Ferromanganese catalyst for Fischer-Tropsch synthesis and method for preparing the same

A Fischer-Tropsch synthesis, manganese catalyst technology, applied in physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc. Problems such as low synthetic activity

Inactive Publication Date: 2005-05-04
SYNFUELS CHINA TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Arakawa et al. (Ind.Eng.Chem.Process Des.Dev.1983,22,97-103) studied the effect of potassium additives on Al 2 o 3 The influence of the activity and selectivity of loaded iron catalysts, it is found that when the iron-potassium atomic ratio is 15, the potassium promoter can significantly improve the activity of iron-based catalysts, promote the shift of hydrocarbon products to the direction of heavy hydrocarbons, and increase the effective hydrocarbon ( C 2-4 ＝ and C 5 + the sum of ) selectivity, but the methane selectivity of the catalyst is very high (>20%)
People such as Soled of Exxon Research Engineering Company have announced in U.S. Patent (USP 5,100,856) the iron-based Fischer-Tropsch synthesis catalyst that is added with zinc, copper, potassium, iron-zinc atomic ratio>5: 1, at 270 ℃, space velocity is . 1000mL / g catalyst / hour, feed gas H 2 Under the condition of / CO ratio of 2:1, light olefins (C 2-4 ＝ ) selectivity (in C 2-4 hydrocarbons) up to 85%, but the Fischer-Tropsch synthesis activity is low, and the CO conversion rate is only 32%
In addition, people such as Fiato and Iglesia of Exxon Research Engineering Company have also announced high specific surface area copper and the first or second main group metal as the ferromanganese Fischer-Tropsch synthesis catalyst (USP 4,621,102, USP 5,118,715) of auxiliary agent, but adopt iron, The hydroxyacetate of manganese is used as a raw material, the preparation procedure is complicated, and the preparation cost is relatively high. At present, there are no reports on iron-manganese Fischer-Tropsch synthesis catalysts containing IIA main group metal element additives

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Weigh Fe(NO 3 ) 3 9H 2 O 194.07 g, Ca(NO 3 ) 2 4H 2 O 22.55 g and a concentration of 50% Mn(NO 3 ) 2 Solution 9.5 grams, with deionized water to prepare a mixed solution with a total concentration of 0.10 mol / liter, place the mixed solution in a water bath at 80°C for preheating; prepare an ammonia solution with a concentration of 2.0 mol / liter, and place it in a water bath at 60°C Preheat, slowly drop the above salt solution into the ammonia solution, stir, the precipitation process takes about 30 minutes, and the pH value of the system is 7.5 when the precipitation is terminated. After the precipitation is completed, let it stand for about 12 hours, filter, wash the filter cake with deionized water until the pH value of the filtrate is 7.3, and filter again, dry the filter cake at 110-120°C for 24 hours; grind the dried filter cake finely , adding 23 mL of potassium carbonate with a concentration of 0.31 mol / L for 3 hours, drying at 70°C; then roasting at 500°C...

Embodiment 2

[0028] As in Example 1, Fe(NO 3 ) 3 9H 2 O194.07g, Ca(NO 3 ) 2 4H 2 O12.50 grams and a concentration of 50% Mn (NO 3 ) 2 85.99 g of the solution was prepared with deionized water to form a mixed solution with a total concentration of 0.30 mol / liter, and the mixed solution was heated in a water bath at 50°C; an ammonia solution with a concentration of 0.50 mol / liter was prepared and preheated in a water bath at 50°C; The above ammonia solution was slowly added dropwise into the salt solution, stirred, and the precipitation process took about 35 minutes. The pH value of the system was 8.5 when the precipitation was terminated. After the precipitation is completed, let it stand for about 12 hours, filter, wash the filter cake with deionized water until the pH value is 7.5, and filter again, dry the filter cake at 110-120°C for 24 hours; grind the dried filter cake finely, Immerse with 16mL of potassium carbonate with a concentration of 0.91 mol / L for 3 hours, dry at 75°C;...

Embodiment 3

[0030] As in Example 1, Fe(NO 3 ) 3 9H 2 O193.78g, Ca(NO 3 ) 2 4H 2 O16.56 grams and a concentration of 50% Mn(NO 3 ) 220.65 g of the solution was prepared with deionized water to form a mixed solution with a total concentration of 0.85 mol / liter, and the mixed solution was heated in a 90° C. water bath; the prepared ammonia solution with a concentration of 2.7 mol / liter was preheated in a 60° C. water bath; Put 100mL of ammonia solution with pH value of 9 in the four-neck round low flask in advance, keep the system temperature at 90°C, add the above ammonia solution and salt solution into the flask slowly and dropwise during the stirring process, the precipitation process takes about 35 minute. After the precipitation is completed, let it stand for about 12 hours, filter, wash the filter cake with deionized water until the pH value is 7.5, and filter again, dry the filter cake at 110-120°C for 24 hours; grind the dried filter cake finely, Immerse in 20mL of potassium ...

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PUM

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Abstract

A Fischer-Tropsch synthesis iron / manganese catalyst whose atomic ratio is composed of: Fe: Mn: IIA main group metal elements: K = 100: 4-100: 1-50: 0.5-10, and the precursor of the catalyst composition is carried out by precipitation method Prepare the catalyst. The present invention has chemical agent activity higher, low carbon olefin (C 2-4 ＝ ) and C 5 + Good selectivity, low methane selectivity, suitable for coal-based synthesis gas with low hydrogen-carbon ratio and natural gas-based synthesis gas with high hydrogen-carbon ratio.

Description

Technical field: [0001] The invention relates to an iron / manganese catalyst, in particular to an iron / manganese catalyst containing IIA main group metal elements for Fischer-Tropsch synthesis reaction and a preparation method thereof. Background technique: [0002] Fischer-Tropsch synthesis refers to synthesis gas (H 2 +CO) is converted into hydrocarbons under the action of a catalyst. Iron-based catalysts are particularly suitable for converting syngas with low hydrogen-to-carbon ratios, such as coal-based syngas, into light olefins (C 2-4 ＝ ) and heavy hydrocarbons (C 5 + ). Low-carbon olefins are not only an important chemical raw material but also gasoline and diesel can be produced through olefin oligomerization, while heavy hydrocarbons (C 5 + ) can produce liquid fuels through hydroisomerization or cracking reactions. In order to improve the performance of iron-based catalysts on low-carbon olefins (C 2-4 ＝ ) and heavy hydrocarbons (C 5 + ) selectivity and...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/889C07C1/04
Inventor 白亮杨勇相宏伟李永旺钟炳
Owner SYNFUELS CHINA TECH CO LTD
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