-C4(stream 7) through the cooler-condenser 8 are received in the separator 9, where the separation H2WITH1and C2. Then the reaction products and unreacted3-C4(stream 11) share the aboutC, a pressure of 12 and at reflux 3. Unreacted3-C4(stream 13) is returned to the process, and liquid products (stream 14) is separated by rectification method in the system columns: in column 15 at 80-81aboutWith and reflux the number 10 at the top is selected benzene (stream 16); in the column 18 to the top of the column is taken toluene at 110aboutWith and reflux 3 (stream 19); in column 21 of the cubic product of the column 18 at 138-142aboutWith and reflux 5 are xylenes (stream 22), and from the cube column shows the fraction of aromatic hydrocarbons WITH9+(stream 23). Xylenes (stream 22) is served in the separation unit xylenes (24), which consists of a distillation column, in which the top at 139aboutWith at reflux including 5-10 produce a mixture of isomers of m - and p-xylenes, and Cuba output o-xylene. A mixture of m - and p-xylenes then divide in an adsorption installation using zeolites or cryogenic installation due to a substantial difference in their melting temperatures. Meta-xylene fraction (stream 6) is sent to the recycling and has the following composition, %: ethylbenzene 8, p-xylene 10, o-xylene 10, m-xylene 72.

Unlike the method described in [2], in the proposed method, the target products are benzene, toluene, o - and p-Xylo is currently qualified use, and m-xylene fraction, if necessary, all returns in recycling, but not in the beginning of the process, as in [2], and in the last along the reactor in order to provide the necessary residence time of the stream containing m-xylene fraction, 0,3-1,8 C. the Increase in time up to 1,8 C leads to a reduction of output, total aromatics, increased flatulence and increase in the proportion WITH9+aromatics.

An unexpected effect in the recycling m-xylene fraction in the last reactor was disproportionation of m-xylene at specified conditions with 100% selectivity without increasing content9+-aromatics. In addition, the yield and selectivity (excluding recirculating m-xylene fraction) formation of o - and p-xylenes in the proposed conditions in the 1.6-2.4 times higher than in [2].

The effectiveness of the proposed method is illustrated by the following examples. For ease of comparison process is 100% conversion of propane.

P R I m e R 1 (the prototype). In the reaction block 6 (see Fig.1) at 560aboutC and a pressure of 5 at serves 100 kg/h of high purity propane (stream 1), this comes from the column 21 stream 2, representing the toluene in the amount of 12,55 kg/h, which is suitable for isoamsa zeolite ZSM-5 with a module 60 and deposited gallium in the amount of 3%. In the reaction of dehydrocyclization receive the mixture of reaction products (stream 7), which is directed to the separation according to Fig.1. The portion allocated toluene and re-circulated into recycling.

In table.1 presents the material balance flow. The conversion of propane to aromatics is 66%.

The yield of aromatics excluding re-circulating flow 66 kg/h Output and the selectivity of the formation of o - and p-xylenes to 3.73 kg/h wt%. The yield of benzene, o - and p-xylenes 21,22 kg/h

P R I m m e R 2. In the reactor unit consisting of three consecutive reactors (see Fig.2) serves to 100 kg/h of propane. The process is carried out on silica zeolite ZSM-5 with silicate module 60, containing 1.5% zinc, at 570aboutAnd bulk supply of liquid propane 2 h-1. Leaving the last reactor, the reaction products are cooled in the refrigerator 8 and fed to the separator 9, where the separated hydrogen and hydrocarbons1-C2. Liquid products are sent to a stabilization column of liquid products 12, where at the top of selected hydrocarbons WITH3-C4. VAT product is sent to the column 15 allocation of benzene. CBM product column 15 serves for the separation in the column 18, where the top emit toluene, and CBM Ola share in block 24 of the separation of xylenes; received m-xylene fraction in the amount of 12 kg/h served in the last (third) of the reactor unit. The volumetric rate of flow of the liquid raw material 2 h-1. The time of contact in the last reactor is 1.8 C. the Compositions of the streams of the source and of the products obtained according to Fig.2 are presented in table.2. The yield of benzene, o - and p-xylenes (without recirculation, m-xylene fraction) was 23.1 kg/h Output and the selectivity of the formation of o - and p-xylenes - 8.9 kg/h (wt.%), which is 2.4 times higher than in the prototype.

