Mesoporous molecular sieve of in-situ doped metal and application thereof

A mesoporous molecular sieve and metal technology, applied in molecular sieve catalysts, hydrocarbon production from carbon oxides, organic chemistry, etc., can solve the problems of low methanation rate, low, unsuitable, high content of precious metals, etc.

Active Publication Date: 2014-05-21
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] CN101185892A discloses a kind of Ni/ZrO 2 Catalyst, which can reduce the carbon monoxide (CO) content in the hydrogen-rich system to below 100ppm, but it is not suitable for the methanation reaction of synthesis gas with high CO concentration; CN101371987A discloses a Ni-Ru-B-ZrO 2 Catalyst, which can reduce the CO outlet concentration in the hydrogen-rich system to less than 22ppm, while maintaining extremely low carbon dioxide (CO 2 ) methanation rate
But it is only suitable for the atmosphere of hydrogen-rich system, that is, the concentration of CO should be very low, and it is not suitable for the atmosphere system of producing methane from high-concentration synthesis gas, and the applicable temperature of the catalyst is 210-250 ° C, which is not suitable for Carry out methanation reaction under high temperature condition; CN101468311A has reported a kind of with Ni as the main active compo

Method used

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  • Mesoporous molecular sieve of in-situ doped metal and application thereof
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  • Mesoporous molecular sieve of in-situ doped metal and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0035]Weigh 2.428g of hexadecyltrimethylammonium bromide (template agent) and dissolve it in deionized water at 40°C, weigh 1.619g of nickel nitrate hexahydrate and dissolve it in 20ml of deionized water, and configure it into an aqueous solution of nickel nitrate, 0.447 gNaOH was dissolved in 10ml of deionized water, and the NaOH aqueous solution was slowly dropped into the template aqueous solution under vigorous stirring, and then 11.565g of tetraethyl orthosilicate was weighed, and the tetraethyl orthosilicate and nickel nitrate aqueous solution were slowly mixed under vigorous stirring. Drop into the templating agent aqueous solution. After the dropwise addition was completed, the mixture was vigorously stirred for 2 hours, and the product was transferred to a hydrothermal reaction kettle, and kept at 120° C. for 72 hours. Then rapidly cool to room temperature, filter and wash until neutral, dry the solid product in an oven, then raise the temperature to 550°C in a muffle...

Embodiment 2

[0038] Except replacing the nickel nitrate in embodiment 1 with lanthanum nitrate and nickel nitrate, other steps and conditions are identical with embodiment 1, obtain mesoporous molecular sieve B (the content of nickel or its oxide is 10wt%, the content of lanthanum or its oxide Content is 1wt%).

[0039] The evaluation method of the catalytic activity of mesoporous molecular sieve B is identical with embodiment 1: under normal pressure and space velocity 12000h -1 Under the above conditions, the conversion rate of carbon monoxide is 100%, and the selectivity of methane is 93.42%.

Embodiment 3

[0041] Except replacing the nickel nitrate in embodiment 1 with ammonium molybdate and nickel nitrate, other steps and conditions are the same as in embodiment 1 to obtain mesoporous molecular sieve C (the content of nickel or its oxide is 10wt%, molybdenum or its oxide The content is 3wt%).

[0042] The evaluation method of the catalytic activity of mesoporous molecular sieve C is identical with embodiment 1: under normal pressure and space velocity 12000h -1 Under the above conditions, the conversion rate of carbon monoxide is 100%, and the selectivity of methane is 97.17%.

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Abstract

The invention relates to a mesoporous molecular sieve of doped metal and an application thereof. The mesoporous molecular sieve is formed by mixing a template, an alkali source, a silicon source and a metal source at the molar ratio of (0.06-0.24):(0.1-0.3):1:(0.01-0.20), and stirring at 20-40 DEG C for 0.5-24 hours to obtain emulsion; carrying out hydrothermal reaction on the emulsion at 80-180 DEG C for at least 12 hours (or reacting in a microwave reactor at the power of 200-2100w for 1-10h), then successively cooling, filtering, washing to be neutral and drying to obtain solid matters; and roasting the solid matters at 400-800 DEG C for 1-15 hours to obtain the molecular sieve, wherein the molecular sieve has a specific area of (BET)200-1500m2/g, pore volume of 0.5-3.0cm3/g and aperture of 2-15nm. The mesoporous molecular sieve has catalytic activity at 200-550 DEG C and the catalytic activity does not decline after roasting at 700 DEG C for 20 hours. The molecular sieve can be used as a catalyst for reaction during methane preparation by synthesis gas, and has commercial value.

Description

technical field [0001] The present invention relates to a metal-doped mesoporous molecular sieve and its application, in particular to a mesoporous molecular sieve doped with metal nickel in situ, or a mixture composed of metal nickel and alkali metal, rare earth elements and / or rare metals. Porous molecular sieves and their uses. Background technique [0002] The preparation of methane from synthesis gas (mixed gas of hydrogen and carbon monoxide) (hereinafter referred to as "carbon monoxide methanation reaction") is one of the main reactions of coal-to-natural gas, which is a strongly exothermic reaction (reaction heat can reach 20 of the calorific value of synthesis gas %about). A strong exothermic reaction will lead to a substantial increase in the temperature of the reaction gas, which will easily cause the sintering of the active components of the catalyst. Therefore, an excellent catalyst for "carbon monoxide methanation reaction" needs to have high activity and hig...

Claims

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Application Information

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IPC IPC(8): C01B39/08B01J29/072C07C1/04C07C9/04
Inventor 辛忠张加赢
Owner EAST CHINA UNIV OF SCI & TECH
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