Method for preparing low-cost high-activity cobalt-based Fischer-Tropsch synthetic catalyst

Abstract

The invention discloses a method for preparing a low-cost high-activity cobalt-based Fischer-Tropsch synthetic catalyst, which comprises the following steps of: firstly carrying out surface modification on a silica gel carrier by using a saccharic acidic solution; and then, loading a metal promoter X1, a metal promoter X2 and an active component Co (cobalt), wherein the metal promoter X1 is one or more of Re, Zr, Hf, Ce and Th, and the metal promoter X2 is one or more of Ni, Mo and W. The catalyst prepared through the method disclosed by the invention has high activity, good stability and lowcost; and the preparation method is simple and is applicable to industrial application.

Description

technical field

[0001] The invention relates to a preparation method of a low-cost and high-activity cobalt-based Fischer-Tropsch synthesis catalyst, in particular to a low-cost, high-activity and stable cobalt-based Fischer-Tropsch catalyst which uses modified silica gel as a carrier and is modified by adding metal additives. Method for the preparation of synthetic catalysts. Background technique

[0002] Fischer-Tropsch synthesis refers to synthesis gas (CO+H 2 ) Catalyze the reaction of synthesizing hydrocarbon liquid fuel on the catalyst. 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 te...

Examples

example 1

[0018] Weigh commercially available silica gel (pore volume is 1.06ml / g, specific surface area is 386.81m 2 / g, the following examples all use the silica gel) 30g, distilled water is added dropwise to initial moistening, and the volume of consumed water is 48ml. The aqueous solution with a sucrose mass concentration of 5% was adjusted to a pH value of 3 with sulfuric acid, and the mass ratio of the silica gel to the mixed solution was 1:4, and the silica gel and the sucrose acidic solution were fully mixed and stirred for 2 hours at a temperature of 60°C. Dry at 60°C for 24 hours, and then bake at 800°C for 10 hours in vacuum or nitrogen atmosphere.

[0019] 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. °C for 10 hours. According to the final cata...

example 2

[0022] Weigh commercially available silica gel, add distilled water dropwise until initial moistening, and the volume of consumed water is 48ml. The aqueous solution with a sucrose mass concentration of 15% was adjusted to a pH value of 2 with hydrochloric acid, and the mass ratio of the silica gel to the mixed solution was 1:9, and the silica gel and the sucrose acidic solution were fully mixed and stirred at a temperature of 70° C. for 3.5 hours. Dry at 100°C for 16 hours, then vacuum bake at 900°C for 8 hours.

[0023]Based on the final catalyst zirconium content of 3wt%, 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. °C for 2 hours. Based on the final catalyst cobalt content of 35wt% and Ni content of 1.5%, the active metal and auxiliary agent Ni are impregnated in two steps. The first step is to w...

example 3

[0025] Weigh commercially available silica gel, add distilled water dropwise until initial moistening, and the volume of consumed water is 48ml. The aqueous solution with a sucrose mass concentration of 20% was adjusted to a pH value of 1 with sulfuric acid, and the mass ratio of the silica gel to the mixed solution was 1:12, and the silica gel and the sucrose acidic solution were fully mixed and stirred for 5 hours at a temperature of 80°C. Dry at 120°C for 8 hours, then vacuum bake at 1000°C for 4 hours.

[0026] 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. °C for 4 hours. According to the final catalyst cobalt content 20wt%, Ni content 1%, weigh 29.64g of cobalt nitrate hexahydrate and nickel nitrate hexahydrate 1.48g, add distilled water to 48...

technical field

[0001] The invention relates to a preparation method of a low-cost and high-activity cobalt-based Fischer-Tropsch synthesis catalyst, in particular to a low-cost, high-activity and stable cobalt-based Fischer-Tropsch catalyst which uses modified silica gel as a carrier and is modified by adding metal additives. Method for the preparation of synthetic catalysts. Background technique

[0002] Fischer-Tropsch synthesis refers to synthesis gas (CO+H 2 ) Catalyze the reaction of synthesizing hydrocarbon liquid fuel on the catalyst. 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 te...

Examples

example 1

[0018] Weigh commercially available silica gel (pore volume is 1.06ml / g, specific surface area is 386.81m 2 / g, the following examples all use the silica gel) 30g, distilled water is added dropwise to initial moistening, and the volume of consumed water is 48ml. The aqueous solution with a sucrose mass concentration of 5% was adjusted to a pH value of 3 with sulfuric acid, and the mass ratio of the silica gel to the mixed solution was 1:4, and the silica gel and the sucrose acidic solution were fully mixed and stirred for 2 hours at a temperature of 60°C. Dry at 60°C for 24 hours, and then bake at 800°C for 10 hours in vacuum or nitrogen atmosphere.

[0019] 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. °C for 10 hours. According to the final cata...

example 2

[0022] Weigh commercially available silica gel, add distilled water dropwise until initial moistening, and the volume of consumed water is 48ml. The aqueous solution with a sucrose mass concentration of 15% was adjusted to a pH value of 2 with hydrochloric acid, and the mass ratio of the silica gel to the mixed solution was 1:9, and the silica gel and the sucrose acidic solution were fully mixed and stirred at a temperature of 70° C. for 3.5 hours. Dry at 100°C for 16 hours, then vacuum bake at 900°C for 8 hours.

[0023]Based on the final catalyst zirconium content of 3wt%, 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. °C for 2 hours. Based on the final catalyst cobalt content of 35wt% and Ni content of 1.5%, the active metal and auxiliary agent Ni are impregnated in two steps. The first step is to w...

example 3

[0025] Weigh commercially available silica gel, add distilled water dropwise until initial moistening, and the volume of consumed water is 48ml. The aqueous solution with a sucrose mass concentration of 20% was adjusted to a pH value of 1 with sulfuric acid, and the mass ratio of the silica gel to the mixed solution was 1:12, and the silica gel and the sucrose acidic solution were fully mixed and stirred for 5 hours at a temperature of 80°C. Dry at 120°C for 8 hours, then vacuum bake at 1000°C for 4 hours.

[0026] 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. °C for 4 hours. According to the final catalyst cobalt content 20wt%, Ni content 1%, weigh 29.64g of cobalt nitrate hexahydrate and nickel nitrate hexahydrate 1.48g, add distilled water to 48...

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