Fischer-Tropsch synthesis cobalt-based catalyst and preparation method thereof

A technology of cobalt-based catalysts and Fischer-Tropsch synthesis, which is applied in chemical instruments and methods, preparation of liquid hydrocarbon mixtures, physical/chemical process catalysts, etc., can solve problems such as difficult product concentration, insufficient CO conversion rate, and increased costs, and achieve The effect of stabilizing catalyst activity, improving product distribution and good dispersion

Inactive Publication Date: 2013-05-01
WANHUA CHEM GRP CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

CN101318133A has reported the eggshell type catalyst that is used for preparing naphtha and diesel oil, and active component and specific auxiliary agent are sprayed on carrier and form eggshell structure, can obtain high C for Fischer-Tropsch synthesis reaction 5 -C 20 Fraction selectivity, lower C 21+ Selectivity, but its CO conversion is mostly below 50%, CH 4 Selectivity close to 20%
The catalyst can be used to obtain isoparaffin-based C 5 -C 12 , its selectivity can reach up to 55%, but the methane selectivity of this type of catalyst is mostly more than 15%
[0007] It can be seen from the existing reports that although the distribution of Fischer-Tropsch synthesis products can be moderately adjusted by using the above-mentioned catalyst or process to obtain a suitable middle distillate selectivity, the products are still difficult to concentrate, such as CH 4 The selectivity is also high; in addition, C 5+ Selectivity and CO conversion are difficult to meet the requirements of high performance at the same time, often high C 5+ In the case of selectivity, the CO conversion rate is not enough, and the raw material needs to be recycled, which will inevitably increase the cost

Method used

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  • Fischer-Tropsch synthesis cobalt-based catalyst and preparation method thereof

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Experimental program
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Effect test

Embodiment 1

[0046] Weigh 40.0g aluminum nitrate (Al(NO 3 ) 3 9H 2 O 375.13), add 400.0g absolute ethanol, stir to dissolve, then add 30.0g silica gel (calculated as silicon dioxide) and 0.5g polyethylene glycol, continue to stir for 1h; Add 20wt% ammonium carbonate dropwise under constant stirring Solution, adjust the pH value to 9.0; adjust the temperature to 90°C, stir and reflux for 3h, move the obtained solid-liquid mixture to an oven and dry at 100°C for 10h, then move to a muffle furnace and bake at 450°C for 4h; Get 2.0g of 3-aminopropyltriethoxysilane, add 100.0g of absolute ethanol, then add the above-mentioned roasted sample, adjust the temperature to 100°C, reflux and stir for 3h; take by weighing 5.0g of boric acid (H 3 BO 3 61.81), add to the above mixed solution, continue to reflux and stir for 6h; filter the obtained solid-liquid mixture, move the obtained filter cake to an oven and dry at 100°C for 15h, then move to a muffle furnace and roast at 450°C for 5h, The obtai...

Embodiment 2

[0050] Weigh 2.18g niobium chloride (NbCl 5 270.17), add a certain amount of deionized water to make a solution with a concentration of 1.0wt%, and stir for 1h; weigh 15.0g of SiO obtained in Example 1 according to the proportioning ratio 2 -Al 2 o 3 -B 2 o 3 Add it into the above solution, stir for 10 hours, and then stand still for 4 hours; evaporate the obtained solid-liquid mixture to dryness at 80°C, and then dry it in vacuum at 70°C for 15 hours; weigh 21.17g of cobalt nitrate (Co(NO 3 ) 2 ·6H 2 O 291.05), add a certain amount of deionized water to make a 5.0wt% solution, stir for 1h; take by weighing 3.79g manganese nitrate (Mn(NO 3 ) 2 4H 2 O 250.94), added to the above solution, and stirred for 0.5h; the sample obtained after vacuum drying was added to the above solution, stirred for 10h, and left standing for 10h; the obtained solid-liquid mixture was evaporated to dryness at 100°C, and then Vacuum drying at ℃ for 24 hours; fully grind the dried solid for 1...

Embodiment 3

[0053] Weigh 40.0g aluminum chloride (AlCl 3 ·6H 2 (241.34), add 400.0g absolute ethanol, stir and dissolve, then add 30.0g fumed silicon dioxide and 1.5g polyvinyl alcohol, continue to stir for 1h; add 10wt% ammonium carbonate solution drop by drop under constant stirring, adjust the pH value 9.0; adjust the temperature to 90°C, stir and reflux for 3h, move the obtained solid-liquid mixture to an oven and dry at 100°C for 10h, then move to a muffle furnace and roast at 450°C for 4h; weigh 4.0g of 3- Aminopropyltriethoxysilane, add 100.0g of absolute ethanol, then add the above-mentioned roasted sample, adjust the temperature to 100°C, reflux and stir for 3h; weigh 8.0g boric acid (H 3 BO 3 61.81), add to the above mixed solution, continue to reflux and stir for 6h; filter the obtained solid-liquid mixture, move the obtained filter cake to an oven and dry at 100°C for 15h, then move to a muffle furnace and roast at 450°C for 5h, The obtained sample is ground into SiO 2 -A...

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Abstract

The invention provides a Fischer-Tropsch synthesis cobalt-based catalyst and a preparation method of the Fischer-Tropsch synthesis cobalt-based catalyst. The catalyst contains a silicon aluminum boron composite oxide, cobalt and an assistant, wherein the assistant contains an oxide/oxides of one or two or more VB-group elements, and an oxide/oxides of one or two or more elements of Mn, Ti, Zr, Fe, W, Ce, La and Ni; according to the total amount of the catalyst, the content of cobalt is 1wt%-30wt%, the content of the oxide/oxides of the VB-group elements is 0.02wt%-9wt%, the content of the oxide/oxides of other assistants is 0.01wt%-6wt%, and the balance is the silicon aluminum boron composite oxide. The invention further provides the silicon aluminum boron composite oxide and a preparation method of the load cobalt catalyst. The catalyst is used for the Fischer-Tropsch synthesis reaction, the CO conversion rate and the C5+ selectivity are both higher than 80%, and the selectivity of kerosene and diesel fraction, namely C10-C20, in the C5+ is up to more than 50%.

Description

technical field [0001] The invention belongs to the field of catalysts, and in particular relates to a Fischer-Tropsch synthesis cobalt-based catalyst and a preparation method of the catalyst. Background technique [0002] The process of converting synthesis gas into hydrocarbons (gasoline, kerosene, diesel, low-carbon olefins, wax and other fuel oils and chemicals) under the action of a catalyst is Fischer-Tropsch synthesis. In recent years, with the continuous consumption of petroleum resources and the increasing demand for energy and resources, the preparation of liquid fuels and high value-added chemicals by Fischer-Tropsch synthesis has been widely recognized. Internationally, Sasol, Shell and other companies already have industrialized production devices based on coal-to-liquids (CTL) and natural gas-to-liquids (GTL). In addition, Exxon Mobil, Syntroleum, BP and many other companies are planning to implement industrial production plants based on Fischer-Tropsch synthes...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/20B01J23/889B01J23/847C10G2/00
Inventor 康金灿张明詹吉山楼银川黎源查志伟华卫琦
Owner WANHUA CHEM GRP CO LTD
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