Fischer-Tropsch synthesis catalyst and preparation method thereof

A Fischer-Tropsch synthesis and catalyst technology, which can be used in catalyst activation/preparation, carbon compound catalysts, catalysts, etc., and can solve the problems of difficult reduction of active components, weak interactions, and easy deactivation.

Active Publication Date: 2018-09-04
NANJING UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] At present, the commonly used Fischer-Tropsch synthesis catalysts are mainly based on oxides (such as Al 2 o 3 , SiO 2 etc.) as the carrier iron-based catalyst, but due to the strong force between the carrier and the active component, the active component is difficult to reduce and is not easy to form catalytically active iron carbide, or the iron carbide is easily oxidized to inactive in the reaction process. Silicate and aluminate, etc. lead to unstable catalyst performance and easy deactivation
Recent studies have shown that new carbon materials (such as carbon nanotubes (CNTs), carbon nanofibers (CNFs), ordered mesoporous carbons, and graphenes) with high specific surface area, excellent chemical stability, and tunable pore structure etc.) Catalysts loaded with Fe exhibit higher C 2 = -C 4 = However, the stability of this type of catalyst is still poor. Due to the weak interaction between the carbon material support and the iron active component, this type of catalyst is easy to sinter, which leads to serious deactivation of the catalyst in a short time.

Method used

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  • Fischer-Tropsch synthesis catalyst and preparation method thereof
  • Fischer-Tropsch synthesis catalyst and preparation method thereof

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preparation example Construction

[0032]The present invention also provides the preparation method of the Fischer-Tropsch synthesis catalyst described in the above technical scheme, comprising the steps of:

[0033] (1) Provide nitrogen-doped hollow carbon nanocages;

[0034] (2) impregnating the nitrogen-doped hollow carbon nanocage in an aqueous ethanol solution of a metal compound to obtain a Fischer-Tropsch synthesis catalyst precursor; the metal compound is a metal salt or a metal complex of iron or cobalt;

[0035] (3) The Fischer-Tropsch synthesis catalyst precursor is sequentially subjected to first calcination and passivation to obtain a Fischer-Tropsch synthesis catalyst.

[0036] (4) When the Fischer-Tropsch synthesis catalyst includes the first auxiliary agent or simultaneously includes the first auxiliary agent and the second auxiliary agent, the Fischer-Tropsch synthesis catalyst is heat-treated, and then mixed with an ethanol aqueous solution of a sodium salt or a potassium salt, Obtain the Fis...

Embodiment 1

[0069] (1) Provide nitrogen content of 12at.%, specific surface area of ​​1800m 2 / g, the pore volume is 4.2cm 3 / g, a particle size of 10-30nm nitrogen-doped hollow carbon nanocage (abbreviated as NCNC);

[0070](2) 1.45g ferric ammonium citrate and 15mL ethanol volume concentration are 20% ethanol deionized aqueous solution to mix, obtain the ethanolic aqueous solution of ferric ammonium citrate; 0.60gNCNC is mixed with the ethanolic aqueous solution of described ferric ammonium citrate, in Stir at 150r / min for 0.5h, then stand at room temperature and impregnate for 6h; dry the impregnated product in a drying oven at 80°C for 6h to obtain a Fischer-Tropsch synthesis catalyst precursor (Fe / NCNC precursor for short);

[0071] (3) Under the protection of Ar flow, the Fe / NCNC precursor was heated to 380 ° C for 2 h, and then naturally cooled to room temperature; then passed into an oxygen-containing inert gas with an oxygen volume content of 1% to passivate at room temperature ...

Embodiment 2

[0076] (1) Provide nitrogen content of 12at.%, specific surface area of ​​1800m 2 / g, the pore volume is 4.2cm 3 / g, a particle size of 10-30nm nitrogen-doped hollow carbon nanocage (abbreviated as NCNC);

[0077] (2) 0.784g ferric ammonium citrate is mixed with the ethanol deionized water solution of 20% ethanol volume concentration to obtain the ethanol water solution of ferric ammonium citrate; 0.60g NCNC is mixed with the ethanol water solution of described ferric ammonium citrate, in Stir at 150r / min for 0.5h, then stand at room temperature and impregnate for 6h; dry the impregnated product in a drying oven at 80°C for 8h to obtain a Fischer-Tropsch synthesis catalyst precursor (Fe / NCNC precursor for short);

[0078] (3) Under the protection of Ar flow, the Fe / NCNC precursor was heated to 380 ° C for 2 h, and then naturally cooled to room temperature; then passed into an oxygen-containing inert gas with an oxygen volume content of 1% to passivate at room temperature for ...

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Abstract

The invention provides a Fischer-Tropsch synthesis catalyst. The catalyst comprises a carrier and active components, wherein the carrier adopts nitrogen doped hollow carbon cage; the active componentsare distributed on the surface of the carrier; the active components belong to metallic oxide nanometer particles; metallic oxide adopts iron oxide or cobalt oxide; the carrying capacity of the metallic oxide is 5 to 51wt percent based on the percentage of metal elements to the carrier; the content of nitrogen in the nitrogen doped hollow carbon cage is 5 to 20at percent. The catalyst takes the nitrogen doped hollow carbon cage with high content of nitrogen as the carrier, nitrogen atom in the carrier has anchoring effect on the metallic oxide, the interaction between the carrier and the active components can be improved, moreover the nitrogen atom has alkalinity, the surface alkalinity of the carrier is improved, and meanwhile the Fischer-Tropsch synthesis catalyst with high selectivity,good sintering resistance and high stability is obtained through the combination of the nitrogen atom, the unique structure of the carrier and the active components.

Description

technical field [0001] The invention relates to the technical field of Fischer-Tropsch synthesis, in particular to a Fischer-Tropsch synthesis catalyst and a preparation method thereof. Background technique [0002] Fischer Tropsch Synthesis refers to the synthesis of synthesis gas (H 2 and CO) into hydrocarbons heterogeneous catalytic reaction process, can be used to produce light olefins (C = 2 -C 4 = ), gasoline, diesel, paraffin and other oxygen-containing organic compounds and other products. Syngas raw materials come from a wide range of sources, and can be obtained by converting coal, natural gas, shale gas and biomass raw materials. The indirect conversion of coal, natural gas, shale gas, and biomass raw materials into fuels and chemical products through Fischer-Tropsch synthesis has strong development prospects, especially for the optimal utilization of fossil energy such as coal, natural gas, and shale gas. The adjustment of energy structure has important str...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/24B01J37/02B01J37/08C10G2/00C07C1/04C07C11/04C07C11/06C07C11/08
CPCB01J27/24B01J35/006B01J35/0073B01J37/0201B01J37/08B01J37/088C07C1/0435C07C1/044C07C1/0445C07C2527/24C10G2/332C07C11/04C07C11/06C07C11/08Y02P20/52
Inventor 卓欧高福杰吴强杨立军王喜章胡征
Owner NANJING UNIV
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