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Preparation method of MOF framework catalyst for biomass catalytic pyrolysis

A catalytic pyrolysis and catalyst technology, which is applied in the field of preparation of MOF skeleton catalysts, can solve the problems of catalyst activity reduction, activity reduction, catalyst pore blockage, etc., achieve the effects of small mass transfer resistance, simple preparation process, and overcome the complex preparation process

Active Publication Date: 2020-11-17
HANGZHOU DIANZI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For microporous or mesoporous ZSM-5 molecular sieve catalysts, the main reason for the decrease in activity is that the acid sites on the outer surface of the catalyst are the active sites of the coking reaction, and the generated macromolecular coke blocks the pores of the catalyst. drop rapidly

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0012] (1) Uniformly disperse 1 mol of 2-methylimidazole and 0.7 mol of acetonitrile in 60 ml of isopropanol at a molar ratio of 1:0.7 to obtain solution A.

[0013] (2) Disperse 1 mol of cadmium chloride and 0.6 mol of sodium pyroantimonate uniformly in 350 ml of isopropanol at a molar ratio of 1:0.6 to obtain solution B.

[0014] (3) Add solution A dropwise to solution B, stir evenly, place in a water bath and heat to 30°C, react for 6 hours, centrifuge the product, wash with ethanol and deionized water, and dry to obtain the surface basic constant The ratio of Kb to the acid constant Ka is 0.7:1, and the catalyst has a pore structure of 0.3-10nm.

[0015] (4) Using rice husk as a raw material, the catalyst of the present invention is used to carry out pyrolysis reaction at 550° C. for 5 hours, and the liquid product is collected. The liquid product yield was 40.5%, and the guaiacol content was 40.1%.

Embodiment 2

[0017] (1) Uniformly disperse 1 mol of 2-methylimidazole and 1 mol of acetonitrile in 80 ml of isopropanol at a molar ratio of 1:1 to obtain solution A.

[0018] (2) Uniformly disperse 1 mol of cadmium chloride and 1 mol of sodium pyroantimonate in 500 ml of isopropanol at a molar ratio of 1:1 to obtain solution B.

[0019] (3) Add solution A dropwise to solution B, stir evenly, place in a water bath and heat to 50°C, react for 10 hours, centrifuge the product, wash with ethanol and deionized water, and dry to obtain the surface basic constant The ratio of Kb to the acid constant Ka is 1.5:1, 40-60nm pore structure.

[0020] (4) Using sawdust as a raw material, the catalyst of the present invention is used to carry out pyrolysis reaction at 650° C. for 3 hours, and the liquid product is collected. The liquid product yield was 42.8%, and the guaiacol content was 41.9%.

Embodiment 3

[0022] (1) Uniformly disperse 1 mol of 2-methylimidazole and 0.8 mol of acetonitrile in 65 ml of isopropanol at a molar ratio of 1:0.8 to obtain solution A.

[0023] (2) Disperse 1 mol of cadmium chloride and 0.7 mol of sodium pyroantimonate uniformly in 350 ml of isopropanol at a molar ratio of 1:0.7 to obtain solution B.

[0024] (3) Add solution A dropwise to solution B, stir evenly, place in a water bath and heat to 35°C, react for 6.5 hours, centrifuge the product, wash with ethanol and deionized water, and dry to obtain surface alkaline The ratio of the constant Kb to the acid constant Ka is 1.1:1, and the catalyst has a 0.5-35nm pore size structure.

[0025] (4) Using wheat straw as raw material, the catalyst of the present invention is used to carry out pyrolysis reaction at 550° C. for 7 hours, and the liquid product is collected. The liquid product yield was 45.6%, and the guaiacol content was 44.8%.

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Abstract

The invention discloses a preparation method of an MOF framework catalyst for biomass catalytic pyrolysis. The method comprises: dropwisely and slowly adding cadmium chloride and sodium pyroantimonateisopropanol solution into 2-methylimidazole and alkene nitrile isopropanol solution, stirring, heating to 30-50 DEG C in a water bath, reacting for 6-10h, centrifugally separating a product, washingwith ethanol and deionized water, and drying to obtain the MOF skeleton catalyst with the surface alkaline constant Kb and the acid constant Ka of 0.7-1.5:1 and the pore diameter structure of 0.3-60 nm. The MOF skeleton catalyst for biomass catalytic pyrolysis is synthesized by taking cadmium chloride and sodium pyroantimonate as metal raw materials and taking 2-methylimidazole and alkene nitrileas organic ligand raw materials, and has the advantages of simple preparation process, high selectivity and yield of guaiacol in a biomass pyrolysis liquid product, easiness in large-scale productionand the like.

Description

technical field [0001] The invention belongs to the technical field of biomass reuse, in particular to a method for preparing a MOF skeleton catalyst used for catalytic pyrolysis of biomass. Background technique [0002] The rapid catalytic pyrolysis of biomass to prepare high-quality bio-oil technology can realize the preparation of chemicals and liquid fuels, and is considered to be one of the effective ways to replace fossil energy. However, bio-oil has disadvantages such as complex components, high oxygen content, and difficulty in separation, so it needs to be upgraded by catalysis before it can be used as an alternative fuel. In order to improve bio-oil yield and target product selectivity, it is crucial to select a suitable catalyst. Microporous (such as ZSM-5, Y-type and type zeolites, etc.) and mesoporous molecular sieves (such as MCM-41, MSU, SBA-15, etc.) are due to their regular pore structure, good hydrothermal stability, suitable acidity and The ideal shape-s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B01J35/10C07C41/01C07C43/23C08G83/00
CPCB01J31/1815B01J31/2265C08G83/008C07C41/01B01J2531/27B01J2531/50B01J35/643B01J35/651B01J35/647C07C43/23Y02E50/10
Inventor 姚志通罗琦予唐俊红刘洁徐少丹韩伟黄进刚吴卫红
Owner HANGZHOU DIANZI UNIV
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