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Embedded microporous-mesoporous composite molecular sieve methanation catalyst and its application

A technology of molecular sieve methane and mesoporous molecular sieve, which is applied in the direction of molecular sieve catalysts, including molecular sieve catalysts, carbon compound catalysts, etc., can solve the problems of low hydrothermal stability and low-temperature catalytic activity to be improved, and achieve superior hydrothermal stability, Excellent reactivity and high temperature resistance

Active Publication Date: 2021-05-18
SHIJIAZHUANG VOCATIONAL TECH INST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Chinese invention patent application number 201210457434.5 discloses in-situ metal-doped mesoporous molecular sieves and their uses. The mesoporous molecular sieve MCM-41 is used as the carrier, and metal Ni is used as the main active component to dope into the MCM-41 framework structure, and used In the methanation reaction, compared with the supported catalyst, it shows good high temperature resistance performance, but its catalytic activity, especially the low temperature catalytic activity needs to be improved, and its hydrothermal stability is not high

Method used

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preparation example Construction

[0025] The preparation method of the embedded microporous-mesoporous composite molecular sieve methanation catalyst comprises the following steps:

[0026] (1) prepare Ni salt solution;

[0027] (2) Disperse the ZSM-5 microporous molecular sieve in the NaOH solution, add the template agent CTAB, stir vigorously, drop the silicon source TEOS at the same time, add the prepared Ni salt solution dropwise, stir vigorously for a certain period of time, and transfer to water Crystallization in a thermal reactor;

[0028] (3) The raw solution after crystallization is cooled to room temperature, suction-filtered, washed until neutral, vacuum-dried, and roasted to obtain a catalyst, and the Ni loading in the catalyst is 1-10 wt%.

[0029] It is worth noting that the Ni salt is nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the solvent used in the Ni salt solution is deionized water, ethanol; the hydrothermal synthesis temperature is 80 ~ 150°C, preferably 100-120°...

Embodiment 1

[0032] Embodiment 1: The preparation method of embedded microporous-mesoporous composite molecular sieve methanation catalyst, its steps are: take by weighing 1.6g nickel nitrate hexahydrate and dissolve in 20ml deionized water, configure nickel nitrate aqueous solution; 3.3gZSM-5 Molecular sieves are dispersed in NaOH solution, the solution is heated to 40°C, a certain amount of template agent (hexadecyltrimethylammonium bromide) is added under vigorous stirring, nickel nitrate aqueous solution and silicon source (orthosilicate) are slowly mixed Add it dropwise into the solution, adjust the pH value of the solution to 11, and the molar ratio of each substance in the solution is: 1.0ZSM-5: 0.12Ni: 0.12CTAB: 1.0TEOS: 0.2NaOH: 100H 2 O. The mixed solution was vigorously stirred and aged for 2 hours, then moved to a hydrothermal reaction kettle, crystallized at 100°C for 72 hours, cooled rapidly to room temperature, filtered, washed until neutral, dried overnight at 100°C, and ca...

Embodiment 2

[0033] Embodiment 2: The preparation method of embedded microporous-mesoporous composite molecular sieve methanation catalyst, its steps are: take 3.2g nickel nitrate hexahydrate and dissolve in 20ml deionized water, configure nickel nitrate aqueous solution; 3.3gZSM-5 Molecular sieves are dispersed in NaOH solution, the solution is heated to 40°C, a certain amount of template agent (hexadecyltrimethylammonium bromide) is added under vigorous stirring, nickel nitrate aqueous solution and silicon source (orthosilicate) are slowly mixed Add it dropwise into the solution, adjust the pH value of the solution to 11, and the molar ratio of each substance in the solution is: 1.0ZSM-5: 0.12Ni: 0.12CTAB: 1.0TEOS: 0.2NaOH: 100H 2 O. The mixed solution was vigorously stirred and aged for 2 hours, then moved to a hydrothermal reaction kettle, crystallized at 100°C for 72 hours, cooled rapidly to room temperature, filtered, washed until neutral, dried overnight at 100°C, and calcined at 55...

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Abstract

The invention discloses an embedded microporous-mesoporous composite molecular sieve methanation catalyst and its application, and relates to the technical field of methanation catalysts. It uses the composite molecular sieve ZSM-5 / MCM-41 composed of mesoporous molecular sieve MCM-41 and microporous molecular sieve ZSM-5 as the carrier, uses Ni as the active component, and uses in-situ synthesis to embed the active component Ni into the micropores -In the framework structure of the mesoporous composite molecular sieve, the mass percentage of Ni is 1-10wt%, and the balance is microporous-mesoporous molecular sieve ZSM-5 / MCM-41. The invention has both micropore and mesoporous structures, higher methane selectivity, low loading of active components, high activity, good high temperature resistance, good hydrothermal stability and long catalyst life, etc., and is very industrialized Application prospect.

Description

technical field [0001] The invention relates to the technical field of methanation catalysts, in particular to a microporous-mesoporous composite molecular sieve ZSM-5 / MCM-41 methanation catalyst embedded with active components in situ and its application in the preparation of SNG. Background technique [0002] In recent years, with the implementation of my country's sustainable development strategy and environmental protection policy, the demand for clean energy is increasing. As a high-quality and efficient clean energy, natural gas is highly sought after by the international market, and the consumer market is growing rapidly. Therefore, my country's demand for natural gas is increasing, the gap between supply and demand is constantly expanding, and the degree of dependence on foreign countries is gradually increasing. As a substitute and supplement for liquefied petroleum gas and natural gas, coal-to-natural gas can optimize the structure of coal deep-processing products,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/46C07C1/04C07C9/04
CPCB01J29/005B01J29/0333B01J29/46B01J2229/183C07C1/0435C07C1/0445C07C2529/46C07C9/04
Inventor 张加赢耿海波郝卓莉郑辉陈力
Owner SHIJIAZHUANG VOCATIONAL TECH INST