A method of alkylation of aromatic hydrocarbons synthesis gas


C07C2/16 - Acids of sulfur; Salts thereof; Sulfur oxides

 

(57) Abstract:

Usage: petrochemistry. Essence: alkylate aromatic hydrocarbons synthesis gas in two ways. 1. Toluene and syngas in the gas phase in contact with a catalyst containing zeolite ZSM-5 or ZSM-5 modified with compounds of silicon and magnesium, and metal oxide component containing, by weight. % Of ZnO 65 - 70, Cr2O329 - 34, W2O51 when the mass ratio of zeolite and metal oxide component is 30 to 70 and 70 to 30, respectively, at 380 - 480oC, space velocity of the synthesis gas 700 - 6000 h-1. Part of the gas stream after separation of the condensed reaction products served on recycling. 2. A mixture of toluene, 2-methylnaphthalene and synthesis gas in contact under these conditions with a catalyst, which may contain in addition to the above-described zeolites zeolite ZSM-12. This increases the selectivity of the process for dimethylnaphthalenes, and/or p-xylene, and p-ethyltoluene. 2 s and 5 C.p. f-crystals, 2 tab.

The invention relates to organic chemistry, namely a process for the production of cyclic hydrocarbons and, in particular, to a method for producing paraxylene, paracetalmol and dimethylnaphthalenes by kataliticheskogo application in the chemical industry as solvents and as intermediates for organic syntheses. For example, paraxylene is used for the production of terephthalic acid which is used in the synthesis of dimethyl terephthalate and various synthetic fibers such as Dacron and others; paracetalmol necessary for the production methylstyrene, and from 2,6-dimethylnaphthalene receive 2,6-naphthaleneboronic acid used in the production of polyesters and polyamides. The main source of raw material for industry alkylaromatic hydrocarbons may be coke and steel companies that produce benzene, toluene and methylnaphthalene as secondary products, as well as having large quantities of CO and H2-containing fuel gases (coke oven, blast furnace gas gases and Ferroalloy production).

Known methods for producing alkylaromatic hydrocarbons of various organic materials in the presence of catalysts based on crystalline aluminosilicates (U.S. patent N 4086289, class C 07 C 3/52, 1978; U.S. patent N 5001295, class C 07 C 2/66, 1991; U.S. patent N 4487984, class C 07 C 1/00, 1984, [1-3]).

A mixture of toluene and syngas (abbr. SG) turn in xylenes catalyst consisting of a zeolite KX (or K-13X) and chromite zinc (Zn 0311 or Zn 0312). The process temperature is 250-650what I have low selectivity and the yield of p-xylene.

Methods of alkylation of naphthalene hydrocarbons (hereinafter naftalina) synthesis gas was not detected in the scientific and patent literature. Therefore, the analogue here is the way to get dialkylamino, in particular, dimethylnaphthalenes by alkylation of 2-alkylnaphthalene, in particular, 2-methylnaphthalene aliphatic C2-C5alcohols, in particular methanol (U.S. patent N 5001295, class C 07 C 2/66, 1991 [2]). According to this method, as the catalyst was used zeolite H-ZSM-5 (10 cm3preliminarily calcined directly in the reactor at 450oC for 3 hours in air flow. The process of alkylation of 2-methylnaphthalene (abbr. 2-MH) with methanol is carried out at atmospheric pressure, a temperature of 270 to 500oC, the weight flow rates in the reactor 4 g/h 2-MH and 4 g/h of methanol. In the proceeding of the reactions at the reactor exit get naphthalene, methylnaphthalene (MN), ethylnaphthalene (ER), dimethylnaphthalene (DMN) and trimethylnaphthalene (TDS). The selectivity of the catalyst DMN was depending on the process temperature from 69 to 87% at complete conversion of the 2-MH from 1 to 19%.

Closest to the present invention is a method of producing xylenes (abbr. KS), atilola the political systems, consisting of a metal oxide component (oxides of copper, zinc and aluminum or chromium and aluminum silicate in crystalline or amorphous form (U.S. patent N 4487984, class C 07 C 1/00, 1984, [3]). According to the selected prototype process is carried out at a temperature of 200-400oC, a pressure of 1-200 bar and a molar relationship of H2/CO and CO2/CO equal to 1-5 and 0.01-1 respectively.