P R I m e R 3. The process is conducted as in example 2, but the reaction block consists of 4 consecutive reactors, and the aromatization serves fraction WITH3-C4with a ratio of 50/50 at 600aboutWith, the catalyst is zinc (3% )-containing zeolite ZSM-5 with the module 60. m-Xylene fraction is fed into the fourth reactor in the amount of 12 kg/h, the residence Time of the stream containing m-xylene fraction, in the last reactor of 0.3 sec.

The results are presented in table.3. The yield of benzene, o - and p-xylenes was 23.3 kg/h, and the yield and selectivity of the formation of o - and p-xylenes 8,8 kg/h (wt.%), what 2.35 times higher than in the prototype.

P R I m e R 4. The process is conducted as in example 3, gallicolae fraction withdrawn from the process.

The results are presented in table. 4. The yield of benzene, o - and p-xylenes (threads 16, 25 and 26) was 20.6 kg/h, and the yield and selectivity of the formation of o - and p-xylenes - 6,0 kg/h ( wt.%), which is 1.6 times higher than in example 1.

P R I m e R 5. The process is conducted as in example 2, but at a temperature of 400aboutWith kalisoderjasimi zeolite (3,0% Ga).

The results are presented in table.5. The yield of benzene, o - and p-xylenes was 23.1 kg/h, and the yield and selectivity of the formation of o - and p-xylenes - the same as in example 2.

P R I m e R 6. The process is conducted as in example 2, but the temperature in the reactor 600aboutWith and contact time m-xylene fraction with a catalyst in the last reactor of 0.1 C. the Results are presented in table.6. The yield of benzene, o - and p-xylenes - 18.8 kg/h, and the yield and selectivity of o - and p-xylenes - 8.3 kg/h (mass. % ), higher than in the prototype, 1.4 times, but much less than in examples 2-4, due to low conversion of m-xylene due to insufficient contact time.

P R I m e R 7. The process is conducted as in example 6, but the time of contact of the stream containing m-xylene fraction with a catalyst in the last reactor of 2.5 C.

The results are presented in table.7. The yield of benzene, o - and p-xylenes 21,9 who in examples 2, 3 and 5, which is explained by the decrease in the degree of preservation of xylenes (60%) at the time of contact of more than 1.8 with.

Comparative data processes of the prototype and the proposed methods are presented in table.8.

1. A METHOD of producing BENZENE, TOLUENE, ORTHO - AND PARAXYLENE by contacting alkanes C3- C4at elevated temperatures with vysokoglinozemistym zinc or kalisoderjasimi zeolite catalyst of the ZSM-5 reactor unit consisting of a cascade of series-connected reactors, with subsequent separation of the reaction products to recycle a fraction of the original alkanes, benzene, toluene, xylene and the fraction of C9+-aromatics, including recycling the fraction of aromatic hydrocarbon to the stage of contact, characterized in that, to increase the yield of ortho - and paraxylene, xylene fraction is subjected to separation and the selected metacello fraction is sent to recycling as a fraction of aromatic hydrocarbons in the last along the reactor, and the process in the reactor is carried out at contact time of 0.3 to 1.8 with.

2. The method according to p. 1, characterized in that the process of contacting is conducted at a temperature of 400-600oC.

 

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The invention relates to the production of aromatic hydrocarbons

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36 cl

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26 cl, 1 dwg, 5 tbl, 4 cl

FIELD: CHEMISTRY.

