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Fischer-Tropsch Synthesis Method of Cobalt-Based Catalyst for Improved Fischer-Tropsch Synthesis by Simultaneous Roasting Reduction in Situ Hydrogen

A technology of cobalt-based catalyst and Fischer-Tropsch synthesis, which is applied in the preparation of liquid hydrocarbon mixtures, the petroleum industry, and the treatment of hydrocarbon oil. It can solve the problems of high sensitivity to temperature and pressure, decreased reaction rate, and narrow operating range. Easy to achieve, good dispersion, simple operation

Active Publication Date: 2018-03-02
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

Compared with the iron-based slurry bed process, the cobalt-based fixed-bed process has the advantages of long carbon chain, low methane selectivity, good stability, and low water-gas shift reaction in the reaction process. 2 The sensitivity of / CO ratio, temperature and pressure is higher than that of iron-based catalysts, the operating range is narrow, and the requirements for devices are high. Cobalt catalysts must be operated at low temperatures to obtain suitable selectivity, resulting in a decrease in reaction rate. The space-time yield is higher than that of iron. The base catalyst is low, which limits its production and application, and finally abandons the cobalt-based fixed bed process and chooses the iron-based slurry bed process

Method used

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  • Fischer-Tropsch Synthesis Method of Cobalt-Based Catalyst for Improved Fischer-Tropsch Synthesis by Simultaneous Roasting Reduction in Situ Hydrogen

Examples

Experimental program
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Effect test

Embodiment 1

[0016] Prepare the cobalt-based catalyst precursor according to the method in Example 7 of patent ZL 201210160020.6: take pseudo-boehmite according to the amount of alumina accounting for 89 (wt)% of the final catalyst, and prepare 4.5mol / L Na at the same time 2 CO 3 solution, the two are mixed to adjust the pH of the pseudo-boehmite slurry to 8.5. Account for 1.0(wt)% of the final catalyst by barium oxide, prepare 1.0mol / L of Ba(NO 3 ) 2 The solution was added dropwise to the pseudo-boehmite lye while stirring with the above lye, kept at 55°C, and the pH at the end point was controlled to be 8.5. After the precipitation was completed, it was statically aged for 5 hours, washed and filtered until there was no impurity. The filter cake was dried at 80°C for 8h, and then calcined at 450°C for 9h to prepare the catalyst carrier. Weigh Co(NO 3 ) 2 ·6H 2 O and PdCl 2 According to the equal-volume impregnation method, measure deionized water, prepare a mixed salt solution and...

Embodiment 2

[0019] Prepare the cobalt-based catalyst precursor according to the method in Example 5 of patent ZL 201010539363.4: prepare a modified zinc oxide-supported cobalt catalyst according to the ratio of Co:W:Zn=16:43:39. Prepare 1.0M ethanol solution of zinc nitrate salt, prepare 1.2M aqueous ammonia solution as a precipitant, precipitate zinc salt at pH=7.5, 50°C, wash the filter cake to neutrality, dry at 110°C, and roast at 400°C for 5 After hours, the obtained sample was broken into powders below 200 mesh for use. According to the set ratio, ammonium paratungstate aqueous solution was prepared, tungsten was loaded on the obtained sample by the equal volume method, dried at 115°C, and roasted at 480°C for 2 hours, and the obtained sample was broken into powder below 200 mesh for use. According to the amount of Ni accounting for 7wt%, Cr accounting for 8% and cobalt in the final catalyst, a mixed solution of nickel nitrate, chromium nitrate and cobalt nitrate was prepared, and t...

Embodiment 3

[0022] Prepare the cobalt-based catalyst precursor according to the method in Example 1 of patent ZL 201210050261.5: add 4500g of deionized water to reactor A, and add 500g of γ-Al after turning on the stirring motor 2 o 3 Mix the powder, add hydrochloric acid and continue mixing until the pH value of the slurry is 5.0. Add 5500g of deionized water to reactor B, and add 500g of γ-Al 2 o 3 powder, after stirring and mixing evenly, mix the slurry in AB two kettles evenly, heat to 80°C and let it stand for 1 hour, continue to stir, add alkaline silica sol, so that the mass ratio of silicon to aluminum is SiO 2 :Al 2 o 3 =20:80, continue to stir and mix evenly. Slowly add the prepared 0.1mol / L zirconium oxychloride solution into the above slurry. The temperature of the slurry is controlled at 25°C. Medium SiO 2 、Al 2 o 3 And 0.5% of the total mass of zirconium oxychloride. The obtained granular powder material was calcined at 650° C. for 6 hours, cooled and cooled for la...

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Abstract

The invention discloses a Fischer-Tropsch synthesis method for modifying a modified Fischer-Tropsch synthesis cobalt-based catalyst through in-situ hydrogenation synchronous calcination and reducing. According to the method, after a precursor of a pre-calcination cobalt-based catalyst to be modified is formed, a fixed bed reactor is filled with the precursor of the pre-calcination cobalt-based catalyst to be modified, the precursor of the cobalt-based catalyst to be modified in the fixed bed reactor is synchronously calcined and reduced to obtain the modified cobalt-based catalyst through reducing, then the reduced modified cobalt-based catalyst is cooled to be 50 DEG C or below, synthesis gas is injected, and then an in-situ Fischer-Tropsch synthesis reaction is performed. The method has the advantage that the catalytic activity of Fischer-Tropsch synthesis can be substantially improved.

Description

technical field [0001] The invention relates to a Fischer-Tropsch synthesis method for preparing a Fischer-Tropsch synthesis cobalt-based catalyst by roasting a cobalt-containing precursor in situ. Background technique [0002] Fischer-Tropsch synthesis is a chemical process that converts synthesis gas into higher hydrocarbons, and is one of the most important ways to efficiently convert and utilize non-petroleum carbon-containing resources (natural gas, coal, residual oil, and biomass, etc.). Syngas generates a series of higher hydrocarbons with different carbon numbers under the action of catalysts (C 1 to C 200 ), mainly straight-chain alkanes, and some low-carbon olefins and alcohols are obtained at the same time. The initial product is further processed (such as separation, hydrocracking or hydroisomerization, etc.) to obtain certain specifications of gasoline, diesel and other oil fuels, as well as chemicals such as ethylene, propylene, lubricating oil and paraffin. ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G2/00
CPCC10G2/331C10G2/341C10G2300/70
Inventor 李德宝刘岩贾丽涛侯博
Owner 中科潞安能源技术有限公司