The main disadvantage of the prototype is the low selectivity of the catalyst formed in p-xylene and p-ethyltoluene at low conversion of toluene and CO (CO2), as well as the lack of examples for obtaining dimethylnaphthalenes.

The present invention is to increase the selectivity of the process for dimethylnaphthalene and/or p-xylene, p-ethyltoluene when the alkylation of 2-methylnaphthalene and/or toluene synthesis gas at high conversion of the feedstock.

The problem is solved in two variants of the method.

1. Method for alkylation of aromatic hydrocarbons synthesis gas by contacting the feedstock - toluene and syngas in the gas phase with a catalyst containing crystalline aluminosilicate and a metal oxide component, at an elevated temperature and pressure, as Cree is magnesium, and metal oxide component contains, by weight. % ZnO - 65,70; Cr2O3- 29-34; W2O5-1, if the mass ratio of zeolite and metal oxide component in the catalyst equal to 30 to 70 and 70 to 30, respectively, the process is carried out at a temperature 380-480oC and space velocity of the synthesis gas 700-6000 h-1in a flow-circulation system with a cooling gas stream after the reactor, separating the condensed reaction products and the flow of the gas stream for recycling.

The problem is solved also by the fact that the weight flow rate of toluene is 0.8-2.8 h -1.

The problem is solved also by the fact that the modified zeolite ZSM-5 contains compounds of silicon and magnesium 1-3 and 4-15 wt.% respectively.

2. Method for alkylation of aromatic hydrocarbons synthesis gas by contacting the feedstock in the gas phase with a catalyst containing crystalline aluminosilicate and a metal oxide component, at an elevated temperature and pressure, as a starting raw material, a mixture of toluene, 2-methylnaphthalene and synthesis gas, and as the crystalline aluminosilicate is used, the zeolite ZSM-5 or ZSM-5 modified with connections going to the>O5- 1, when the mass ratio of zeolite and metal oxide component in the catalyst equal to 30 to 70 and 70 to 30, respectively, the process is carried out at a temperature 380-480oC and space velocity of the synthesis gas 700-6000 h-1in a flow-circulation system with a cooling gas stream after the reactor, separating the condensed reaction products and the flow of the gas stream for recycling.

The problem is solved also by the fact that the weight flow rate of toluene is 0.8-2.8 h-1.

The problem is solved also by the fact that the weight feed rate of 2-methylnaphthalene is 0,04-0,07 h-1.

The problem is solved also by the fact that the modified zeolite ZSM-5 contains compounds of silicon and magnesium 1-3 and 4-15 wt.% respectively.

Distinctive features of the invention are: a) the method uses a catalyst, which includes as a crystalline aluminosilicate vysokoglinozemistyj zeolite ZSM-5 or zeolite ZSM-5 modified with compounds of silicon and magnesium, or zeolite ZSM-12.

b) as a metal oxide component using the composition of the metal oxide composition, wt.%:

ZnO : Cr2O3: W2OPole reactor, Department of condensed reaction products and the flow of the gas stream for recycling,

d) the mass ratio of zeolite to the metal oxide component in the catalyst is 30-70/70-30,

d) the process is carried out at a temperature 380-480oC, the weight of the feed speed of toluene and 0.8-2.8 h-1weight feed speed 2-methylnaphthalene 0,04-0,07 h-1and space velocity of the synthesis gas 700-6000 h-1,

(e) zeolite ZSM-5 contains compounds of silicon and magnesium 1-3 and 4-15 wt.% respectively.