SUBSTANCE: zeolite catalyst for process of conversion of straight-run gasoline to high-octane number component is described. The said catalyst contains high-silica zeolite with SiO2/Al2O3=60 and residual content of Na2О of 0.02 wt.% maximum, metal-modified, Pt, Ni, Zn or Fe metals being in nanopowder form. Content of the said metals in the catalyst is 1.5 wt.% maximum. Method to manufacture zeolite catalyst for conversion of straight-run gasoline to high-octane number component is described. The said method implies metal modification of zeolite, Pt, Ni, Zn or Fe metals being added to zeolite as nanopowders, produced by electric explosion of metal wire in argon, by dry pebble mixing in air at room temperature. Method to convert straight-run gasoline using the said catalyst is also described.

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4 cl, 3 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: method involves hydrocarbon transformation in a reactor in the presence of modified catalyst containing, mass %: 53.0-60.0 of ZSM-5 high-silica zeolite with the ratio of SiO2/Al2O3=39, 34.0-38.0 of Al2O3, 2.0-5.0 of B2O3, 1.0-5.0 of Zn, 0.0-5.0 of W, 0.0-3.0 of La, 0.0-3.0 of Ti at 300÷700°C, including separation of liquid and solid transformation products, followed by burning oxidation of gaseous products and addition of the obtained mix of carbon dioxide and water vapour to the source hydrocarbons at the rate of 2.0÷20.0 mass %. Before the raw material intake the reaction system is flushed by an inert gas (nitrogen), starting from 300°C and to the transformation temperature. Hydrocarbons used are alkanes, olefins or alkane olefin mixes C2-C15 without preliminary separation into fractions. Gaseous transformation products undergo burning and complete oxidation in the presence of an oxidation catalyst of vanadium/molybdenum contact piece, V2O5/MoO3. To sustain continuous process two identical reactors are used, where the catalyst is transformed and recovered in turns.

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2 ex

FIELD: chemistry.

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4 cl, 8 tbl, 12 ex

FIELD: chemistry.

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6 cl, 5 tbl, 1 dwg

FIELD: chemistry.

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2 cl, 5 ex, 1 dwg

FIELD: chemistry.

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30 cl, 3 dwg, 4 tbl, 2 ex

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1 cl, 5 ex, 5 tbl

FIELD: chemistry.

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15 cl, 2 tbl, 5 ex

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3 cl, 3 tbl

FIELD: petroleum chemistry and petroleum processing.

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2 cl, 1 tbl, 7 ex

FIELD: petrochemical process catalysts.

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16 cl, 2 dwg, 2 tbl

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides high-silica zeolite catalyst comprising molybdenum and a second modifying element, namely nickel, content of the former in catalyst being no higher than 4.0 wt % and that of the latter from 0.1 to 0.5 wt %. Preparation of the catalyst involves modifying zeolite with molybdenum and second promoting element, the two being introduced into zeolite in the form of nano-size metal powders in above-indicated amounts.

EFFECT: enhanced efficiency of non-oxidative methane conversion process due to increased activity and stability of catalyst.

3 cl, 1 tbl, 7 ex

FIELD: gas treatment.

SUBSTANCE: invention relates to catalytic treatment of natural gas to remove higher hydrocarbons and sulfur compounds contained therein while simultaneously converting hydrocarbons into aromatics and methane. Catalyst comprises crystalline aluminosilicate expressed by molar ratio in following way: xQ : (0.01-0.1)M2O : (0-0.08)Z2O3 : SiO2 : (0.0001-0.5)Me, wherein Q denotes tetrapropylammonium bromide; Z aluminum, gallium, or mixture thereof; x = 0-0.5; M represents at least proton or metal cation selected from sodium and potassium cations; and Me is at least one metal selected from zinc and copper. Preferably, zeolite H-ZSM-5 is employed and gas is treated at temperature above 600°C and pressure, which is prevalent in gas transportation pipelines.

EFFECT: improved gas treatment process.

