Cobalt-based Fischer-Tropsch synthesis catalyst with high heavy hydrocarbon selectivity as well as preparation method and application thereof

A catalyst and Tropsch synthesis technology, applied in the field of cobalt-based Fischer-Tropsch synthesis catalysts and their preparation, can solve the problems of large differences in thermal stability of cobalt catalysts, expensive SiC support, limited practical application, etc., and achieves good reproducibility , enhance the interaction force, the effect of simple preparation process

Active Publication Date: 2020-04-21
SOUTH CENTRAL UNIVERSITY FOR NATIONALITIES
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Carriers with different characteristics have different mass and heat transfer properties, and can form different interaction forces with Co metal, which makes the thermal stability of the supported cobalt catalysts vary greatly.
Using SiC carrier with high thermal

Method used

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  • Cobalt-based Fischer-Tropsch synthesis catalyst with high heavy hydrocarbon selectivity as well as preparation method and application thereof
  • Cobalt-based Fischer-Tropsch synthesis catalyst with high heavy hydrocarbon selectivity as well as preparation method and application thereof
  • Cobalt-based Fischer-Tropsch synthesis catalyst with high heavy hydrocarbon selectivity as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Example Embodiment

[0041] Example 1:

[0042] In the first step, add 20g of titanium isopropoxide to 5g of citric acid (the mass ratio of titanium to carbon is 1:2.7) and 26mL of absolute ethanol, stir well at 60℃, and transfer the resulting mixture In a reactor with PTFE lining, the product was collected after solvothermal reaction at 200℃ for 24h, filtered under reduced pressure, dried at 100℃ for 12h, and placed in a tube furnace in NH 3 Nitriding at 1000°C in an atmosphere to obtain TiN carrier;

[0043] The second step is to dissolve 4.7g of cobalt acetate tetrahydrate with 300mL of ethanol aqueous solution (water and absolute ethanol at a volume ratio of 50:1) as the solvent, and then add 25mL of 15mol / L ammonia, and neutralize with acid and alkali The precursor of nano cobalt oxide was obtained by the method, and the nano cobalt oxide particles were prepared after hydrothermal treatment at 180°C for 5 hours, drying at 100°C for 12 hours, and firing at 300°C for 3 hours;

[0044] In the third st...

Example Embodiment

[0047] Example 2:

[0048] The catalyst A was placed in a fixed bed reactor (TORCH) for catalytic reaction performance evaluation. The activation conditions were: normal pressure, H 2 In the atmosphere, the temperature is 300℃ and the volumetric space velocity is 1000h -1 , The activation time is 8h; the reaction conditions are: the reaction temperature is 240℃, 260℃ and 300℃, H 2 :CO (volume ratio) is 2:1, volume flow rate is 600h -1 , The pressure is 2.0MPa. Take N 2 Make an internal standard to calculate the conversion rate of CO. After the reaction, the tail gas is connected to Agilent GC3000A gas chromatograph for online analysis. The average reaction data within 100h of stable operation when the catalytic reaction reaches the target temperature is shown in Table 1.

Example Embodiment

[0049] Example 3:

[0050] Take the 4g TiN carrier and 0.96g nano cobalt oxide particles prepared in Example 1, first grind it by mechanical dispersion for 2h, mix them evenly, and then add 60mL ethanol aqueous solution (the volume ratio of ethanol to water is 1:2) and ultrasonically disperse for 1h , 60 ℃ vacuum rotary steaming for 3 hours, 100 ℃ drying for 12 hours to obtain catalyst B.

[0051] The mass of Co element in catalyst B accounts for about 15% of the mass of the catalyst (theoretical calculation value).

[0052] The catalyst evaluation test was carried out in a fixed bed reactor (TORCH), and the activation conditions were: under normal pressure, H 2 In the atmosphere, the temperature is 300℃ and the volumetric space velocity is 1000h -1 , The activation time is 8h; the reaction conditions are: the reaction temperature is 240℃, 260℃ and 300℃, H 2 :CO (volume ratio) is 2:1, volume flow rate is 600h -1 , The pressure is 1.0MPa. The reaction time is to reach the target reac...

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Abstract

The invention relates to the technical field of preparation of high-quality liquid fuel and chemicals by catalytic conversion of synthesis gas, and particularly discloses a cobalt-based Fischer-Tropsch synthesis catalyst with high heavy hydrocarbon (C<5+>) selectivity. In the catalyst, nano TiN is adopted as a carrier, cobaltosic oxide nanoparticles are loaded on the carrier; the particle size distribution range of the TiN particles is 18-48 nm, the particle size distribution range of the cobaltosic oxide particles is 6-14 nm, and the mass of the cobalt element in the catalyst accounts for 10%-15% of the mass of the catalyst. The cobalt-based Fischer-Tropsch synthesis catalyst provided by the invention is relatively wide in suitable reaction temperature range, and relatively low CH4 and CO2 selectivity and high heavy hydrocarbon selectivity can be maintained at a relatively high reaction temperature (240-300 DEG C).

Description

technical field [0001] The invention relates to the technical field of preparing high-quality liquid fuels and chemicals through catalytic conversion of syngas, in particular to a high-heavy hydrocarbon (C 5+ ) Selective cobalt-based Fischer-Tropsch synthesis catalyst and its preparation method and application. Background technique [0002] In recent years, the rapid consumption of petroleum resources has caused serious energy and environmental problems, and it is urgent to develop clean energy production technologies that can replace petroleum resources. Fischer-Tropsch synthesis (FTS) technology, which converts carbon-based raw materials such as coal, natural gas, biomass, and organic waste, into clean fuels and high value-added chemicals through syngas, has received extensive attention. The product selectivity of FTS reaction generally follows the ASF distribution, and the product composition is relatively complex. The selectivity is affected by factors such as catalyst ...

Claims

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Application Information

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IPC IPC(8): B01J27/24C10G2/00
CPCB01J27/24B01J35/0066C10G2/332Y02P20/52
Inventor 赵燕熹龙彩燕刘成超李金林张煜华林爱华
Owner SOUTH CENTRAL UNIVERSITY FOR NATIONALITIES
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