The use of metal oxide component of the catalyst allows to synthesize methanol from gas mixtures containing CO, CO2and H2that on the zeolite component of the catalyst alkiliruet benzene ring of toluene to form xylenes or naphthalene ring 2-methylnaphthalene with the formation of dimethylnaphthalenes. In addition to performing the functions of the alkylating agent is methanol is easily converted into dimethyl ether and then to ethylene, with high reactivity in the reactions of alkylation of the benzene ring. As a result of interaction of toluene with ethylene in the acidic centers of the zeolite are formed ethyltoluene. Use as a zeolite component vysokokremnezemnstogo of xylenes and ethyltoluene, contributes to the predominant formation in the channels of zeolite least bulky prisonerof of xylenes and ethyltoluene, and modification of the external surface of the zeolite crystals of compounds of silicon and magnesium prevents the reactions of isomerization of p-xylene and p-ethyltoluene in meta - and artisanry. Claimed in the invention the number entered in the zeolite of silicon and magnesium are chosen experimentally. To achieve a higher conversion of 2-methylnaphthalene in dimethylnaphthalene having dimensions of molecules, somewhat larger than the channels of zeolite ZSM-5, was used for alkylation naftalina zeolite ZSM-12, the channels of which are close on the effective diameter to the size of molecules dimethylnaphthalenes. High molar ratio of SiO2:Al2O3and the unique crystal structure of zeolite ZSM-12 was possible to achieve selectivity by the sum of dimethylnaphthalenes at higher conversion of 2-methylnaphthalene in comparison with similar (see reference (U.S. patent N 5001295, class C 07 C 2/66, 1991, [2])). Use the process as a catalyst only metal oxide component or only the zeolite does not allow to achieve set forth in the invention results. It is the combination of the catalyst meth/or toluene) and synthesis gas in the direction of formation of dimethylnaphthalenes (and/or p-xylene and p-ethyltoluene). Decontamination of active centers of coke formation on the external surface of the zeolite by modification of compounds of silicon and magnesium, as well as the use of metal oxide in the catalyst component, active in hydrogenation reactions of unsaturated compounds, the precursors of coke, in combination with high blood pressure and recovery of the reaction environment contribute to high stability used in the invention catalysts. All used in the invention, the catalysts prepared according to known methods.

The choice of conditions for the process of obtaining p-xylene and p-ethyltoluene of toluene and syngas and p-xylene, p-ethyltoluene and dimethylnaphthalenes of toluene, 2-methylnaphthalene and synthesis gas due to the following factors. The lower limit of the temperature is 380oC is the limit of the minimal catalytic activity of the used catalyst in the transformation of raw materials, the upper limit temperature (480oCo) is associated with deterioration of thermal stability of the metal oxide component of the catalyst. High blood pressure is necessary for deeper conversion of synthesis gas, toluene and 2-methylnaphthalene, and consumption data for toluene and synthesis gas ovo derivatives of naphthalene, is a crystalline substance, therefore, to supply 2-methylnaphthalene in the reactor and the allocation of naphthalene reaction products requires the use of a solvent. In the proposed method, the solvent used toluene in a weight ratio of toluene/2-methylnaphthalene=95/5. Low concentrations of 2-methylnaphthalene in the supply of the liquid raw material was selected in order to completely prevent the deposition of crystals naftalina in the contact devices of the laboratory setup. In the practical use of the proposed method in an enlarged scale of the concentrations of 2-methylnaphthalene in the liquid raw material can be greatly increased. Raw synthesis gas may vary within wide limits - from 50 to 80 mol.% H2the rest is CO and/or CO2.

To improve the catalyst selectivity for p-xylene, p-ethyltoluene and dimethylnaphthalenes use circulation gas flow through the reactor extension products formed from the circulation loop. The effect of forced circulation of the cooling gas stream after the reactor the reactions is that whenever the recycle gas stream through the reactor due to the presence of high l what about the promotes the formation of the primary products of alkylation, namely, p-xylene, p-ethyltoluene, dimethylnaphthalene and eliminates the secondary flow transformations data products for the reactions of isomerization, alkylation and coke formation. Cooling the circulating gas and separating the condensed products from the gas in the separator prevents further contact of the formed p-xylene, p-ethyltoluene and dimethylnaphthalenes with catalyst. Due to the fact that the initial toluene has a significantly higher volatility compared to the p-xylene and p-ethyltoluene experimentally chosen such conditions condensation products in which part of toluene remains in the circulation gas and is fed into the reactor for re-alkylation of p-xylene and p-atitool. Entering the alkylation original synthesis gas is mixed with the circulating gas and a metal oxide component is converted to methanol and then to the zeolite in ethylene. A large part of the educated methanol on a modified zeolite alkiliruet toluene with the formation of p-xylene and ethylene basically turns together with toluene in n-atitool. Low conversion of the original synthesis gas for each pass through the reactor provides a layer of high catalyst molar ratio that is wala. As a result, multiple passing the synthesis gas through the reactor achieved a high degree of conversion of CO to the target product, and removing of recycle formed during water suppresses side conversion of CO to CO2by the reaction of water gas. Non-condensable products of the conversion of synthesis gas and toluene is continuously removed from the circulation circuit in proportion to their education.

