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Cobalt-based catalysts and their applications in f-t synthesis

A cobalt-based catalyst and catalyst technology, applied in the preparation of liquid hydrocarbon mixtures, petroleum industry, etc., can solve the problems of multi-equipment investment, complex synthesis process, etc., and achieve simple preparation process, easy industrial production, high reactivity and liquid hydrocarbon The effect of product-like selectivity

Active Publication Date: 2016-11-30
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Therefore, compared with the iron-based catalyst slurry-bed F-T synthesis process (the iron-based catalyst can be directly reductively activated and reacted in the slurry-bed reactor), the slurry-bed F-T synthesis process using cobalt-based catalysts is more complicated and requires more Much equipment investment (need to design another reduction reactor and catalyst transfer pipeline)

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment （1）

[0036] will be 96cm 3 A mixed alcohol solution containing methanol and polyethylene glycol 400 (the volume ratio of methanol and polyethylene glycol 400 is 15 / 1) and 270cm 3 Deionized aqueous solution was made into a solution, and then 5.5 grams of cobalt nitrate hexahydrate and 0.06 grams of Ru(NO)(NO 3 ) 3 added to the above solution. After treatment at 90°C to form an impregnating solution, 9 g of Al 2 o 3 and SiO 2 mixture (mass ratio of SiO 2 / Al 2 o 3 =80) into the above impregnation solution. With stirring, the temperature was raised to 100°C to evaporate the solvent. The obtained paste solid was put into a muffle furnace, and calcined at 400° C. for 4 hours to obtain a cobalt-based catalyst. The specific surface area and pore volume of the catalyst were calculated using N 2 Determination of adsorption method. During the test, the sample was first degassed and pretreated at 250°C for 10 hours to remove the physically adsorbed moisture in the sample, and then...

Embodiment （2）

[0038]The F-T synthesis reaction performance evaluation test of the cobalt-based catalyst prepared in Example 1 was carried out in a slurry bed reactor. F-T synthesis reaction conditions are T=250℃, P=2MPa, H 2 / CO=2. Gas phase products are directly analyzed online for qualitative and quantitative analysis by gas chromatography. 15 grams of cobalt-based catalysts prepared in Example (1) were directly added to 1000 cm 3 Liquid paraffin slurry bed reactor. Then carry out the reduction treatment in the slurry bed reactor (T=260℃, normal pressure, H 2 Air velocity = 3600cm 3 (g-catalyst h) -1 ) for 16 hours. After the reduction treatment is finished, the temperature of the slurry bed reactor is gradually lowered to 250° C., and the pressure is raised to 2 MPa to carry out the F-T synthesis reaction. The reaction results show that within 30 hours after reaching the reaction temperature, the conversion rate of CO can reach ~65-49%, and the selectivity of liquid hydrocarbon pr...

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Abstract

The invention discloses a cobalt-based catalyst and its application in F-T synthesis. A cobalt-based catalyst I with silicon oxide and aluminum oxide as a carrier is an oxide of Co and Ru loaded on a carrier, wherein SiO 2 and Al 2 o 3 The mass ratio is 20-200, wherein the mass ratio of Co to the support is 5-40:100, and the mass ratio of Ru to the support is 0.05-0.5:100; its preparation method includes the following steps: (a) will contain Co and Ru The inorganic salt was dissolved into a mixed solution containing deionized water and polyethylene glycol to prepare solution A; (b) SiO 2 and Al 2 o 3 The mixture is added to the solution A prepared by the step (a), and then the solvent is removed to obtain the precursor B; (c) the precursor B obtained by the step (b) is roasted at 300-600°C to obtain a Co-based catalyst I. The present invention also provides the cobalt-based catalyst II obtained by reducing the cobalt-based catalyst I in hydrogen, and the reduction temperature is lower than 300°C. The invention provides the application of the cobalt-based catalyst in the F-T synthesis reaction.

Description

(1) Technical field [0001] The invention relates to a cobalt-based catalyst and its application in F-T synthesis, in particular to the application in the F-T synthesis carried out in a slurry bed reactor. (2) Background technology [0002] Fischer-Tropsch synthesis (F-T synthesis) refers to synthesis gas (CO+H 2 ) into a mixture dominated by organic hydrocarbons. Through this reaction process, various important chemical products (such as low-sulfur gasoline, diesel oil, wax, etc.) can be synthesized from natural gas, coal, biomass and other non-petroleum resources as raw materials. Cobalt-based and iron-based catalysts are two F-T synthesis catalysts with industrial application prospects. Compared with iron-based catalysts, cobalt-based catalysts have a stable reaction process and liquid products (C 5+ ) The advantages of high selectivity. Therefore, cobalt-based catalysts have more development potential and advantages in the field of low-temperature F-T synthesis. [0...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/89C10G2/00
Inventor 姚楠李小年姚曼
Owner ZHEJIANG UNIV OF TECH