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Hierarchical hzsm-5 catalyst

A catalyst and layered technology, applied in catalysts, molecular sieve catalysts, carbon compound catalysts, etc., can solve the problems of low yield of cellulose catalytic thermal cracking aromatics, uneven distribution of mesopore pore size, and high yield of thermal cracking aromatics. Good distribution, enhanced heterogeneous mass transfer, and the effect of a large number of mesopores

Active Publication Date: 2020-06-09
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0008] In order to solve the problems in the prior art that the number of mesopores of the HZSM-5 molecular sieve catalyst is small, the distribution of mesopore diameters is not concentrated, and the yield of aromatic hydrocarbons in cellulose catalytic pyrolysis is low, the present invention intends to provide a catalyst for preparing aromatic hydrocarbons by catalytic cracking of biomass, The number of mesopores is large, the distribution of mesopore diameter is relatively concentrated, and the yield of aromatic hydrocarbons in cellulose catalytic pyrolysis is high.

Method used

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preparation example Construction

[0023] The first aspect of the present invention provides a kind of preparation method of hierarchical HZSM-5 catalyst, comprises the following steps:

[0024] In the first step, the organic template agent, aluminum source, water, and hard template agent are mixed according to the mass ratio of 1~6: 0.1~1.0: 50~150: 0.1~1.0, stirred to form a mixed solution, and passed into the above mixed solution Gaseous tetraethyl orthosilicate, the temperature is 170~250℃, and the feeding time is 1~12h;

[0025] In the second step, the liquid after the reaction in the first step is stirred, left to stand for aging, transferred to a high-pressure reactor, and reacted in a closed manner at 120-200°C for 1-8 days; the solid product after the reaction is washed, dried, and roasted;

[0026] In the third step, put the product of the second step in 50~90℃, 0.1~2.0mol / L NH 4 Soak in Cl solution for 8~12h, wash, dry, repeat the above process of soaking, washing, and drying 2~4 times, and roast. ...

Embodiment 1

[0040] (1) Mix 10g of tetrapropylammonium hydroxide, 27g of water, 0.3g of sodium metaaluminate, and 0.3g of nanocellulose, and then magnetically stir for 3 hours at room temperature to form a mixed solution. 2 as the carrier, the temperature of TEOS gas is 200°C, the flow rate of TEOS gas is 200mL / min, N 2 The flow rate is 200mL / min, and the feeding time is 6h;

[0041] (2) Stir the reacted liquid from (1), let it stand for aging for 12 hours, transfer it to a high-pressure reactor for crystallization at 170°C for 5 days, wash the reacted solid product, dry it, and roast it at 550°C for 10 hours;

[0042] (3) Put the solid product obtained in (2) in 1.0mol / L NH at 80°C 4 In the Cl solution for 8 hours, carry out ion exchange, filter, wash and dry, repeat the above process twice, and roast at 550°C for 6 hours to obtain the hierarchical HZSM-5 catalyst C1.

[0043] figure 1 is the transmission electron microscope picture of catalyst C1, figure 1 It can be seen that there...

Embodiment 2

[0047] (1) Mix 10g of tetrapropylammonium hydroxide, 27g of water, 0.3g of sodium metaaluminate, and 0.3g of nanocellulose, and then magnetically stir for 3 hours at room temperature to form a mixed solution. 2 as the carrier, the temperature of TEOS gas is 180°C, the flow rate of TEOS gas is 200mL / min, N 2 The flow rate is 200mL / min, and the feeding time is 6h;

[0048] (2) Stir the reacted liquid from (1), let it stand for aging for 12 hours, transfer it to a high-pressure reactor for crystallization at 170°C for 5 days, wash the reacted solid product, dry it, and roast it at 550°C for 10 hours;

[0049] (3) Put the solid product obtained in (2) in 1.0mol / L NH at 80°C 4 In the Cl solution for 8 hours, perform ion exchange, filter, wash, and dry, repeat the above process twice, and roast at 550° C. for 6 hours to obtain the hierarchical HZSM-5 catalyst C2.

[0050] Catalyst C2 and cellulose were ground and mixed evenly at a mass ratio of 20:1, and the catalytic cracking rea...

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Abstract

The invention provides a layered HZSM-5 catalyst. The layered HZSM-5 catalyst is prepared through the following treatment processes: preparing a silicon source and a template agent into a mixed solution, wherein the silicon source is introduced in a gaseous state, then carrying out standing and aging, carrying out a closed reaction at a high temperature and high pressure, soaking an obtained material into an NH4Cl solution, carrying out ion exchange, and carrying out washing, drying, calcination, etc. The layered HZSM-5 catalyst provided by the invention has a silicon-to-aluminum ratio of (25-40): 1, a specific surface area of 350 to 450 m2 / g and a pore volume of 0.25 to 0.40 cm3 / g, wherein a mesopore volume accounts for 50 to 80% of the pore volume. In the preparation process of the layered HZSM-5 catalyst provided by the invention, a molecular sieve has easily-controllable silicon-to-aluminum ratio; and the catalyst has high silicon-to-aluminum ratio, a plurality of mesopores and good pore size distribution, and is used in a reaction for preparation of aromatic hydrocarbon through biomass catalysis, and greatly improves the yield of the aromatic hydrocarbon.

Description

technical field [0001] The invention relates to a hierarchical catalyst prepared by using HZSM-5 molecular sieve as a raw material, in particular to a catalyst for producing aromatics by catalytic cracking of biomass. Background technique [0002] Aromatics is a general term for hydrocarbons containing benzene ring structure, and is an important raw material for organic chemical industry. Among them, monocyclic aromatic hydrocarbons are more prominent. Benzene and xylene are raw materials for the manufacture of various synthetic resins, synthetic rubber, and synthetic fibers. Toluene can be converted to xylene and benzene. Higher alkylbenzenes are important raw materials for the manufacture of surfactants. Biphenyl in polycyclic aromatic hydrocarbons is used as heat carrier in chemical process. Naphthalene in fused aromatic hydrocarbons is an important raw material for the manufacture of dyes and plasticizers. Certain aromatic hydrocarbons or their mixtures such as benz...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/40C01B39/40C07C1/20C07C15/02C10G1/00
CPCB01J29/40C01B39/40C01P2006/12C01P2006/14C01P2006/17C07C1/20C07C2529/40C10G1/00C10G2300/1014C07C15/02
Inventor 傅杰马会霞程浩周峰乔凯黄和
Owner CHINA PETROLEUM & CHEM CORP
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