5 cl, 5 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: method involves hydrocarbon transformation in a reactor in the presence of modified catalyst containing, mass %: 53.0-60.0 of ZSM-5 high-silica zeolite with the ratio of SiO2/Al2O3=39, 34.0-38.0 of Al2O3, 2.0-5.0 of B2O3, 1.0-5.0 of Zn, 0.0-5.0 of W, 0.0-3.0 of La, 0.0-3.0 of Ti at 300÷700°C, including separation of liquid and solid transformation products, followed by burning oxidation of gaseous products and addition of the obtained mix of carbon dioxide and water vapour to the source hydrocarbons at the rate of 2.0÷20.0 mass %. Before the raw material intake the reaction system is flushed by an inert gas (nitrogen), starting from 300°C and to the transformation temperature. Hydrocarbons used are alkanes, olefins or alkane olefin mixes C2-C15 without preliminary separation into fractions. Gaseous transformation products undergo burning and complete oxidation in the presence of an oxidation catalyst of vanadium/molybdenum contact piece, V2O5/MoO3. To sustain continuous process two identical reactors are used, where the catalyst is transformed and recovered in turns.

EFFECT: longer working transformation cycle due to the continuous process scheme; higher yearly output of aromatic hydrocarbons; reduced energy capacity and improved ecology of the process.

2 ex

FIELD: chemistry.

SUBSTANCE: invention can increase the efficiency of processes of nonoxidising conversion of methane due to increase in activity of W-containing zeolite catalysts. Described is the zeolite catalyst ZSM-5 for process of nonoxidising conversion of methane which has in its composition tungsten in the form of nano-sized powder, thus the content of tungsten in the catalyst is from 4.0 up to 10.0 mass %. Also the method of the preparation of zeolite catalyst for the process of nonoxidising conversion of methane is described, including modification of zeolite by tungsten as a solid, thus tungsten is introduced into zeolite in the form of nano-sized powder of the metal, obtained by the method of electrical explosion of the conductor in the environment of argon, thus the content of tungsten in the obtained catalyst is from 4.0 up to 10.0 mass %. The method of nonoxidising conversion of methane in the presence of zeolite catalyst is described.

EFFECT: obtaining of a catalyst with higher activity during conversion of methane in aromatic hydrocarbons.

3 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of producing aromatic hydrocarbons and hydrogen. Gaseous raw material, containing inferior hydrocarbons, undergoes reforming through contact with a catalyst at high temperature. As a result, aromatic hydrocarbons and hydrogen are formed. The given method is characterised by that, it involves the following operation: addition of gaseous raw material together with hydrogen gas with amount of gaseous raw material more than 2% vol and less than 10% vol. Addition of gaseous raw material is delayed by a given time interval while continually adding a given amount of hydrogen gas.

EFFECT: use of this method enables to maintain constant catalytic activity, which allows for efficient production of aromatic hydrocarbons and hydrogen.

9 cl, 9 dwg, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing liquid hydrocarbons from methane. Disclosed is a method of converting methane into liquid hydrocarbons, in which material containing methane is brought into contact with a dehydrocyclisation catalyst under conditions suitable for conversion of said methane to aromatic hydrocarbons, including naphthalene, and obtaining a first effluent containing hydrogen and at least 5 wt % aromatic hydrocarbons more than said starting material. At least a portion of aromatic hydrocarbons from the first effluent then reacts with hydrogen to form a second effluent having lower content of benzene compared to said first effluent, and at least a portion of hydrogen from the first effluent reacts with carbon monoxide, carbon dioxide or mixture thereof to obtain an additional effluent containing water and a hydrocarbon, and at least a portion of the hydrocarbon in said additional effluent is returned to said contact step.

EFFECT: improved method of converting methane to liquid hydrocarbons when methane is contained in a stream of natural gas with large amount of carbon dioxide.

32 cl, 3 dwg, 4 ex

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