Method for controllable modulating of distribution of Fischer-Tropsch reaction product through Co-based catalyst

A Fischer-Tropsch reaction and catalyst technology, applied in chemical instruments and methods, catalyst activation/preparation, physical/chemical process catalysts, etc., can solve the problems of improving the difficulty of product separation and purification and catalyst recovery process, and achieve sensitive and high-speed product switching. Effects of reactivity, high olefin selectivity

Active Publication Date: 2019-03-29
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the modification agent (organic, inorganic acid-base and metal salt, etc.) added to the reaction system in this method increases the process difficulty of product separation and purification and catalyst recovery.
[0005] It has not been reported that a simple and efficient controllable adjustment of product distribution can be achieved on a catalyst

Method used

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  • Method for controllable modulating of distribution of Fischer-Tropsch reaction product through Co-based catalyst
  • Method for controllable modulating of distribution of Fischer-Tropsch reaction product through Co-based catalyst

Examples

Experimental program
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Effect test

Embodiment 1

[0019] 0.74g Co(NO 3 ) 2 ·6H 2 O, 0.04mL mass fraction is 50% Mn(NO 3 ) 3 4H 2 O aqueous solution, 0.05gZr(NO 3 ) 4 ·5H 2 O, 0.015g Ce(NO 3 ) 3 ·6H 2 O was dissolved in 20mL of water and stirred evenly to make a mixed solution. Weigh 0.85gSiO2 2 Carrier, mix the mixture with the carrier evenly, impregnate in vacuum at room temperature for 5 hours, separate solid and liquid, wash with water, and dry at 100°C for 12 hours to obtain a solid powder; mix the obtained solid powder with 0.5g of phenylalanine, and the mixed powder is heated at 500°C Calcined for 5 hours, ground, pressed into tablets, and sieved to obtain 15%Co-1%Mn-1%Zr-0.5%Ce-0.05%N-0.1%C / SiO 2 catalyst.

[0020] 0.5g 15%Co-1%Mn-1%Zr-0.5%Ce-0.05%N-0.1%C / SiO 2 The catalyst is mixed with an equal volume of quartz sand, placed in a fixed-bed reactor, and pure H 2 Gas (H 2 =99.9%), heated up to 450°C at a rate of 5°C / min, maintained for 5h, then cooled to 180°C, fed into synthesis gas, and carried out the...

Embodiment 2

[0024] 0.50g Co 2 (CO) 8 , 0.09g Mn(Ac) 2 , 0.047g Zr(NO 3 ) 3 ·6H 2 O, 0.03g Ce(NO 3 )3 ·6H 2 O was dissolved in 20mL of ethanol and stirred evenly to make a mixed solution. Weigh 1.0g SiO2 2 Carrier, mix the mixed solution with the carrier evenly, impregnate in vacuum at room temperature for 5 hours, separate solid and liquid, wash with water, and dry at 100°C for 12 hours to obtain a solid powder; mix the obtained solid powder with 1.0g of phenylalanine, and the mixed powder is heated at 500°C Roast for 5h, grind, press into tablets, and sieve to get 20%Co-2%Mn-1%Zr-1%Ce-0.1%N-0.1%C / SiO 2 catalyst.

[0025] 0.5g 20%Co-2%Mn-1%Zr-1%Ce-0.1%N-0.1%C / SiO 2 The catalyst is mixed with an equal volume of quartz sand, placed in a fixed-bed reactor, and pure H 2 Gas (H 2 =99.9%), heated up to 450°C at a rate of 5°C / min, maintained for 5h, then cooled to 180°C, fed into synthesis gas, and carried out the Fischer-Tropsch reaction of synthesis gas to hydrocarbon products acco...

Embodiment 3

[0029] 0.50g Co(NO 3 ) 2 ·6H 2 O, 0.02mL 50% Mn(NO 3 ) 3 4H 2 O, 0.10g Zr(NO 3 ) 4 ·5H 2 O, 0.031g Ce(NO 3 ) 3 ·6H 2 O was dissolved in 20mL of water and stirred evenly to make a mixed solution. Weigh 1.0g Al 2 o 3 Carrier, mix the mixed liquid with the carrier evenly, impregnate in vacuum at room temperature for 5 hours, separate solid and liquid, wash with water, and dry at 100°C for 5 hours to obtain a solid powder; mix the obtained solid powder with 0.5g melamine, and roast the mixed powder at 500°C for 5 hours, Grinding, tableting, and sieving to obtain 10%Co-0.5%Mn-2%Zr-1%Ce-0.08%N-0.05%C / Al 2 o 3 catalyst.

[0030] 0.5g 10%Co-0.5%Mn-2%Zr-1%Ce-0.08%N-0.05%C / Al 2 o 3 The catalyst is mixed with an equal volume of quartz sand, placed in a fixed-bed reactor, and pure H 2 Gas (H 2 =99.9%), heated up to 450°C at a rate of 5°C / min, maintained for 5h, then cooled to 180°C, fed into synthesis gas, and carried out the Fischer-Tropsch reaction of synthesis gas to...

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Abstract

The invention discloses a method for controllable modulating of distribution of a Fischer-Tropsch reaction product through a Co-based catalyst. The Co-based catalyst in the method is prepared from thefollowing active components in percentage by mass: 10 to 30 percent of Co, 0.1 to 10 percent of Mn, 0.1 to 10 percent of Zr, 0.1 to 10 percent of Ce, 0.02 to 0.1 percent of C, 0.02 to 0.1 percent ofN and the balance of O, and silicon oxide or aluminum oxide is used as a carrier. The catalyst is prepared by adopting an impregnation method, accurate modulation on the distribution of a synthesis gas Fischer-Tropsch reaction product can be realized through simple regulation on reaction temperature, pressure and air speed, i.e., high-selectivity synthesis of low carbon olefin (C2-C4<=>), alpha-olefin (alpha-C>=4<=>), gasoline component (C5-C11), diesel component (C10-C20) and solid wax (C20+) can be respectively realized. The catalyst prepared by the invention has the characteristics of highactivity, good long-period stability, high target product yield and the like; the catalyst has the advantages of simple preparation, wide raw material source and small amplification effect of large-scale preparation.

Description

technical field [0001] The invention belongs to the technical field of carbon monoxide hydrogenation, and in particular relates to a method for controllably adjusting the distribution of Fischer-Tropsch reaction products with a Co-based catalyst. Background technique [0002] Fischer-Tropsch synthesis is the synthesis of coal, natural gas, biomass, etc. through synthesis gas (CO+H 2 ) into clean liquid fuels or high value-added chemicals plays an important role in the clean and efficient utilization of coal resources. However, Fischer-Tropsch synthesis products are complex and have a wide carbon number distribution (C 1 -C 120 ) and is limited by Anderson-Schulz-Flory (ASF) polymerization kinetics, poor selectivity to specific target products such as olefins, gasoline, diesel oil. Therefore, designing and synthesizing catalysts with high stability and high activity, which can controllably adjust the target product with high selectivity, is the key and difficulty in the cu...

Claims

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Application Information

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IPC IPC(8): B01J27/24B01J37/02B01J37/08B01J35/10C10G2/00
CPCC10G2/332B01J27/24B01J37/0201B01J37/082B01J35/617B01J35/638B01J35/653B01J35/657B01J35/613B01J35/651B01J35/635B01J35/633B01J35/615B01J35/647
Inventor 刘忠文朱敏莉宋永红刘昭铁
Owner SHAANXI NORMAL UNIV
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