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A method for controlling the distribution of Fischer-Tropsch reaction products with CO-based catalysts

A Fischer-Tropsch reaction and catalyst technology, which is applied in chemical instruments and methods, catalyst activation/preparation, physical/chemical process catalysts, etc., can solve the problems of improving product separation and purification and catalyst recovery process difficulty, and achieve corresponding sensitive and efficient product switching. The effect of stable catalyst performance and high olefin selectivity

Active Publication Date: 2022-03-04
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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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  • A method for controlling the distribution of Fischer-Tropsch reaction products with CO-based catalysts
  • A method for controlling the distribution of Fischer-Tropsch reaction products with CO-based catalysts

Examples

Experimental program
Comparison scheme
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 controllably adjusting the distribution of Fischer-Tropsch reaction products by a Co-based catalyst. In the method, the mass percent content of each element in the active component of the Co-based catalyst is: Co 10%-30%, Mn 0.1% ~10%, Zr 0.1%~10%, Ce 0.1%~10%, C 0.02%~0.1%, N 0.02%~0.1%, the rest is oxygen element; the carrier is silicon oxide or aluminum oxide. The catalyst is prepared by the impregnation method, and by simply adjusting the reaction temperature, pressure and space velocity, the precise control of the distribution of hydrocarbon products in the Fischer-Tropsch synthesis of synthesis gas can be realized, including the realization of low-carbon olefins (C 2 -C 4 ＝ ), α‑olefins (α‑C ≥4 ＝ ), gasoline components (C 5 -C 11 ), diesel components (C 10 -C 20 ) and solid wax (C 20+ ) highly selective synthesis. The catalyst has the characteristics of high activity, good long-term stability, high yield of the target product, etc., the catalyst is simple to prepare, the source of raw materials is wide, and the amplification effect of large-scale preparation is small.

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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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/24B01J37/02B01J37/08B01J35/10C10G2/00
CPCC10G2/332B01J27/24B01J35/1014B01J35/1019B01J35/1023B01J35/1038B01J35/1042B01J35/1047B01J35/1061B01J35/1066B01J35/1071B01J35/1076B01J37/0201B01J37/082
Inventor 刘忠文朱敏莉宋永红刘昭铁
Owner SHAANXI NORMAL UNIV
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