A kind of cobalt-based Fischer-Tropsch synthesis catalyst and preparation method thereof

A technology for catalyst and Tropsch synthesis, applied in the field of cobalt-based Fischer-Tropsch synthesis catalyst and its preparation, can solve the problems of reducing methane selectivity, fragile catalyst, and increasing production cost, so as to improve activity and stability, and is conducive to popularization and application , reduce the effect of hydrothermal effect

Active Publication Date: 2014-10-15
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Shi Lihong et al. used silanization to prepare alkyl-modified SiO2 supports in "Journal of Catalysis", No. 11, Volume 28, P999~1002 "Organic Modified Silica and Its Fischer-Tropsch Synthesis Reaction Performance of Supported Cobalt Catalysts". The supported cobalt catalyst was prepared by the equal volume impregnation method, and it was pointed out that the modification of SiO2 by organic groups improved the activity of the catalyst and reduced the methane selectivity, but the product distribution would be affected due to steric hindrance
[0006] The above-mentioned method of modifying the support or adding noble metal additives improves the activity of the catalyst, but the problem of low mechanical strength of the catalyst generally exists
Especially in the slurry bed Fischer-Tropsch synthesis process, the friction and collision between the catalysts and between the catalyst and the reactor are relatively severe, the catalyst is easily broken, and it is difficult to separate the broken catalyst from the Fischer-Tropsch synthetic oil, resulting in poor oil quality decline, and even affect the subsequent processing of synthetic oil
In the prior art, there are few reports on how to improve the anti-wear and collision resistance of Fischer-Tropsch synthesis catalysts. Most of the research focuses on improving the Fischer-Tropsch synthesis process conditions and the activity of the catalyst. In addition, in order to prepare highly active catalysts, it is often necessary to The addition of noble metal additives increases production costs and is not conducive to industry. Therefore, it is of great significance to develop Fischer-Tropsch synthesis catalysts with high activity stability, strong mechanical properties and low cost.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

[0022] Weigh commercially available silica gel (the pore volume is 1.06ml / g, the specific surface area is 386.81m 2 / g, the silica gel used in the following examples) 30g, distilled water was added dropwise to initial moistening, and the volume of consumed water was 48ml. Put the silica gel into the tube furnace, pass in nitrogen for replacement, and then pass in a mixture of ethylene and helium with a volume ratio of 4:1, and the volumetric space velocity of ethylene is 1000h -1 , the feed time was 6 hours, the tube furnace temperature was 700°C, and the temperature was lowered to obtain a modified silica gel carrier with a final catalyst nano-carbon fiber content of 8.5%. Based on the final catalyst zirconium content of 1wt%, weigh 1.41g of zirconium nitrate trihydrate, add distilled water to 48g, wait for complete dissolution, add the above-mentioned modified carrier silica gel for impregnation, aging for 3 hours, and dry at 50°C for 24 hours. Baking at 280°C for 10 hours ...

example 2

[0025] Weigh 30g of commercially available silica gel, add distilled water dropwise until initial moistening, and the volume of consumed water is 48ml. Put the silica gel into the tube furnace, pass in nitrogen for replacement, and then pass in a mixture of ethylene and helium with a volume ratio of 5:1, and the volumetric space velocity of ethylene is 500h -1 , the feed time was 10 hours, the tube furnace temperature was 600° C., and the temperature was lowered to obtain a modified silica gel carrier with a final catalyst nano-carbon fiber content of 12 wt%. Based on the final catalyst zirconium content of 3.1wt%, weigh 4.23g of zirconium nitrate trihydrate, add distilled water to 48g, wait for complete dissolution, add the above-mentioned modified carrier silica gel for impregnation, aging for 3 hours, and dry at 150°C for 8 hours. Baking at 600°C for 2 hours under vacuum or in an inert atmosphere. Based on the final catalyst cobalt content of 35wt% and Ni content of 1.5%, ...

example 3

[0027] Weigh 30g of commercially available silica gel, add distilled water dropwise until initial moistening, and the volume of consumed water is 48ml. Put the silica gel into the tube furnace, pass in nitrogen for replacement, and then pass in a mixture of ethylene and helium with a volume ratio of 3:1, and the volumetric space velocity of ethylene is 1000h -1 , the feed time was 4 hours, the temperature of the tube furnace was 700°C, and the temperature was lowered to obtain a modified silica gel carrier with a final catalyst nano-carbon fiber content of 4.7%. Based on the final catalyst zirconium content of 2wt%, weigh 2.82g of zirconium nitrate trihydrate, add distilled water to 48g, wait for complete dissolution, add the above-mentioned modified carrier silica gel for impregnation, aging for 3 hours, and dry at 80°C for 12 hours. Baking at 350°C for 4 hours under vacuum or in an inert atmosphere. According to the final catalyst cobalt content 20wt%, Ni content 1%, take b...

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PUM

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Abstract

The invention discloses a cobalt-based Fischer-Tropasch synthetic catalyst and a preparation method, the cobalt-based Fischer-Tropasch synthetic catalyst comprises the following components by weight: 1-15% of carbon nanofiber,, 5-35% of active component cobalt, 0.5-6% of metal auxiliary agent X1, 0.1-3% of metal auxiliary agent X2 and the balance of silica. The metal auxiliary agent X1 is one or more of Re, Zr, Hf, Ce, Th and the like, the metal auxiliary agent X2 is one or more of Ni, Mo and W. The preparation method of the cobalt-based Fischer-Tropasch synthetic catalyst comprises the following steps: in-situ loading the carbon nanofiber on a silica gel carrier, then an immersion method is employed for loading the metal auxiliary agent X1, the metal auxiliary agent X2 and the active component Co. The cobalt-based Fischer-Tropasch synthetic catalyst has the advantages of good wear resistance, strong collision resistance capability, low cost and high activicity stability, and is adapted to the slurry bed or boiling bed ft synthesis reaction.

Description

technical field [0001] The invention relates to a cobalt-based Fischer-Tropsch synthesis catalyst and a preparation method thereof, in particular to a cobalt-based Fischer-Tropsch synthesis catalyst with strong anti-collision ability and high activity stability and a preparation method thereof. Background technique [0002] Fischer-Tropsch synthesis refers to synthesis gas (CO+H 2 ) on the catalyst to catalyze the reaction of synthesizing hydrocarbon liquid fuel. With the increasing depletion of petroleum resources, the preparation of liquid fuels by Fischer-Tropsch synthesis has attracted more and more attention from all over the world. Catalyst is one of the key technologies of Fischer-Tropsch synthesis reaction. In the research of Fischer-Tropsch catalyst in the past 80 years, it has been found that Fe, Co and Ru are metals with Fischer-Tropsch activity. High activity, when the reaction temperature is high, the catalyst is prone to carbon deposition and poisoning, and t...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/755B01J23/882B01J23/888B01J32/00C07C1/04C07C9/04
Inventor 李杰袁长富张舒冬宋喜军张喜文倪向前
Owner CHINA PETROLEUM & CHEM CORP
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