As a result, the method of circulation with the separation of liquid reaction products can increase not only the selectivity of the catalyst on primary products (in this case, p-xylene, p-ethyltoluene and dimethylnaphthalenes), but also to increase the yield of p-xylene, p-ethyltoluene and dimethylnaphthalenes filed on toluene.

The main products of the alkylation of toluene synthesis gas in the claimed method are xylenes and ethyltoluene with a high content of prisonera, but mainly the products of alkylation of 2-methylnaphthalene are dimethylnaphthalene containing up to 60-90% of 2,6-DMN mixed with 2,7-isomer. Side of hydrocarbon products are paraffins C1-C4trimethylbenzene, etincelle and tetramethylbenzene, and in the case of 2-methylnaphthalene in the reaction products is not hydrocarbons are practically absent in the reaction products. By-products of the conversion of synthesis gas are mainly H2O and a little CO2the number of which is proportional to the number of converted synthesis gas. The content of methanol and dimethyl ether in the reaction products is less than 3 wt.% the sum of all of the formed products (except for examples of the use of zeolite ZSM-12).

Industrial applicability of the proposed method is illustrated by examples 1-12, the example 0 - prototype.

Example 0 - prototype. Metal oxide component containing at 41.5 wt.% copper, a 14.1 wt. % zinc and 5.0 wt.% aluminum and impregnated with boric acid, was mixed with the powder in a volume ratio of 1:1. Received a combined catalyst treated gaseous mixture containing 2% H2and 98% N2at a temperature of 220oC for 16 hours and used for the conversion of toluene and syngas (68% mol.% H2, 26 mol.% CO and 6 mol.% CO2). Conditions and key process indicators are presented in table.2.

Examples 1-4. A mixture of toluene and syngas (66 mol.% H2, 33 mol.% CO 1 mol. % CH2) is in contact with a catalyst consisting of a zeolite HZSM-5 (molar ratio SiO2:Al2O3=70), treated with solutions tetrade. The content introduced in the zeolite items, and bulk compositions of the metal oxide component and the catalyst are shown in table. 1. Conditions and key process indicators are presented in table. 2.

Examples 5. A mixture of toluene and syngas (72 mol.% H2, 28 mol.% CO) is in contact with a catalyst consisting of a zeolite HZSM-5 (molar ratio SiO2: Al2O3= 100), and metal oxide component containing metal oxides of zinc, chromium and vanadium. Bulk composition of the catalyst and metal oxide component are shown in table.1. Conditions and key process indicators are presented in table. 2.

Examples 6-7. A mixture of toluene, 2-methylnaphthalene and synthesis gas (67 mol.% H2, 30 mol.% CO., 2 mol.% CO2and 1 mol.% CH4) is in contact with a catalyst consisting of a zeolite HZSM-5 (molar ratio SiO2:Al2O3=70), treated with a solution of tetraethoxysilane and magnesium acetate, and a metal oxide component containing metal oxides of zinc, chromium and vanadium. The content introduced in the zeolite items, and bulk compositions of the metal oxide component and the catalyst are shown in table. 1. Conditions and key process indicators presented the% CO2and 1 mol.% CH4) is in contact with a catalyst consisting of a zeolite HZSM-5 (molar ratio SiO2:Al2O3=27) and metal oxide component containing metal oxides of zinc, chromium and vanadium. Bulk composition of the catalyst and metal oxide component are shown in table.1. Conditions and key process indicators are presented in table. 2.

