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High active and high stable catalyst of ferro manganese Fischer-Tropsch synthesis and preparation method

A high stability, catalyst technology, applied in physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, hydrocarbon production from carbon oxides, etc., can solve problems that are not conducive to the separation of catalysts and waxes, and the spherical shape of catalysts Poor, expensive and other problems, to achieve the effect of improving activity and selectivity, increasing strength and reducing production cost

Active Publication Date: 2005-01-12
SYNFUELS CHINA INNER MONGOLIA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The preparation method does not involve spray drying, and the particles of the catalyst are small and continuously distributed, which is unfavorable for the separation of the catalyst and the wax in the slurry bed reaction; American Rentech Company has developed a Fischer-Tropsch synthetic iron for slurry bed reactor The preparation method (USP 5504118 and CN 1113905A) of base catalyst is specifically: use nitric acid to dissolve metallic iron and copper to obtain the mixed solution of ferrous nitrate, ferric nitrate and copper nitrate, then ammoniacal liquor is added in the hot nitrate mixed solution, precipitation Slurry, add potassium carbonate solution after washing, beating, the weight percentage of the catalyst in the slurry is about 8-12%, then spray dry with a spray dryer, the diameter range is 5-50μm, and finally roast at 315 ° C, but the catalyst The spherical shape of the catalyst is poor, and no wear-resistant SiO is added to the catalyst 2 Binder with small particles
[0004] The report about spray-drying Fe / Mn catalyzer is extremely rare, and U.S. Patent (USP 4618597,4621102,1986) has announced the preparation method of a kind of Fe / Mn catalyzer: use the more expensive glycolic acid ammonium (PH=6.5) precipitation Fe / Mn mixed salt solution, precipitated and dried, then impregnated with the salt solution of the first or second main group metal, and did not use spray drying technology, and did not add SiO that can significantly improve the mechanical strength of the catalyst 2

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Weigh 10 kg Fe(NO 3 ) 3 9H 2 O, 624 grams of 50wt% Mn (NO 3 ) 2 solution, 1.47 kg Ca(NO 3 ) 2 4H 2 O and 693 g SiO 2 Acidic silica sol with a content of 30wt% is dissolved in deionized water to make a solution with a total metal ion concentration of 1.0 mol / liter, which is co-precipitated with 3.0 mol / liter of ammonia at 55°C and a pH of 10.5. After the precipitate was washed and filtered, 17.5 kg of filter cake (solid content: 15.3 wt%) was obtained, and 74 g of potassium carbonate and 2.0 kg of deionized water were added to the filter cake for beating to obtain a catalyst slurry with a solid content of 13.7 wt%. The above slurry was centrifugally spray-dried under the condition that the air inlet temperature was 270°C and the outlet air temperature was 95°C, and the obtained dried microspheres were calcined at 450°C for 6 hours to remember the finished catalyst. The ratio of active components of the catalyst is: 100Fe / 7 Mn / 18 Ca / 3 K / 15 SiO 2 , its main techni...

Embodiment 2

[0029] Weigh 10 kg Fe(NO 3 ) 3 9H 2 O, 4.0 kg containing Mn(NO 3 ) 2 For a 50wt% solution, 410 grams of Ca(NO 3 ) 2 4H 2 O and 1.21 kg SiO 2 Acidic silica sol with a content of 40wt% is dissolved in deionized water to make a solution with a total metal ion concentration of 4.5 mol / liter, and the solution is co-precipitated with 0.5 mol / liter of ammonia at 95 ° C and a pH of 7.7. After washing and filtering the precipitate, 8.25 kilograms of filter cake (solid content: 41.9wt%) were obtained, and 178 grams of potassium bicarbonate and 2.0 kilograms of deionized water were added to the filter cake for beating to obtain a catalyst slurry with a solid content of 33.7wt%. . The above-mentioned slurry was centrifugally spray-dried under the condition that the air inlet temperature was 230°C and the outlet air temperature was 115°C, and the obtained dried microspheres were calcined at 370°C for 7 hours to remember the finished catalyst. The ratio of active components of the ...

Embodiment 3

[0031] Weigh 10 kg Fe(NO 3 ) 3 9H 2 O, 1.07 kg of 50wt% Mn(NO 3 ) 2 Solution, 982 g Ca(NO 3 ) 2 4H 2 O and 1.85 kg SiO 2 Acidic silica sol with a content of 15wt% was dissolved in deionized water to make a solution with a total metal ion concentration of 2.0 mol / liter, and the solution was co-precipitated with 1.0 mol / liter of ammonia at 80°C and a pH of 8.5. After the precipitate was washed and filtered, 7.52 kg of filter cake (solid content: 36.3 wt%) was obtained. 140 g of potassium acetate and 3.0 kg of deionized water were added to the filter cake for beating to obtain a catalyst slurry with a solid content of 25.9 wt%. The above slurry was centrifugally spray-dried under the condition that the air inlet temperature was 250°C and the outlet air temperature was 100°C, and the obtained dried microspheres were calcined at 500°C for 5 hours to remember the finished catalyst. The ratio of active components of the catalyst is: 100 Fe / 12 Mn / 12 Ca / 4 K / 20 SiO 2 , its main...

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PUM

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Abstract

A Fe-Mn catalyst with high activity and stability for Fischer-Tropsch synthesis contains Fe, Mn, Ca, K and SiO2. It is prepared through codepositing of the assistant containing Fe, Mn and Ca, silicon sol and ammonia water, feeding the deposit slurry and the catalyst slurry prepared from potassium carbonate solution in drier, drying and calcining.

Description

Technical field: [0001] The invention belongs to a preparation method of a catalyst, in particular to a preparation method of an iron-manganese catalyst with high activity and high stability used in Fischer-Tropsch synthesis. technical background: [0002] Fischer-Tropsch synthesis refers to synthesis gas (CO+H 2 ) catalyzes the reaction of synthesizing hydrocarbon liquid fuels on a catalyst. Since the 1950s, the large-scale industrialization of coal-based synthetic liquid fuels has been realized in Sasol Company in South Africa (Dry, M.E., Catalysis Today, 1990, 6(3) 183-206) . Fischer-Tropsch synthesis usually uses iron-based catalysts, and the reactors used include fixed-bed reactors, fluidized-bed reactors and slurry-bed reactors. Due to the high production efficiency of the slurry bed reactor, the catalyst is easy to load and unload, and the low H 2 Coal-based syngas with a CO / CO ratio shows great technical advantages and is currently the most important synthetic liq...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/889C07C1/04
Inventor 相宏伟杨勇陶智超田磊李永旺
Owner SYNFUELS CHINA INNER MONGOLIA CO LTD
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