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A kind of cobalt-based catalyst with silicon oxide mesoporous foam as carrier and its application

A technology of cobalt-based catalyst and silicon oxide, applied in the direction of physical/chemical process catalysts, chemical instruments and methods, chemical/physical processes, etc., can solve the problems of low CH4 selectivity, high specific surface area, and high reactivity, and achieve specific surface area High, good dispersion, uniform effect of active metal particles

Active Publication Date: 2014-10-01
SOUTH CENTRAL UNIVERSITY FOR NATIONALITIES
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

[0007] Chinese patent CN 102139214A discloses a method for preparing a cobalt-based Fischer-Tropsch catalyst with a double-pore structure with ordered pores intercommunicating. The catalyst prepared by this method has orderly arrangement of pores, high specific surface area, high reactivity, and CH4 selectivity Low
Similarly, through the investigation of existing literature, it is found that MCF, a new type of material, has not been applied in the field of Fischer-Tropsch synthesis at present. In view of its structural characteristics, it meets the selection conditions of Fischer-Tropsch synthesis carriers (mesoporous structure, large specific surface area, Adjustable pore size and narrow distribution, etc.), we tried to use it as a carrier for the preparation of cobalt-based catalysts. After testing the catalyst for Fischer-Tropsch synthesis reaction activity, we were surprised to find that the cobalt-based catalyst supported by this material has excellent and unexpected Catalytic performance for Fischer-Tropsch synthesis

Method used

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  • A kind of cobalt-based catalyst with silicon oxide mesoporous foam as carrier and its application
  • A kind of cobalt-based catalyst with silicon oxide mesoporous foam as carrier and its application
  • A kind of cobalt-based catalyst with silicon oxide mesoporous foam as carrier and its application

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] At room temperature, 6.00 g of triblock polymer surfactant P123 (Aldrich, EO 20 PO 70 EO 20 , MA=5800) was dissolved in 210mL of 2mol / L hydrochloric acid, stirred for 1h, added 5.34mL of benzene, continued to stir for 1h, then added 13.50mL of tetraethyl orthosilicate (TEOS), stirred for 24h and transferred to polytetrafluoroethylene In a reaction tank, crystallize at 100°C for 24h, filter, wash and dry in the air, dry in an oven at 120°C for 12h, and finally bake at 550°C for 5h to obtain a carrier MCF (24) with a pore size of 24nm. The 24 after the MCF means the carrier is spherical The pore size of the pores is 24 nm.

[0031] The pore structure parameters of the carrier MCF(24) were tested by a physical chemical adsorption instrument (Kanta, USA), and the results are shown in Table 1.

[0032] Take 2.00g of the above carrier, and impregnate the metal cobalt element by the full-hole impregnation method. Based on the mass fraction of the cobalt element in the final...

Embodiment 2

[0035] At room temperature, 6.00 g of triblock polymer surfactant P123 (Aldrich, EO 20 PO 70 EO 20 , MA=5800) was dissolved in 210mL of 2mol / L hydrochloric acid, stirred for 1h, added 9.32mL of benzene, continued to stir for 1h, then added 13.50mL of tetraethyl orthosilicate (TEOS), stirred for 24h and transferred to polytetrafluoroethylene In a reaction tank, crystallize at 100°C for 24h, filter, wash and dry in the air, dry in an oven at 120°C for 12h, and finally bake at 550°C for 5h to obtain a carrier MCF (32) with a pore size of 32nm, where 32 means that the spherical pore size of the carrier is 32nm.

[0036] Take 2.00 g of the above carrier, and impregnate atomic cobalt with a mass fraction of 15% by the full-hole impregnation method. Dissolve 1.74g of cobalt nitrate hexahydrate in 5.50mL of distilled water, impregnate the solution evenly on the carrier, dry it in an oven at 120°C for 12h, and then bake it in a muffle furnace at 350°C for 5h in an air atmosphere. A...

Embodiment 3

[0039] At room temperature, 18 g of triblock polymer surfactant P123 (Aldrich, EO 20 PO 70 EO 20 , MA=5800) dissolved in 630mL of 2mol / L hydrochloric acid, stirred for 1h, added 39.90mL of benzene, continued to stir for 1h, then added 40.50mL of tetraethyl orthosilicate (TEOS), stirred for 24h and then transferred to polytetrafluoroethylene In a reaction tank, crystallize at 100°C for 24h, filter, wash and dry in the air, dry in an oven at 120°C for 12h, and finally bake at 550°C for 5h to obtain a carrier MCF (45) with a pore size of 45nm, where 45 means that the spherical pore size is 45nm.

[0040] The pore structure parameters of the carrier MCF (45) were tested by a physical chemical adsorption instrument, and the results are shown in Table 1.

[0041] Take 2.00 g of the above carrier and impregnate it with a full-pore impregnation method to prepare a catalyst with an atomic cobalt mass fraction of 15%. Dissolve 1.74g of cobalt nitrate hexahydrate in 6.50mL of distill...

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Abstract

The invention belongs to the technical field of novel Fischer-Tropsch synthesis catalyst preparation, and specifically discloses a preparation method for a cobalt-base catalyst adopting silicon oxide mesoporous foam MCF as a carrier, and an application of the cobalt-base catalyst in Fischer-Tropsch synthesis. According to the present invention, the carrier of the present invention has a three-dimensional ordered pore structure; the specific surface area of the carrier can be up to 1000 cm<2> / g; the pore size of the carrier can be adjusted in a range of 20-50 nm; the pore volume of the carrier is 1.5-3.0 cm<3> / g; the pore presents a spherical structure; the spherical pores are communicated through windows; the diffusion effect is good; the prepared catalyst has a high surface area; the active metal loading is high; and the active metal particles are uniformly dispersed, and the dispersity is good. Compared with the activity of the conventional silicon oxide carrier loaded cobalt-base catalyst, the activity of the cobalt-base catalyst of the present invention is increased by more than two times. In addition, the activity and the heavy hydrocarbon selectivity of the cobalt-base catalyst of the present invention are significantly increased compared with SBA-15 loaded cobalt-base catalysts having the same structured ordered structure, and the catalyst shows excellent performances after adjuvant element impregnating or doping.

Description

technical field [0001] The present invention relates to the technical field of preparation of novel Fischer-Tropsch synthesis catalysts, in particular to a preparation method of a cobalt-based catalyst supported by silica mesoporous foam (Siliceous Mesocellular Foams, MCF) and its application in Fischer-Tropsch synthesis . Background technique [0002] Fischer-Tropsch synthesis is a reaction that converts carbon monoxide and hydrogen into a range of hydrocarbons. The reaction product can be processed to obtain clean liquid fuels, such as gasoline, diesel, aviation kerosene, etc. Therefore, the research on obtaining clean liquid fuels by Fischer-Tropsch synthesis has attracted great attention from all over the world. [0003] The cobalt-based catalysts used to catalyze the Fischer-Tropsch synthesis reaction have the characteristics of high activity and high linear alkane selectivity, as well as low water gas shift reaction activity and are not easy to deactivate, so they ha...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/75B01J23/89B01J23/83B01J35/10C10G2/00
Inventor 李金林韦良张煜华赵燕熹胡春玲
Owner SOUTH CENTRAL UNIVERSITY FOR NATIONALITIES
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