Examples 9-10. A mixture of toluene, 2-methylnaphthalene and synthesis gas (67 mol.% H2, 30 mol. % CO, 2 mol.% CH4) is in contact with a catalyst consisting of a zeolite HZSM-5 (molar ratio SiO2:Al2O3=27) and metal oxide component containing metal oxides of zinc, chromium and vanadium. In these examples (in contrast to example 7) used the zeolite with a different morphology of crystals. Bulk composition of the catalyst and metal oxide component are shown in table. 1. Conditions and key process indicators are presented in table. 2.

Example 11-12. A mixture of toluene, 2-methylnaphthalene and synthesis gas (67 mol.% H2, 30 mol. % CO, 2 mol.% CO2and 1 mol.% CH4) is in contact with a catalyst consisting of a zeolite HZSM-12 (molar ratio SiO2:Al2O3=200) and metal oxide component containing oxides metl. 1. Conditions and key process indicators are presented in table. 2.

Shown in invention examples 1 to 12 show that the objective - increase catalyst selectivity for p-xylene and p-ethyltoluene at alkylation of toluene synthesis gas, and getting dimethylnaphthalene with high selectivity by alkylation of 2-methylnaphthalene synthesis gas is solved by the distinguishing features set forth in the claims.

Sources of information

1. U.S. patent N 4086289, class C 07 C 3/52, 1978.

2. U.S. patent N 5001295, class C 07 C 2/66, 1991.

3. U.S. patent N 4487984, class C 07 C 1/00, 1984.

1. A method of alkylation of aromatic hydrocarbons synthesis gas by contacting the feedstock - toluene and syngas in the gas phase with a catalyst containing crystalline aluminosilicate and a metal oxide component, at an elevated temperature and pressure, characterized in that the crystalline aluminosilicate is used, the zeolite ZSM-5 or ZSM-5 modified with compounds of silicon and magnesium, and metal oxide component contains, wt%:

ZnO - 65 - 70

Cr2O3- 29 - 34

W2O5- 1

at mass the SS carried out at a temperature of 380 - 480oC and space velocity of the synthesis gas 700 - 6000 h-1in a flow-circulation system with a cooling gas stream after the reactor, separating the condensed reaction products and the flow of the gas stream for recycling.

2. The method according to p. 1, characterized in that the weight flow rate of toluene is 0.8 - 2.8 h-1.

3. The method according to PP.1 and 2, characterized in that the modified zeolite ZSM-5 contains compounds of silicon and magnesium 1 to 3 and 4 to 15 wt.% respectively.

4. A method of alkylation of aromatic hydrocarbons synthesis gas by contacting the feedstock in the gas phase with a catalyst containing crystalline aluminosilicate and a metal oxide component, at an elevated temperature and pressure, characterized in that as starting raw material, a mixture of toluene, 2-methylnaphthalene and synthesis gas, and as the crystalline aluminosilicate is used, the zeolite ZSM-5 or ZSM-5 modified with compounds of silicon and magnesium, or zeolite ZSM-12, and the metal oxide component contains, wt%:

ZnO - 65 - 70

Cr2O3- 29 - 34

W2O5- 1

when the mass ratio of zeolite and metal oxide the space velocity of the synthesis gas 700 - 6000 h-1in a flow-circulation system with a cooling gas stream after the reactor, separating the condensed reaction products and the flow of the gas stream for recycling.

5. The method according to p. 4, characterized in that the weight flow rate of toluene is 0.8 - 2.8 h-1.

6. The method according to PP. 4 and 5, characterized in that the weight of the feed speed 2-methylnaphthalene is 0,04 - 0,07 h-1.

7. The method according to PP.4 to 6, characterized in that the modified zeolite ZSM-5 contains compounds of silicon and magnesium 1 to 3 and 4 to 15 wt.% respectively.

 

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EFFECT: higher content of ethane than methane in the light gas fraction enables use of exhaust gas as raw material for cracking apparatus.

15 cl, 2 tbl, 5 ex

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