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Catalyst for Fischer-Tropsch synthesis and preparation method of catalyst

A Fischer-Tropsch synthesis and catalyst technology, which is applied in the preparation of liquid hydrocarbon mixtures, the petroleum industry, and the treatment of hydrocarbon oils. It can solve the constraints on the industrial application of Fischer-Tropsch synthesis processes, the high cost of catalysts per ton of oil, and the difficulty in controlling the shape of metals. and other problems, to achieve the effects of metal crystal form and controllability, high selectivity of C5+ hydrocarbon products, and low cost

Inactive Publication Date: 2017-06-27
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, since most of the above-mentioned catalysts are prepared by impregnation, the morphology of the metal is difficult to control, and the loading capacity of the metal is not high enough.
In addition, the carrier and metal cobalt react chemically to form cobalt aluminate (cobalt silicate, cobalt titanate) compounds that are difficult to reduce. 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 with the carrier and the limited life of the catalyst lead to the high cost of the catalyst per ton of oil, which restricts the industrial application of the Fischer-Tropsch synthesis process

Method used

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  • Catalyst for Fischer-Tropsch synthesis and preparation method of catalyst
  • Catalyst for Fischer-Tropsch synthesis and preparation method of catalyst
  • Catalyst for Fischer-Tropsch synthesis and preparation method of catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Weigh Co(NO 3 ) 3 ·6H 2 O 118g, Ru(NO 3 ) 2 solution (in terms of Ru, the concentration is 17.25g / L) 20ml, with deionized water to prepare a mixed salt solution with a total concentration of 0.9mol / L, and in the prepared mixed salt solution, add 150g of (NH 2 ) 2 CO, continuously stirred for 2h, poured into a 500mL hydrothermal reaction kettle and sealed for hydrothermal reaction, put it into a blast drying oven for drying, the reaction temperature was 120°C, and the reaction time was 10h. Then stand for aging for 5 hours, filter with suction, and wash the precipitate repeatedly with deionized water. Add 50 mL of deionized water to the filter cake, then sonicate for 10 minutes to make a slurry. 200 g of silica support was prepared as a 25% slurry. The above two slurries were mixed, then dried at 120°C for 10 hours, and finally calcined at 500°C for 9 hours, cooled, pressed into tablets, shaped and broken, and 60-80 mesh was selected as the fixed-bed Fischer-Trops...

Embodiment 2

[0036] Weigh Co(NO 3 ) 3 ·6H 2 O 118g, Ru(NO 3 ) 2 Solution 100ml, be mixed with deionized water to make total concentration and be 1.5mol / L mixed salt solution, in the mixed salt solution that adds quality is 100g (NH 2 ) 2CO, continuously stirred for 2h, poured into a 500mL hydrothermal reaction kettle, sealed, and put into a blast drying oven, the reaction temperature was 90°C, and the reaction time was 8h. Then stand and age for 5 hours, filter with suction, and wash the precipitate repeatedly with deionized water. Add 50 mL of deionized water to the filter cake, and then sonicate for 10 minutes to make a slurry. 150 g of silica support was prepared as a 20% slurry. Mix the above two slurries, dry the slurry at 120°C for 20 hours, and finally roast at 400°C for 5 hours, cool, press into tablets, form and break, and select 60-80 mesh as the fixed-bed Fischer-Tropsch synthesis catalyst. The weight ratio of the catalyst is Co:Ru:support=20:1.5:78.5.

[0037] The cata...

Embodiment 3

[0039] Weigh Co(NO 3 ) 3 ·6H 2 O 128g, Ru(NO 3 ) 2 Solution 30ml, be mixed with deionized water to make total concentration and be 0.3mol / L mixed salt solution, in the mixed salt solution that adds quality is 200g (NH 2 ) 2 CO, continuously stirred for 2h, poured into a 1000mL hydrothermal reaction kettle and sealed, put into a blast drying oven, the reaction temperature was 120°C, and the reaction time was 10h. Then stand and age for 5 hours, filter with suction, and wash the precipitate repeatedly with deionized water. Add 50 mL of deionized water to the filter cake, and then sonicate for 10 minutes to make a slurry. 70 g of alumina support was prepared as a 10% slurry. The above two slurries were mixed, then dried at 120°C for 10 hours, and finally calcined at 500°C for 9 hours, cooled, pressed into tablets, shaped and broken, and 60-80 mesh was selected as the fixed-bed Fischer-Tropsch synthesis catalyst. The weight ratio of the catalyst is Co:Ru:support=37:0.7:62....

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Abstract

The invention relates to a catalyst for Fischer-Tropsch synthesis and a preparation method of the catalyst. The catalyst for the Fischer-Tropsch synthesis comprises an active component and a carrier, wherein the active component is an oxide of Co and Ru, the carrier is silicon oxide or aluminum oxide, and the mass ratio of Co to Ru to the carrier in the catalyst is (10-40) to (0.1-10) to (50-89.9). The preparation method comprises the steps of preparing a catalyst active component precursor, preparing a carrier suspension liquid, mixing the catalyst active component precursor with the carrier suspension liquid so as to obtain catalyst slurry, and carrying out drying, roasting and formation on the catalyst slurry, so as to obtain a finished product. The catalyst has the characteristics of high metal loading capacity and reduction degree; and the catalyst has proper pore diameter distribution, high activity and stability, low methane selectivity and high C5<+> hydrocarbon product selectivity.

Description

technical field [0001] The invention relates to a preparation method of a catalyst, in particular to a Co-Ru catalyst for Fischer-Tropsch synthesis and a preparation method thereof. Background technique [0002] Fischer-Tropsch synthesis refers to the synthesis gas (H 2 +CO) is the process of producing hydrocarbons and other chemicals by catalytic reaction of raw materials. Iron-based catalysts are cheap and easy to obtain and have high reactivity for Fischer-Tropsch synthesis, and have high WGS reactivity, making them especially suitable for low H 2 Fischer-Tropsch synthesis of coal-based syngas at / CO ratio. In the 1950s, the catalyst used by Sasol, which successfully realized the large-scale industrialization of Fischer-Tropsch synthesis in South Africa, was an iron-based catalyst. In contrast, cobalt-based catalysts have become the most commonly used type of Fischer-Tropsch synthesis catalysts for the preparation of liquid fuels from natural gas-based syngas due to th...

Claims

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Application Information

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IPC IPC(8): B01J23/89C10G2/00
CPCB01J23/89C10G2/332C10G2300/70
Inventor 肖海成孔繁华刘晓彤陈建刚刘克峰李庆勋王林王宗宝鲁玉莹于天学
Owner PETROCHINA CO LTD