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A kind of cobalt-based catalyst and its preparation method and application

A cobalt-based catalyst and system technology, applied in catalyst carriers, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of reducing catalyst activity and selectivity, reducing catalyst life, affecting product distribution, etc., and achieving excellent products. Selectivity, CO2 selectivity decrease, C5+ selectivity increase effect

Active Publication Date: 2015-09-02
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Shi Lihong et al. "Fischer-Tropsch synthesis reaction performance of organically modified silica and its supported cobalt catalyst" in "Journal of Catalysis", Vol. 28, No. 11, P999~1002 Alkyl-modified SiO2 supports were prepared by silanization, and supported cobalt catalysts were prepared by isometric impregnation method. It was pointed out that SiO2 was modified by organic groups After that, the activity of the catalyst is improved and the methane selectivity is reduced, but the product distribution will be affected due to steric hindrance
[0007] After the above-mentioned modification of the silica gel carrier, the catalyst system has high activity and selectivity under certain reaction conditions, but the above-mentioned modified silica gel carrier still chemically interacts with the active center cobalt to form silicic acid that is difficult to reduce Cobalt compounds reduce the activity and selectivity of the catalyst, making CH 4 The content in the reaction product increased significantly, C 5 + Selectivity greatly reduced
When the catalyst operates in a slurry bed or in a fixed bed for a long time, the hydrothermal effect promotes the reaction of cobalt and the carrier, which greatly reduces the life of the catalyst

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

[0029] Turn on the electric stirrer and the water bath thermostat, add the water glass solution with a concentration of 1.70g / ml into the reaction kettle, control the temperature of the water bath at 40°C, and add the dilute sulfuric acid solution with a concentration of 2.0g / ml at a flow rate of 5ml / min, At the same time, the concentration of 0.1g / ml titanium sulfate solution was added at a flow rate of 2ml / min. When the pH value of the solution reached 10.5, the addition of a constant temperature was stopped for 1 hour; ml of dilute sulfuric acid solution and 0.1g / ml zirconium sulfate solution until the pH value of the solution is 9.5, stop adding and keep the temperature for 3 hours, then raise the temperature to 70°C and age for 10 hours; finally wash with distilled water and dry at 50°C for 24 hours , baked at 280° C. for 10 hours to obtain the silica gel product containing titanium and zirconium prepared in the present invention. Titanium content (W / W%) 0.1%, zirconium c...

example 2

[0033] Turn on the electric stirrer and the water bath thermostat, add the water glass solution with a concentration of 2.0g / ml into the reaction kettle, control the temperature of the water bath at 60°C, and add the dilute sulfuric acid solution with a concentration of 1.6g / ml at a flow rate of 8ml / min, At the same time, the concentration of 0.2g / ml titanium sulfate solution was added at a flow rate of 2ml / min. When the pH value of the solution reached 12, the addition of constant temperature was stopped for 3 hours; ml dilute sulfuric acid solution and 0.5g / ml zirconium sulfate solution until the pH value of the solution is 8.5, stop adding and keep the temperature for 4 hours, then raise the temperature to 120°C and age for 3 hours; finally wash with distilled water and dry at 150°C for 8 hours, 600 The silica gel product containing titanium and zirconium prepared by the present invention is obtained by roasting at ℃ for 2 hours. Titanium content (W / W%) 0.5%, zirconium cont...

example 3

[0036] Turn on the electric stirrer and water bath thermostat, add the water glass solution with a concentration of 1.90g / ml into the reaction kettle, control the temperature of the water bath at 50°C, and add dilute sulfuric acid solutions with a concentration of 1.8g / ml at a flow rate of 6.5ml / min , and at the same time, add a concentration of 0.15g / ml titanium sulfate solution at a flow rate of 4ml / min. When the pH value of the solution reaches 11, stop adding and keep the temperature for 2 hours; then add a concentration of 1.8g at 4ml / min and 6ml / min / ml dilute sulfuric acid solution and 0.3g / ml nitric acid solution until the pH value of the solution is 9, stop adding and keep the temperature for 3.5 hours, then raise the temperature to 100°C and age for 6 hours; finally wash with distilled water and dry at 100°C for 16 hours, 400 The silica gel product containing titanium and zirconium prepared by the present invention is obtained by roasting at 8°C for 8 hours. Titanium...

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PUM

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Abstract

The invention discloses a cobalt-based catalyst, and a preparation method and applications thereof. According to the cobalt-based catalyst, modified silica gel, which is modified with titanium and zirconium, is taken as a carrier; cobalt is taken as an active component; the modified silica gel comprises, by weight, 0.1 to 0.5% of titanium, and 0.5 to 2% of zirconium; and the obtained Fischer-Tropsch synthesis catalyst comprises 5 to 35% of the active component cobalt. The preparation method of the cobalt-based catalyst comprises preparation processes of the modified silica gel which is modified with titanium and zirconium, and immobilizing processes of the active component cobalt. The cobalt-based catalyst possesses advantages such as high activity, stability and selectivity in slurry bed Fischer-Tropsch synthetic reaction processes.

Description

technical field [0001] The invention relates to a cobalt-based catalyst and its preparation method and application, in particular to a cobalt-based Fischer-Tropsch synthesis catalyst and its preparation method and application. Background technique [0002] Fischer-Tropsch synthesis refers to synthesis gas (CO+H 2 ) on the catalyst to catalyze the reaction of synthesizing hydrocarbon liquid fuel. 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 temperature is high, the catalyst is prone to carbon deposition and poisoning, and the chain growth ability is poor, which is not conducive to the synthe...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/75B01J32/00B01J21/06C10G2/00
Inventor 李杰林朝阳张舒冬尹泽群刘全杰倪向前
Owner CHINA PETROLEUM & CHEM CORP