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A kind of stable superfine Ft synthesis catalyst and its preparation method and application and Fischer-Tropsch synthesis method

A Fischer-Tropsch synthesis and catalyst technology, applied in chemical instruments and methods, preparation of liquid hydrocarbon mixtures, physical/chemical process catalysts, etc., to achieve high activity stability, increased activity, and improved C5+ selectivity

Active Publication Date: 2022-03-11
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

There are some problems with the stability of the colloidal catalyst under the actual Fischer-Tropsch synthesis reaction conditions

Method used

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  • A kind of stable superfine Ft synthesis catalyst and its preparation method and application and Fischer-Tropsch synthesis method
  • A kind of stable superfine Ft synthesis catalyst and its preparation method and application and Fischer-Tropsch synthesis method
  • A kind of stable superfine Ft synthesis catalyst and its preparation method and application and Fischer-Tropsch synthesis method

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Experimental program
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Embodiment approach

[0045] According to a preferred embodiment of the present invention, the method further includes performing a stabilization treatment on the core-shell structure product obtained in step (2), the manner of the stabilization treatment comprising dispersing the core-shell structure product in a liquid medium, Contact with soluble salts of stabilizers, non-metallic alkaline substances under stabilizing conditions.

[0046] According to this embodiment, the nano-oxide or hydroxide colloid of the IVB group metal element is prepared first, and then nano-cobalt is synthesized in situ outside the colloid, forming cobalt as the shell, and the oxide or hydroxide of the IVB group metal element as the core The core-shell nanostructure is finally stabilized.

[0047] The stabilization reaction is preferably carried out under a reducing atmosphere containing 5-60% by volume of hydrogen and / or CO, wherein the concentration of hydrogen and / or CO can be any concentration within the range of 5%...

Embodiment 1

[0060] (1) Preparation of zirconium hydroxide colloid

[0061] Mix 268 mL of zirconium oxychloride aqueous solution with a concentration of 0.05 mol / L and 3.84 g of urea, heat up to 85°C for 1 hour, cool to 30°C and age for 8 hours, then centrifugally filter, wash with deionized water three times until the filtrate is washed with silver nitrate The solution was detected without precipitation. TEM shows that the average particle size of zirconium hydroxide colloid is 15nm.

[0062] (2)Co / Zr(OH) 4 Preparation of core-shell structure

[0063] Under the protection of inert gas, in the there-necked flask, the above-mentioned zirconium hydroxide colloid was dispersed in 350ml distilled water, then added 30.8g protective agent PVP-30k (Sinopharm Group, analytically pure) and 6.69g cobalt chloride hexahydrate (Bailingwei, Analytical pure), kept at normal temperature for 15 minutes, after the solid was slowly dissolved, 80 g of an aqueous solution containing 5.8 g of potassium boroh...

Embodiment 2

[0069] (1) Titanium hydroxide colloid

[0070] Under the protection of an ice-water bath, 623 mL of TiCl with a concentration of 0.1 mol / L 4 The solution was precipitated with 1.0 wt% ammonia solution to maintain a pH value of 9-11. After aging for 8 hours, it was centrifugally filtered and washed 3 times until the filtrate was detected by silver nitrate solution and no precipitation was formed. TEM shows that the average particle size of titanium hydroxide colloid is 17nm.

[0071] (2)Co / Ti(OH) 4 core-shell structure

[0072] Under the protection of an inert gas, the above-mentioned titanium hydroxide colloid was dispersed in 410ml distilled water, 30.8g protective agent PVP-30k (Sinopharm Group, analytically pure) and 7.0g cobalt acetate tetrahydrate (Bailingwei, analytically pure), and kept for 15 Minutes, after the solid slowly dissolves, use a syringe to quickly inject 80 g of an aqueous solution containing 5.6 g of sodium borohydride (Beijing Reagent, analytically pure)...

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Abstract

A catalyst, its preparation method and application, and a Fischer-Tropsch synthesis method. The catalyst is a core-shell nanostructure, wherein Co and a stabilizer form a shell, and oxides and / or hydroxides of group IVB metal elements form a core. The catalyst provided by the invention greatly improves the utilization rate of cobalt, the stability and catalytic performance of the catalyst, and is applicable to reactors such as microchannels and slurry beds.

Description

technical field [0001] The invention relates to a stable superfine Fischer-Tropsch synthesis catalyst, its preparation method and application, and the Fischer-Tropsch synthesis method. Background technique [0002] As global oil resources become more and more scarce, people pay more and more attention to environmental protection, and more and more people pay more and more attention to using coal and natural gas as raw materials to prepare clean fuels and chemicals. Fischer-Tropsch synthesis technology is one of the key technologies for the clean utilization of coal and natural gas. [0003] The main products of the Fischer-Tropsch synthesis reaction in which syngas is converted into hydrocarbons on catalysts include alkanes and olefins, which can be further processed to obtain high-quality liquid fuels and high value-added chemicals. [0004] At present, the supported cobalt-based catalyst is a kind of Fischer-Tropsch synthesis catalyst with industrial application value. G...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/78C10G2/00
Inventor 吴玉晋超李学锋孙霞阎振楠侯朝鹏夏国富李明丰
Owner CHINA PETROLEUM & CHEM CORP
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