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Supported cobalt-base catalyst and preparation method thereof, and application of catalyst in Fischer-Tropsch synthesis

A cobalt-based catalyst, supported technology, applied in chemical instruments and methods, heterogeneous catalyst chemical elements, physical/chemical process catalysts, etc. The effect of high stability, rich pore structure and large specific surface area

Inactive Publication Date: 2017-05-31
中科潞安能源技术有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] In order to solve the problem that the above-mentioned Fischer-Tropsch synthesis reaction is limited by the law of ASF and the selectivity of the target product is low

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Weigh 100g of pitch-based carbon microspheres (prepared according to patent CN 201310208313.1), and activate treatment with an excess of 7.5mol / L NaOH for 2h to obtain activated carbon microspheres (specific surface area of ​​1000m 2 / g, the pore volume is 1.0cm 3 / g, the pore size is 15nm); 144.96g Co(NO 3 ) 2 ·6H 2 O, 0.78g RuCl 3 ·3H 2 O and 35.91gLa(NO 3 ) 3 ·6H 2 O was dissolved in water and immersed in the above activated carbon microspheres in equal volume, dried in an oven at 60°C for 24 hours, and then calcined in a tube furnace at 450°C in a nitrogen atmosphere for 4 hours to prepare the final catalyst with a weight composition of Co 3 O 4 : RuO 2 : La 2 O 3 :Activated carbon microspheres=40:0.5:10:100.

[0028] Take 5ml of the above catalyst and pack it in a fixed bed reactor (Ф10×500mm) without dilution. The reduction conditions are: 450℃, 0.3MPa, constant temperature for 12h, 1500h -1 (v / v), using hydrogen in nitrogen, H 2 The content is 10% (v / v). The reaction ...

Embodiment 2

[0030] Weigh 100g starch-based carbon microspheres (prepared according to patent CN 201610225264.6), and activate treatment with an excess of 6mol / L KOH for 4h to obtain activated carbon microspheres (specific surface area of ​​2000m 2 / g, the pore volume is 1.2cm 3 / g, the pore size is 10nm); 181.2g Co(NO 3 ) 2 ·6H 2 O, 0.23g H 2 PtCl 6 ·6H 2 O and 32.53g(N ZrO O 3 ) 2 ·2H 2 O was dissolved in water and immersed in the above activated carbon microspheres in equal volume, dried in an oven at 70°C for 20 hours, and then calcined in a tube furnace at 420°C in a helium atmosphere for 4 hours to prepare the final catalyst with a weight composition of Co 3 O 4 : PtO 2 : ZrO 2 :Activated carbon microspheres=50:0.1:15:100.

[0031] Take 5ml of the above catalyst and pack it in a fixed bed reactor (Ф10×500mm) without dilution. The reduction conditions are: 430℃, 0.2MPa, constant temperature for 16h, 1300h -1 (v / v), using hydrogen in nitrogen, H 2 The content is 5% (v / v). The reaction condi...

Embodiment 3

[0033] Weigh 100g of pitch-based carbon microspheres (prepared according to patent CN 200610141086.5) and activate them with a mixture of 5mol / L NaOH and 5mol / L KOH for 6 hours to obtain activated carbon microspheres (specific surface area of ​​2500m 2 / g, the pore volume is 1.5cm 3 / g, the pore size is 5.0nm); 186.06g C 4 H 6 O 4 ·Co·4H 2 O, 0.44g Pd(NO 3 ) 2 ·2H 2 O and 30.27g Ce(NO 3 ) 3 ·6H 2 O is dissolved in water and immersed in the above activated carbon microspheres in equal volume, dried in an oven at 80°C for 16h, and then calcined in a tube furnace at 400°C under argon atmosphere for 12h to prepare the final catalyst with a weight composition of Co 3 O 4 : PdO: CeO 2 :Activated carbon microspheres=60:0.2:12:100.

[0034] Take 5ml of the above catalyst and pack it in a fixed bed reactor (Ф10×500mm) without dilution. The reduction conditions are: 410℃, 0.3MPa, constant temperature 20h, 1200h -1 (v / v), using hydrogen in nitrogen, H 2 The content is 15% (v / v). The reaction ...

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Abstract

The invention relates to a supported cobalt-base catalyst which is composed of the following components in parts by weight: 15-60 parts of tricobalt tetraoxide, 0-1 part of noble metal aid oxide, 0-15 parts of non-noble metal aid oxide and 100 parts of activated carbon microspheres. The supported cobalt-base catalyst has the advantages of large specific area, centralized and adjustable pore size distribution, abundant pore structures, uniform and adjustable cobalt particle size and high selectivity for target products.

Description

Technical field [0001] The invention relates to a Fischer-Tropsch synthesis catalyst and a preparation method and application thereof, in particular to a cobalt-based Fischer-Tropsch synthesis catalyst supported by activated carbon microspheres and a preparation method and application thereof. [0002] technical background [0003] The global consumption of fossil fuels, increasing energy demand and the resulting environmental pollution make the clean use of coal an urgent problem to be solved. Among them, the Fischer-Tropsch synthesis technology has always been a research hotspot for oil companies and scientific research institutions in various countries. Fischer-Tropsch synthesis is one of the effective ways for syngas to produce clean liquid fuels and chemicals with low sulfur, nitrogen-free, metal-free, and low aromatic content under the action of a catalyst. [0004] After more than 80 years of development, Fischer-Tropsch synthesis has made great progress in catalysts, reactor...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/89B01J23/78B01J23/889B01J35/10C10G2/00
CPCC10G2/332C10G2/333B01J23/002B01J23/78B01J23/8892B01J23/8913B01J23/894B01J23/8986B01J2523/00C10G2300/70B01J35/618B01J35/638B01J35/643B01J35/647B01J2523/3706B01J2523/821B01J2523/845B01J2523/48B01J2523/828B01J2523/3712B01J2523/824B01J2523/74B01J2523/822
Inventor 李德宝贾丽涛侯博刘岩
Owner 中科潞安能源技术有限公司
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