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Supported hierarchical-pore HZSM-5 catalyst

A multi-level pore, supported technology, applied in molecular sieve catalysts, catalyst activation/preparation, physical/chemical process catalysts, etc., can solve problems such as low coke yield, high yield of pyrolysis aromatics and olefins, and affecting the surface activity of molecular sieves , to achieve the effect of reducing coke yield and increasing olefin yield

Active Publication Date: 2018-06-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] In order to solve the problem in the prior art that the surface of the supported HZSM-5 molecular sieve catalyst is covered by metal, which affects the surface activity of the molecular sieve, the present invention intends to provide a supported HZSM-5 catalyst, the active metal of which is loaded in the pores of the molecular sieve, and at the same time introduced Mesoporous, the supported HZSM-5 has high catalytic activity, high yield of aromatic hydrocarbons and olefins in catalytic pyrolysis of cellulose, and low coke yield

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0020] The first aspect of the present invention provides a kind of preparation method of supported type hierarchical porous HZSM-5 catalyst, comprises the following steps:

[0021] (1) NiO, CoO, ZnO, Fe 2 o 3 At least one of , Pt, CuO is deposited onto the carbon nanoparticles;

[0022] (2) Al in the aluminum source 2 o 3 meter, SiO in silicon source 2 Meter, organic template agent and water are mixed and stirred according to the molar ratio of 1:25~40:5~8:600~1000 to obtain the synthetic ZSM-5 precursor solution;

[0023] (3) Immerse the carbon nanoparticles in (1) into the precursor solution in (2), transfer to a closed reaction kettle, react at 120~200°C for 1~8 days, wash the product, filter, dry, and roast ;

[0024] (4) Put the solid product in (3) 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.

[0025] In the above preparation method, in step (1), each metal o...

Embodiment 1

[0037] (1) Deposit NiO on carbon nanoparticles with a particle size of 2-8nm for 100 laps by atomic layer deposition;

[0038] (2) 10g of tetrapropylammonium hydroxide, 27g of water, 0.3g of sodium metaaluminate, and 15g of tetraethyl orthosilicate were magnetically stirred at room temperature for 3 hours to obtain a precursor solution for the synthesis of ZSM-5;

[0039] (3) Add 10g of carbon nanoparticles in (1) to the precursor solution in (2), transfer to a closed reaction kettle, react at 170°C for 5 days, wash the product, filter, dry, and bake at 550°C for 20h ;

[0040] (4) Put the product in (3) in 1.0mol / L NH at 80°C 4 Soak in Cl solution for 8 hours, wash, dry, repeat the above process twice, and calcined at 550° C. for 6 hours to obtain supported hierarchical porous HZSM-5 catalyst C1.

[0041] Catalyst C1 has a silicon-aluminum ratio of 30 and a specific surface area of ​​388m 2 / g, the total pore volume is 0.31cm 3 / g, the mesopore volume is 0.20cm 3 / g, the...

Embodiment 2

[0044] (1) Deposit CoO on carbon nanoparticles with a particle size of 2-8nm for 100 cycles by atomic layer deposition;

[0045] (2) 10g of tetrapropylammonium hydroxide, 27g of water, 0.3g of sodium metaaluminate, and 15g of tetraethyl orthosilicate were magnetically stirred at room temperature for 3 hours to obtain a precursor solution for the synthesis of ZSM-5;

[0046] (3) Add 10g of carbon nanoparticles in (1) to the precursor solution in (2), transfer to a closed reaction kettle, react at 170°C for 5 days, wash the product, filter, dry, and roast at 550°C 20h;

[0047] (4) Put the product in (3) in 1.0mol / L NH at 80°C 4 Soak in Cl solution for 8 hours, wash, dry, repeat the above process twice, and bake at 550°C for 6 hours to obtain supported hierarchical porous HZSM-5 catalyst C2.

[0048] Catalyst C2 has a silicon-aluminum ratio of 30 and a specific surface area of ​​376m 2 / g, the total pore volume is 0.30cm 3 / g, the mesopore volume is 0.19cm 3 / g, the micropo...

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Abstract

The invention discloses a supported hierarchical-pore HZSM-5 catalyst. The catalyst is prepared by the following steps: depositing active metal on carbon nano particles by an atomic layer deposition method, putting the carbon nano particles into a precursor solution prepared from an aluminum source, a silicon source, an organic template agent and water, carrying out a hydrothermal reaction, and carrying out ion exchange with a NH4Cl solution, so as to obtain the supported hierarchical-pore HZSM-5 catalyst. The supported hierarchical-pore HZSM-5 is synthesized with the combination of the atomiclayer deposition technology, and the active metal is positioned in the pore canals of a molecular sieve, so that the active metal is introduced, and meanwhile mesoporous is also introduced. Differentfrom the common impregnation method, the preparation method provided by the invention reduces the metal supported on the surface of the molecular sieve, and thereby reduces the acidity influence on the surface of the molecular sieve. Meanwhile, when the catalyst provided by the invention is applied to the catalytic pyrolysis reaction of cellulose, the yield rates of aromatic hydrocarbons and olefins are greatly improved compared with the yield rates of aromatic hydrocarbons and olefins by using a conventional molecular sieve, and the coke yield rate is greatly reduced compared with the coke yield rate by using the conventional molecular sieve.

Description

technical field [0001] The invention relates to a supported multi-stage porous HZSM-5 catalyst, in particular to a catalyst for preparing 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 benzene, xylene, toluene, etc. can be us...

Claims

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Application Information

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IPC IPC(8): B01J29/40B01J29/44B01J29/46C10B53/02C10G1/00
CPCC10B53/02C10G1/00B01J29/405B01J29/44B01J29/46B01J37/0201B01J2229/186C10G2300/1014C10G2400/30B01J35/615B01J35/633Y02E50/10
Inventor 傅杰周峰程浩马会霞乔凯黄和
Owner CHINA PETROLEUM & CHEM CORP
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