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Fischer-Tropsch synthesis catalyst and preparation method and application thereof

A Fischer-Tropsch synthesis and catalyst technology, which is used in catalyst activation/preparation, chemical instruments and methods, preparation of liquid hydrocarbon mixtures, etc., can solve the problems of poor product selectivity, unfeasible, low activity, etc., and achieve mild production conditions. , low production cost, and the effect of improving the structure

Inactive Publication Date: 2010-10-27
SYNFUELS CHINA TECH CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, no structural additives are added to the catalyst, and the catalyst has poor anti-wear ability, so it is not feasible for practical application, and the index data such as catalyst strength, space-time yield and production capacity cannot be provided.
U.S. Patent US4340503 provides a Fe-Mn fixed bed catalyst supported by molecular sieves, but the methane selectivity of the catalyst is high and the activity is low
[0005] Chinese patent CN1817451A provides a precipitation-type Fe / Cu / Cr / K / Na catalyst suitable for high-temperature fluidized bed Fischer-Tropsch synthesis operation, but the activity of the catalyst is low, at 350 ° C, 1400-1450ml / ml Catalyst / h, 2.5MPa conditions, with H 2 The synthesis gas with a / CO ratio of 3.0 is used as the raw material gas for evaluation, but the conversion rate of the synthesis gas is low (<50%), the product selectivity is poor, and the methane selectivity is greater than 10%
[0006] At present, there is no patent report on a high-performance catalyst with high activity, reasonable product distribution, and strong wear resistance that is particularly suitable for advanced slurry-bed Fischer-Tropsch synthesis. At the same time, the existing slurry-bed catalysts can only be used at relatively low temperatures. Operation (220-240°C), the operating temperature cannot be increased, which is not conducive to improving the overall energy conversion efficiency of the Fischer-Tropsch synthesis process

Method used

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

Examples

Experimental program
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Effect test

Embodiment 1

[0038] 2000 kg Fe(NO 3 ) 3 9H 2 O, 36 kilograms of 50wt% Mn (NO 3 ) 3 Aqueous solution, 10.65 kg Cr(NO 3 ) 3 ·3H 2 O and 6.3 kg of Zn(NO 3 ) 2 ·6H 2 O was dissolved in 1050 kg of deionized water, and after fully dissolved, SiO was added to the mixed salt solution 2 45 kg of silica sol with a content of 30 wt%, Al 2 o 3 Content is 1.2 kilograms of aluminum sols of 25wt%, this solution is warmed up to 50 ℃ under stirring, and the total concentration of nitrate in the gained mixed solution is 12.22wt%, and the weight ratio of each component in the described mixed salt solution is Fe: Mn :Cr:Zn:SiO 2 :Al 2 o 3 =100:2.0:0.5:0.5:4.88:0.11.

[0039] Prepare 10.0wt% ammonia solution at the same time and heat up to 30°C. Preset 1500 kg of deionized water in the precipitation tank and preheat it to 50°C. After the temperature rises to the set temperature, add the salt solution and ammonia solution Co-current co-precipitation, keeping the temperature of the slurry in the ...

Embodiment 2

[0043] 2000 kg Fe(NO 3 ) 3 9H 2 O, 324 kg of 50wt% Mn (NO 3 ) 3 Aqueous solution, 127.5 kg Cr(NO 3 ) 3 ·3H 2 O and 201.5 kg of Zn(NO 3 ) 2 ·6H 2 O was dissolved in 1360 kg of deionized water, and after fully dissolved, Al was added to the mixed salt solution 2 o 3 Content is 24.0 kilograms of silica sols of 25.0wt%, this solution is warmed up to 90 ℃ under stirring, and the total concentration of nitrate in the gained mixed solution is 39.6wt%, and the weight ratio of each component in the described salt solution is Fe: Mn :Cr:Zn:Al 2 o 3 =100:20.0:5.0:15.0:2.0.

