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A kind of catalyst of modified silicon dioxide and its loaded cobalt, preparation method and application

A silica and catalyst technology, applied in the field of modified silica and cobalt-supported catalysts and preparations, can solve the problems of pore volume reduction, difficulty in reduction, and inactivity, etc., so as to improve the degree of dispersion and reduction, increase Dispersion degree and reduction degree, effect of improving activity and stability

Active Publication Date: 2017-08-25
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

However, studies have shown [Shi Lihong, Li Xiaofeng, Li Debao, Sun Yuhan, Deactivation behavior of cobalt-based catalysts in the Fischer-Tropsch reaction, Journal of Catalysis, 2010, 31: 1483-1488] [Shi Lihong, Li Xiaofeng, Li Debao, Sun Yuhan , SiO 2 The effect of silylation of cobalt-based catalysts on the catalytic performance of Fischer-Tropsch synthesis, Journal of Fuel Chemistry, 2012, 40: 737-740], under certain reaction conditions, metal cobalt and silica support will interact, Generates cobalt silicate that is not easy to reduce and has no activity, and leads to a decrease in the specific surface area of ​​the catalyst, a decrease in pore volume, and a smaller pore channel. At the same time, it leads to a decrease in the content of effective active metal cobalt, and directly leads to a decrease in the activity and stability of the Fischer-Tropsch reaction.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] A certain amount of Cu(NO 3 ) 2 ·3H 2 O. Methyl orthosilicate and citric acid were dissolved in ethanol, and the mixed solution was stirred and evaporated to a certain volume in a 60°C water bath, and then the equal volume was impregnated in a certain amount of silica (Shanghai Ximeng, active silica, ratio Surface area is 200m 2 g -1 , pore volume 0.35cm 3 g -1 , average pore diameter 8nm), where Cu 2+ : Methyl Orthosilicate : Citric Acid : SiO 2 =2:1:1.5:7.5 (mol / mol) to obtain the carrier precursor; after drying the carrier precursor at 110°C for 12h, transfer it to a muffle furnace, and roast it at 750°C for 4h to obtain modified silica Cu 2 SiO 4 -SiO 2 ;Press Co 3 o 4 Accounting for 25(wt.)% of the final catalyst, weigh Co(NO 3 ) 2 ·6H 2 O, prepare a solution, impregnate the above-mentioned modified silica with equal volume, dry at 100°C for 8h, transfer to a muffle furnace, and roast at 350°C for 6h to obtain the final catalyst Co 3 o 4 / Cu 2 SiO ...

Embodiment 2

[0022] A certain amount of Zn(NO 3 ) 2 ·6H 2 O, tetraethyl orthosilicate and tartaric acid are dissolved in ethanol, after stirring and evaporating the mixed solution in a water bath at 70°C to a certain volume, the equal volume is impregnated in a certain amount of silica (Shandong Ruichuan Silicon Industry, activated silica, The specific surface area is 350m 2 g -1 , pore volume 0.9cm 3 g -1 , average pore size 5.5nm), where Zn 2+ : Ethyl Tetrasilicate : Tartaric Acid : SiO 2 =2:1:1:6.25 (mol / mol) to obtain the carrier precursor; after drying the carrier precursor at 150°C for 10h, transfer it to a muffle furnace, and roast it at 650°C for 6h to obtain the modified silica Zn 2 SiO 4 -SiO 2 . Press Co 3 o 4 Accounting for 35(wt.)% of the final catalyst, weigh Co(NO 3 ) 2 ·6H 2 O, prepare the solution, impregnate the above-mentioned modified silica in equal volume, dry at 90°C for 18h, transfer to the muffle furnace, and roast at 250°C for 10h to obtain the fina...

Embodiment 3

[0025] A certain amount of Ni(NO 3 ) 2 ·6H 2 O, propyl orthosilicate and malic acid are dissolved in ethanol, and after the mixed solution is stirred and evaporated to a certain volume in a water bath at 80° C., an equal volume is impregnated in a certain amount of silicon dioxide (Degussa Company, active silicon dioxide, The specific surface area is 400m 2 g -1 , pore volume 1.0cm 3 g -1 , average pore diameter 8nm), where Ni 2+ : Orthopropyl silicate: Malic acid: SiO 2 =2:1:1.5:15 (mol / mol) to obtain a carrier precursor; after drying the carrier precursor at 80°C for 24h, transfer it to a muffle furnace, and roast it at 700°C for 10h to obtain a modified silica Ni 2 SiO 4 -SiO 2 . Press Co 3 o 4 Accounting for 15 (wt.)% of the final catalyst, weigh C 4 h 6 o 4 ·Co·4H 2 O, prepare a solution, impregnate the above-mentioned modified silica with equal volume, dry at 120°C for 2h, transfer to a muffle furnace, and roast at 300°C for 8h to obtain the final catalys...

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PUM

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Abstract

A modified silicon dioxide and its cobalt-loaded catalyst, its preparation method and application. A Fischer-Tropsch synthesis catalyst for modified silicon dioxide and its loaded cobalt, characterized in that the catalyst is made up of tricobalt tetroxide and modified silicon dioxide, wherein the mol ratio of silicate and silicon dioxide in the modified silicon dioxide is 1: 6.25~25, the weight composition of tricobalt tetroxide accounts for 10%~40% of the final catalyst. The catalyst of the invention has the advantages of high activity and high stability when used in Fischer-Tropsch synthesis reaction.

Description

technical field [0001] The invention relates to a catalyst, in particular to a modified silicon dioxide and a cobalt-supported catalyst, a preparation method and an application thereof. Background technique [0002] Fischer-Tropsch synthesis is an important way to convert synthesis gas, coal bed methane, and natural gas into liquid fuels, increasing the C 5 + Hydrocarbon selectivity and methane selectivity reduction are the main research goals of Fischer-Tropsch synthesis, and the key to realize this goal is the research and development of high-activity and high-selectivity Fischer-Tropsch synthesis catalysts. Cobalt-based catalysts have become an important catalyst system for Fischer-Tropsch synthesis due to their high activity, high selectivity to heavy linear hydrocarbons, and low water-gas shift. For supported cobalt-based catalysts, the surface properties of the support affect the dispersion and reduction of cobalt, the interaction between cobalt and the support, and ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/75B01J23/80B01J23/755C10G2/00
Inventor 李德宝刘岩贾丽涛侯博刘亚纯肖勇
Owner 中科潞安能源技术有限公司
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