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Co catalyst with controllable Fischer-Tropsch product distribution, preparing and applications thereof

A Fischer-Tropsch synthesis and cobalt catalyst technology, applied in catalyst activation/preparation, molecular sieve catalyst, physical/chemical process catalyst, etc., can solve the problems of high product methane selectivity, cobalt particle agglomeration and low catalyst activity, etc. Simple preparation process

Inactive Publication Date: 2008-07-23
SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, because the carrier is easy to form refractory cobalt species with cobalt oxide, the reduction degree of the supported cobalt catalyst is low, resulting in low catalyst activity and high product methane selectivity (> 15%)
Moreover, due to the difference in the channel distribution of the carrier, the interaction strength between the carrier and the cobalt species is different, which leads to the agglomeration and growth of the cobalt particles during the drying and calcination of the catalyst, which limits the uniformity of the particle size of the cobalt species and the degree of dispersion on the carrier surface. The effect of leading to the selective synthesis of products is not obvious

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Prepare 0.1mol / L complexing agent solution with ethylenediaminetetraacetic acid (EDTA) and deionized water. Weigh 7.4 grams of cobalt nitrate hexahydrate and add it to 50ml of complexing agent solution to obtain a cobalt salt solution. Add 8.0g of carrier to the cobalt salt solution. Dry at 60°C for 24h, fully grind the dried solid, then calcinate at 500°C for 10h, shape the calcined solid powder, and sieve 40-80 mesh to obtain 15% Co / SiO 2 catalyst

[0031]The catalytic reaction is carried out in a pressurized fixed-bed reactor. Weigh 1ml of the above catalyst and put it into a reaction tube. The reducing conditions are 500°C, 0.4MPa, 800h -1 (V / V), 12h. The temperature is programmed to rise to 500°C for reduction, and then the temperature is lowered to below 40°C, the synthesis gas is switched, and the pressure of the synthesis gas is adjusted to 2.0 MPa. The reaction conditions are: 180°C, 2.0MPa, 1000h -1 (V / V),H 2 / CO=3 / 1. In order to ensure that the Fischer-...

Embodiment 2

[0033] Triethylenetetraaminehexaacetic acid (TTHA) and deionized water were made into a 0.5mol / L complexing agent solution. Measure 15 grams of cobalt nitrate hexahydrate and add it to 50 ml of complexing agent solution to obtain a cobalt salt solution. Add 26.2 g of molecular sieve carrier (0.51*0.55 nm in pore size) into the cobalt salt solution. ℃ for 12 hours, and then dried in an oven at 60 ℃ for 24 hours. After the dried solid was fully ground, it was calcined at 400 ℃ for 8 hours. ZSM-5 catalyst

[0034] The catalytic reaction is carried out in a pressurized fixed-bed reactor. Weigh 1mL of the above catalyst and put it into a reaction tube. The reducing conditions are 400°C, 0.3MPa, 1000h -1 (V / V), 24h. Program the temperature to 400°C for reduction, then cool down to below 40°C, switch the synthesis gas, and adjust the pressure of the synthesis gas to 2.0MPa. The reaction conditions are: 190°C, 3.0MPa, 500h -1( V / V), H 2 / CO=2 / 1. Catalytic reaction performance ev...

Embodiment 3

[0036] Mix citric acid and deionized water into a 2mol / L complexing agent solution. Take by weighing 10 grams of cobalt nitrate hexahydrate and join in the 50ml complexing agent solution to obtain cobalt salt solution, 37.7g Y type molecular sieve carrier (average aperture is 0.74nm) is joined in the cobalt salt solution, after stirring, at immersion temperature Stand at 30°C for 18h, then dry in an oven at 80°C for 12h, grind the dried solid thoroughly, and then calcinate at 450°C for 5h, shape the calcined solid powder, and sieve 40-80 mesh to obtain 5% Co / Y Catalyst

[0037] The catalytic reaction is carried out in a pressurized fixed-bed reactor. Weigh 1mL of the above catalyst and put it into a reaction tube. The reducing conditions are 300°C, 0.3MPa, 500h -1 (V / V), 24h. The temperature is programmed to rise to 300°C for reduction, and then the temperature is lowered to below 40°C, the synthesis gas is switched, and the pressure of the synthesis gas is adjusted to 2.0 ...

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Abstract

A cobalt catalyst on which the distribution of Fischer-Tropsch synthesis is controllable is composed of metallic cobalt and a carrier by the weight percentage of 5-35% and 65-95% respectively. The catalyst is prepared by an impregnation method which aims at different carrier pore paths and pore diameter distribution as well as changes the interaction between the modulator cobalt and the carrier through adding a complexing agent during impregnation to achieve the even distribution of cobalt particle on the carrier surface, thus controlling the distribution of Fischer-Tropsch syntheses. The invention has the advantages of high reactivity and low selectivity of methane and achieving the selective synthesis of the products in the sections with specified carbon number.

Description

technical field [0001] The invention belongs to a catalyst and its preparation method and application, in particular to a cobalt-based catalyst with controllable distribution of Fischer-Tropsch synthesis products, its preparation method and application. Background technique [0002] Fischer-Tropsch synthesis is a method jointly discovered by Germans Fischer and Tropsch in the 1920s, using synthesis gas (carbon monoxide and hydrogen) as raw materials to synthesize hydrocarbons on a catalyst. The main hydrocarbon products include gasoline and diesel. , wax, naphtha, light olefins, etc., and by-products of carbon dioxide, water and oxygen-containing organic compounds. Syngas can be produced from carbonaceous raw materials such as coal, natural gas, coal bed methane, coke, and biomass. [0003] my country's energy is characterized by rich coal, little oil and gas. It is of great practical significance to develop the process of converting coal / natural gas into liquid fuel throug...

Claims

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Application Information

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IPC IPC(8): B01J23/75B01J29/064B01J29/03B01J37/02C07C1/04
Inventor 孙予罕贾丽涛李德宝穆仕芳
Owner SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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