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Cobalt-based Fischer-Tropsch synthesis catalyst supported by mixed oxide carrier and preparation method thereof

A cobalt-based catalyst, mixed oxide technology, applied in the preparation of liquid hydrocarbon mixtures, metal/metal oxide/metal hydroxide catalysts, hydrocarbon production from carbon oxides, etc., can solve the problem of shortening catalyst operating life, oil and wax Difficulty in separation, difficult to restore, etc.

Active Publication Date: 2020-03-06
SHANGHAI ADVANCED RES INST CHINESE ACADEMY OF SCI +3
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the Co-Al 2 o 3 There is a strong interaction between them, and it is easy to form CoAl which is difficult to reduce and has no catalytic activity during the reaction process. 2 o 4 Substances, which will reduce its catalytic activity to a certain extent, improve methane selectivity and shorten the operating life of catalysts, these phenomena are undesirable for researchers in this field
while ZrO 2 Although the carrier has weak Co-ZrO 2 Interaction, high catalytic activity and C5+ selectivity, but it is easy to pulverize during the high temperature, high pressure and slurry bed F-T synthesis process in the presence of water vapor, which will make the subsequent separation of oil and wax difficult, and the fine particles after pulverization are easy to clog Gas distributor causes uneven diffusion of syngas and high catalyst loss rate

Method used

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  • Cobalt-based Fischer-Tropsch synthesis catalyst supported by mixed oxide carrier and preparation method thereof
  • Cobalt-based Fischer-Tropsch synthesis catalyst supported by mixed oxide carrier and preparation method thereof
  • Cobalt-based Fischer-Tropsch synthesis catalyst supported by mixed oxide carrier and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0051] Determine the consumption of various raw materials according to the weight ratio listed in Table 1 below. Dissolve 50 g of zirconium nitrate in water together with citric acid and ethylene glycol, and stir for 2 hours to form an aqueous solution of zirconium ions that can be used for isometric impregnation of alumina microspheres. Wherein the molar ratio of ethylene glycol, zirconium nitrate and citric acid is 1:2:4. Add weighed alumina microspheres to form a suspension and keep stirring for 16 hours. The suspension is spray-dried under stirring to obtain a microspherical solid, which is transferred to a muffle furnace and heated at a rate of 5°C / min. to 600° C., maintained at this temperature for 5 hours, and then cooled to room temperature to obtain spherical carrier particles of mixed oxides as carriers. The particle size measured by Malvern particle size analyzer was 85-100 microns, and it was found by SEM that a zirconia layer was formed on the entire outer surfa...

Embodiment 2

[0053] Determine the consumption of various raw materials according to the weight ratio listed in Table 1 below.Dissolve 50 g of zirconium nitrate in water together with citric acid and ethylene glycol, and stir for 2 hours to form an aqueous solution of zirconium ions that can be used for isometric impregnation of alumina microspheres. Wherein the molar ratio of ethylene glycol, zirconium nitrate and citric acid is 1:2:4. Add weighed alumina microspheres to form a suspension and keep stirring for 16 hours. The suspension is spray-dried under stirring to obtain a microspherical solid, which is transferred to a muffle furnace and heated at a rate of 5°C / min. to 600° C., maintained at this temperature for 5 hours, and then cooled to room temperature to obtain spherical carrier particles of mixed oxides as carriers. The particle size measured by a Malvern particle size analyzer is 55-95 microns, and it is found by SEM that a zirconia layer is formed on the entire outer surface ...

Embodiment 3

[0055] The steps of the above Example 1 were repeated, with the difference that the calcination temperature used in the preparation of the mixed oxide spherical carrier particles was 800° C. and the calcination time was 5 hours. The catalyst prepared above was named Cat-3.

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Abstract

A cobalt-based Fischer-Tropsch synthesis catalyst supported by a spherical carrier is disclosed. The catalyst comprises 1-51% by weight of cobaltous oxide, 49-99% by weight of mixed oxide spherical carrier particles the particle size of which is 10-100 mum, and less than 0.1% by weight of an optional precious metal. The mixed oxide spherical carrier particles comprise microspheres and an auxiliary agent. The microspheres are microspheres made of materials selected from silicon oxide, aluminum oxide, zirconium oxide or a mixture thereof. The auxiliary agent is an oxide of an element selected from Ni, Ca, Mg, La, Zr, Ce, Ti, Mn, V and Nb, or a mixture thereof. A method of preparing the catalyst is also provided.

Description

technical field [0001] The invention relates to the field of catalytic synthesis. Specifically, the invention provides a supported cobalt-based catalyst suitable for Fischer-Tropsch synthesis and a preparation method thereof. Background technique [0002] With the enhancement of environmental protection awareness and the continuous rise of crude oil prices, combined with my country's energy consumption structure, using Fischer-Tropsch synthesis to convert coal into clean liquid fuels is a feasible way to solve the current energy crisis in my country. The key to realizing coal-to-oil conversion lies in the development of high-performance catalysts and the selection of matching reactors. At present, due to the advantages of cobalt-based catalysts and slurry bed reactors in practical applications, they have become a research hotspot. [0003] Fischer-Tropsch (F-T) synthesis is synthesis gas (CO+H 2 ) in the process of reacting to generate hydrocarbons under the action of a ca...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/75B01J23/755B01J23/889B01J23/78B01J23/83C10G2/00C07C1/04C07C9/04
Inventor 孙予罕李晋平肖亚宁谢荣永王春玲王慧赵铁均刘斌孙志强张小莽罗艳宁安杰逻·阿莫里
Owner SHANGHAI ADVANCED RES INST CHINESE ACADEMY OF SCI