[0044] Prepare 20.0wt% ammonia solution at the same time and heat up to 60°C. Preset 1500 kg of deionized water in the precipitation tank and preheat to 90°C. After the temperature rises to the set temperature, add the salt solution and ammonia solution For co-current co-precipitation, the temperature of the slurry in the precipitation tank is kept at 90° C., the pH of the mixed synthetic slurry is 9.0±...

Embodiment 3

[0048] 2000 kg Fe(NO 3 ) 3 9H 2 O, 270 kg of 50wt% Mn (NO 3 ) 3 Aqueous solution, 127.5 kg Cr(NO 3 ) 3 ·3H 2 O is dissolved in 2500 kilograms of deionized water, after fully dissolving, this solution is warmed up to 80 ℃ under stirring, and the total concentration of nitrate in the gained mixed salt solution is 29.5wt%, and the weight ratio of each component in this salt solution is Fe:Mn:Cr=100:15.0:6.0.

[0049] Prepare 12.5wt% ammonia solution at the same time and heat up to 40°C. Preset 1500 kg of deionized water in the precipitation tank and preheat it to 80°C. After the temperature rises to the set temperature, add the salt solution and ammonia solution For co-precipitation, the temperature of the slurry in the precipitation tank is kept at 80° C., the pH of the mixed synthetic slurry is 8.5±0.3, and the mixing and co-precipitation process is completed within 30 minutes. Leave to age for 30 minutes.

[0050] The aged slurry was washed with deionized water until ...

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Abstract

The invention relates to a micro-spherical iron-based catalyst which contains transition metal additive, has high performance and is applicable to the Fischer-Tropsch synthesis of a slurry reactor, and a preparation method and the application thereof; and the weight composition of the catalyst is as follows: Fe: transition metal additive M: structural additive (SiO2 or / and Al2O3):K=100:1 to 50:1 to 50:0.5 to 10. The preparation method of the catalyst comprises the following steps: adding the structural additive into Fe / M mixed nitrate solution, co-precipitating with ammonia to prepare slurry; filtering and washing the slurry to obtain a filter cake; and adding the required amount of K additive and water into the filter cake, beating, spraying, drying and calcining to obtain the Fischer-Tropsch synthesis iron-based catalyst of the micro-spherical slurry reactor. The catalyst prepared by the method has good anti-wear performance, the distribution scope of the grain size of the catalyst is narrow, the synthesis gas conversion capability is high, the product selectivity is good and the time-space yield is high, and the Fischer-Tropsch synthesis reaction of the slurry reactor can be carried out within a wider scope of temperature simultaneously.

Description

technical field [0001] The present invention relates to a Fischer-Tropsch synthesis catalyst capable of performing slurry bed Fischer-Tropsch synthesis (Fischer-Tropsch synthesis, referred to as F-T synthesis) with high performance in a wide temperature range, a preparation method thereof and the preparation method of the catalyst in a slurry bed Fischer-Tropsch synthesis. applications in synthesis. Background technique [0002] Fischer-Tropsch synthesis is the synthesis gas (CO+H 2 ) into hydrocarbon products and other chemicals. Typical catalysts for syngas conversion involve Group VIII transition metals such as iron, cobalt, ruthenium and nickel. Among the catalysts of the above systems, ruthenium-based catalysts are expensive, and the methanation reaction of nickel-based catalysts is too serious. Only iron and cobalt-based catalysts have industrial development and application value. Among them, cobalt-based catalysts are suitable for H due to their weak water-gas shif...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/889B01J23/86B01J35/08B01J37/03B01J8/22C07C1/04C10G2/00
CPCC10G2/342B01J23/80B01J23/8892B01J37/031B01J23/862B01J37/0045B01J23/002C10G2300/70B01J35/023B01J2523/00C10G2/332B01J2523/13B01J2523/27B01J2523/31B01J2523/67B01J2523/72B01J2523/842B01J2523/41
Inventor 杨勇吴宝山李永旺相宏伟
Owner SYNFUELS CHINA TECH CO LTD
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