Supported cobalt-based catalyst for Fischer-Tropsch synthesis, and preparation method and application thereof

A cobalt-based catalyst and Fischer-Tropsch synthesis technology, applied in chemical instruments and methods, preparation of liquid hydrocarbon mixtures, chemical elements of heterogeneous catalysts, etc., can solve the problems of easily oxidized mechanical strength, sintering of active components, and decrease of specific surface area etc. to achieve the effects of good mechanical strength, good thermal conductivity, and concentrated product distribution

Inactive Publication Date: 2017-04-26
中科潞安能源技术有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, the thermal conductivity of alumina and silica is relatively poor, and it is difficult to transfer the reaction heat in time during the strong exothermic process of the Fischer-Tropsch reaction to form a "hot spot", resulting in a decrease in its specific surface area and even sintering of the loaded active components.
Although carbon materials have good thermal conductivity, they have problems such as easy oxidation at high temperature and poor mechanical strength.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Weigh 100g of tungsten carbide according to the final catalyst composition (prepared according to patent CN 201510184222.8, specific surface area 200m 2 / g, pore volume 0.6cm 3 / g, pore diameter 5nm), with 5mol / L NaOH activation treatment for 6h, get activated tungsten carbide carrier (specific surface area is 50m 2 / g, the pore volume is 0.3cm 3 / g, the pore size is 20nm); 36.24g Co(NO 3 ) 2 ·6H 2 O, 3.12g RuCl 3 ·3H 2 O and 36.40g Zn(NO 3 ) 2 ·6H 2 O is dissolved in water and impregnated in the above-mentioned tungsten carbide carrier with an equal volume, dried in an oven at 90°C for 20h, and then calcined in a muffle furnace at 450°C for 4h to obtain the final catalyst. The weight composition is Co 3 o 4 : RuO 2 :ZnO:WC=10:2:15:100.

[0025] Take 5ml of the above catalyst without dilution and fill it in a fixed bed reactor (Ф10×500mm). The reduction conditions are: 450°C, 0.3MPa, constant temperature for 12h, 1000h -1 (v / v), using hydrogen in nitrogen, ...

Embodiment 2

[0027] Weigh 100g tungsten carbide according to the final catalyst composition (prepared according to patent CN 200910153606.8, specific surface area 180m 2 / g, pore volume 0.7cm 3 / g, pore size 10nm), activated with 1mol / L KOH for 8h, to obtain activated tungsten carbide carrier (specific surface area is 100m 2 / g, the pore volume is 0.4cm 3 / g, the pore diameter is 16nm); 93.03g C 4 h 6 o 4 ·Co·4H 2 O, 9.38g Rh(NO 3 ) 3 ·6H 2 O and 69.68g Zr(NO 3 ) 4 ·5H 2 O is dissolved in water and impregnated in the above-mentioned tungsten carbide carrier with an equal volume, dried in an oven at 100°C for 16h, and then calcined in a muffle furnace at 420°C for 8h to obtain the final catalyst. The weight composition is Co 3 o 4 : Rh 2 o 3 : ZrO 2 :WC=30:3.0:20:100.

[0028] Take 5ml of the above catalyst without dilution and fill it in a fixed bed reactor (Ф10×500mm). The reduction conditions are: 420°C, 0.5MPa, constant temperature for 16h, 900h -1 (v / v), using hydrogen...

Embodiment 3

[0030] Weigh 100g tungsten carbide according to the final catalyst composition (prepared according to patent CN 201510151369.7, specific surface area 150m 2 / g, pore volume 0.4cm 3 / g, pore size 15nm), activated with 3mol / L NaOH for 4h to obtain activated tungsten carbide carrier (specific surface area is 150m 2 / g, the pore volume is 0.5cm 3 / g, the pore size is 15nm); the 144.96g Co(NO 3 ) 2 ·6H 2 O, 5.70gH 2 PtCl 6 ·6H 2 O and 35.91g La(NO 3 ) 3 ·6H 2 O is dissolved in water and impregnated in the above-mentioned tungsten carbide carrier with an equal volume, dried in an oven at 110°C for 12h, and then calcined in a muffle furnace at 400°C for 12h to obtain the final catalyst. The weight composition is Co 3 o 4 : PtO 2 : La 2 o 3 :WC=40:2.5:10:100.

[0031] Take 5ml of the above catalyst without dilution and fill it in a fixed bed reactor (Ф10×500mm). The reduction conditions are: 400°C, 0.7MPa, constant temperature for 20h, 800h -1 (v / v), using hydrogen in n...

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Abstract

The invention provides a supported cobalt-based catalyst for Fischer-Tropsch synthesis. The supported cobalt-based catalyst is composed of cobaltosic oxide, an oxide of a precious-metal aid, an oxide of a non-precious-metal aid and a tungsten carbide carrier in a weight ratio of (10-80): (0-3): (0-20): 100. The supported cobalt-based catalyst has the advantages of high mechanical strength and good thermal conductivity.

Description

technical field [0001] The invention relates to a Fischer-Tropsch synthesis catalyst and its preparation method and application, in particular to an activated tungsten carbide supported cobalt-based Fischer-Tropsch synthesis catalyst, its preparation method and its application. [0002] technical background [0003] With the development of the world economy, the demand for refined oil has increased rapidly, while the reserves and production of oil resources have gradually decreased and become inferior. The contradiction between demand and reserves has become increasingly prominent. At the same time, the requirements of international and domestic environmental protection regulations have become increasingly Therefore, obtaining high-quality liquid fuel products through new methods is a major problem facing China and the world. Clean fuels and other high value-added chemicals can be produced on a large scale through Fischer-Tropsch synthesis. The raw material syngas for Fische...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/22B01J23/89C10G2/00
CPCB01J27/22B01J23/002B01J23/83B01J23/8913B01J23/894B01J23/8946B01J23/8953B01J23/8986B01J2523/00C10G2/333B01J2523/27B01J2523/821B01J2523/845B01J2523/48B01J2523/822B01J2523/3706B01J2523/828B01J2523/22B01J2523/824B01J2523/74
Inventor 李德宝侯博贾丽涛刘岩
Owner 中科潞安能源技术有限公司
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