Composite carrier material supported cobalt-based catalyst and preparation and application thereof

A technology of cobalt-based catalyst and composite carrier, which is applied in the field of catalysis, can solve the problems of reduced reduction degree, poor metal dispersion, and weak interaction force of metal Co, and achieves increased pore volume and pore size, high selectivity, and good catalytic performance. Effect

Pending Publication Date: 2022-07-29
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The oxide support promotes the dispersion of metal Co nanoparticles due to its strong interaction with metal Co, but it is easy to generate metal composite oxides during the reduction process, which inhibits the reduction of metal Co and reduces the degree of reduction.
And carbon materials, such as: carbon nanotubes, carbon fibers, carbon black, carbon spheres and other supports, have weak interaction with metal Co, which promotes the reduction of metal Co but the metal dispersion is poor, so the construction of support composite materials Still needs further research

Method used

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  • Composite carrier material supported cobalt-based catalyst and preparation and application thereof
  • Composite carrier material supported cobalt-based catalyst and preparation and application thereof
  • Composite carrier material supported cobalt-based catalyst and preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] 1. Preparation of ZIF-9@SiO 2 : Co(NO 3 ) 2 ·6H 2 O (5.82g, 0.02mol) and benzimidazole (6.16g, 0.075mol) were dissolved in 150mL methanol, respectively, and then mixed with 2g SiO 2 Mix quickly and evenly, stir at room temperature for 24 hours, centrifuge the solid at high speed (10000r / min) and wash it with methanol 3 times, and dry at 60°C to obtain ZIF-9@SiO 2 , the structure of the catalyst precursor can be observed by scanning electron microscopy.

[0020] 2. Preparation of Co-CN@SiO 2 : 2g ZIF-9@SiO 2 It was placed in a quartz tube and passed through a tube furnace, and was heated from room temperature to 1000 °C in an Ar atmosphere at a heating rate of 5 °C / min for in situ pyrolysis for 2 h, and the Ar gas space velocity was 1000 h. -1 , get Co-CN@SiO 2 .

[0021] The specific surface area, pore volume, pore size of the catalyst determined by physical adsorption characterization and the structure and physical properties of the catalyst such as Co content ...

Embodiment 2

[0024] 1. Preparation of ZIF-9@SiO 2 : Co(NO 3 ) 2 ·6H 2 O (5.82g, 0.02mol) and benzimidazole (6.16g, 0.075mol) were dissolved in 150mL methanol, respectively, and then mixed with 2g SiO 2 Mix quickly and evenly, stir at room temperature for 24 hours, centrifuge the solid at high speed (10000r / min) and wash with MeOH 3 times, and dry at 80°C to obtain ZIF-9@SiO 2 , the structure of the catalyst precursor can be observed by scanning electron microscopy.

[0025] 2. Preparation of Co-CN@SiO 2 : 2g ZIF-9@SiO 2 It was placed in a quartz tube and passed through a tube furnace, and was heated from room temperature to 800 °C in an Ar atmosphere at a heating rate of 5 °C / min for in situ pyrolysis for 2 h, and the Ar gas space velocity was 1000 h. -1 , get Co-CN@SiO 2 .

[0026] The specific surface area, pore volume, pore size of the catalyst determined by physical adsorption characterization and the structure and physical properties of the catalyst such as Co content detected...

Embodiment 3

[0029] 1. Preparation of ZIF-9@Al 2 O 3 : Co(NO 3 ) 2 ·6H 2 O (5.82g, 0.02mol) and benzimidazole (6.16g, 0.075mol) were dissolved in 150mL methanol, respectively, and then mixed with 2g SiO 2Mix quickly and evenly, stir at room temperature for 24 hours, centrifuge the solid at high speed (10000r / min) and wash it with MeOH 3 times, and dry at 60°C to obtain ZIF-9@Al 2 O 3 , the structure of the catalyst precursor can be observed by scanning electron microscopy.

[0030] 2. Preparation of Co-CN@Al 2 O 3 : 2g ZIF-9@Al 2 O 3 It was placed in a quartz tube and passed through a tube furnace, and was heated from room temperature to 1000 °C in an Ar atmosphere at a heating rate of 5 °C / min for in situ pyrolysis for 2 h, and the Ar gas space velocity was 1000 h. -1 , get Co-CN@Al 2 O 3 .

[0031] The specific surface area, pore volume, pore size of the catalyst determined by physical adsorption characterization and the structure and physical properties of the catalyst such...

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Abstract

The invention relates to a preparation method of a composite carrier material supported cobalt-based catalyst and application of the composite carrier material supported cobalt-based catalyst in Fischer-Tropsch synthesis reaction. The catalyst takes Co as an active component. According to the catalyst, ZIF-9 containing SiO2, Al2O3 and TiO2 is taken as a precursor and a template, and a Co catalyst with a composite carrier is generated through pyrolysis. Wherein the cobalt content is 25-60 wt%, the catalyst metal prepared through pyrolysis has strong interaction with the oxide, the pore volume and pore diameter are increased, the metal Co loading capacity is high, a certain self-reduction rate capability is achieved, and the Fischer-Tropsch synthesis catalyst is high in activity, good in stability and high in C5 < + > hydrocarbon selectivity.

Description

technical field [0001] The invention relates to a technology for catalyzing and efficiently converting synthesis gas, and belongs to the field of catalysis. In particular, it relates to the catalytic conversion of syngas to C 5+ A method for preparing a composite carrier material-supported cobalt-based catalyst for the Fischer-Tropsch synthesis reaction of hydrocarbons. More specifically, it relates to the preparation of a cobalt catalyst using ZIFs material and oxide support as composite precursors, wherein its performance is further regulated by additives. The active component is metallic Co. Background technique [0002] As the active center of common Fischer-Tropsch synthesis catalysts, Co has suitable Fischer-Tropsch synthesis catalytic activity and hydrogenation performance, and promotes the formation of long-chain alkanes such as high-quality gasoline and diesel, and is widely used in industry. The influence of the support material on the catalyst is very important...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/24B01J35/10C10G2/00
CPCB01J27/24B01J35/1028B01J35/1042B01J35/1057C10G2/33C10G2/332
Inventor 赵子昂李怡蕙丁云杰朱何俊卢巍龚磊峰
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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