Iron base catalyst used for Fischer-Tropsch synthesis and preparation method and application thereof

An iron-based catalyst and Fischer-Tropsch synthesis technology, applied in catalyst activation/preparation, chemical instruments and methods, preparation of liquid hydrocarbon mixtures, etc., can solve problems such as low reserves, metal loss, and catalysts that have not entered the stage of industrial application

Active Publication Date: 2010-08-25
SYNFUELS CHINA TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, only four metals, Fe, Co, Ni, and Ru, have sufficiently high CO hydrogenation reactivity, and they have application value for Fischer-Tropsch synthesis, among which Ru has the highest activity, and can obtain quite high reactivity even at 150 °C. High hydrocarbon yield, but low reserves and high price limit its large-scale industrial application
The activity of the Ni-based catalyst is also relatively high, but it has two main disadvantages: one is the strong hydrogenation ability that makes the CH in the Fischer-Tropsch synthesis product of the Ni catalyst 4 The amount of production is much higher than that of Fe-based and Co-based catalysts; second, under typical industrial Fischer-Tropsch synthesis operating conditions, Ni is prone to generate volatile metal carbonyl compounds, resulting in continuous loss of metals
[0010] The above-mentioned catalysts have their own characteristics in terms of composition, preparation method and application according to the different synthesis gas sources and target products, but some of them have not yet entered the stage of substantive industrial application

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0076] Embodiment 1 catalyst preparation

[0077] 1.0T of FeSO 4 ·7H 2 O soluble in 3.0m 3 In deionized water, add 70L of 3mol / L sulfuric acid solution. Add 15% H to the mixed solution 2 o 2 450L of aqueous solution was oxidized under vigorous stirring at 20°C for 2 hours. 47kg of CuSO 4 ·5H 2 O was dissolved in 100L of deionized water and added to the ferric sulfate solution prepared above. 0.7T of Na 2 CO 3 dissolve into 2.5m 3 An aqueous solution of sodium carbonate was obtained in deionized water. The two solutions are respectively heated to 70° C. for co-precipitation, the temperature of the precipitation tank is kept at 75° C., the pH of the mixed solution is 7-7.5, and the mixed coprecipitation process is completed within 15 minutes. Leave to age for 30 minutes. Filter and wash with deionized water until no sulfate is detected. Add water to the filter cake to re-beat, and add an appropriate amount of Li according to the ratio of Fe / Li=100 / 2 2 CO 3 Aqueo...

Embodiment 2

[0078] Example 2 Catalyst preparation

[0079] 1.0T of Fe(NO 3 ) 3 9H 2 O soluble in 2.0m 3 In deionized water, prepare liquid ammonia water to make 10wt% ammonia solution 2.0m 3 . The two solutions are respectively heated to 40° C., co-currently precipitated, the temperature of the precipitation tank is kept at 65° C., the pH of the mixed solution is 8.5-9, and the mixed coprecipitation process is completed within 10 minutes. Leave to age for 20 minutes. Filter and wash with appropriate amount of deionized water. After adding water to the filter cake, re-beating, add an appropriate amount of silver nitrate aqueous solution according to the ratio of Fe / Ag=100 / 0.5, and stir well; according to Fe / K / SiO 2 The ratio of =100 / 6 / 16 is added with a modulus of 3.3 containing 25wt% SiO 2 Potassium silicate water glass solution, after fully stirring, shear at high speed, and then spray dry the slurry. Take the required amount of dried spherical catalyst, impregnate the same vo...

Embodiment 3

[0080] Example 3 catalyst preparation

[0081] 0.5T iron ingot and 10kg copper scrap are reacted with an appropriate amount of nitric acid solution with a weight percentage of 20wt%. After the tail gas is absorbed by spraying with deionized water, it is then absorbed by soda ash solution. will be 4.0m 3 The obtained ferric nitrate and copper nitrate mixed solution is poured into the acid tank; the water in the alkali tank is mixed with saturated ammonium carbonate solution 4.0m 3 . The two solutions are respectively heated to 80° C. for co-precipitation, the temperature of the precipitation tank is kept at 85° C., the pH of the mixed solution is 7.0 to 7.5, and the mixed coprecipitation process is completed within 40 minutes. Leave to age for 10 minutes. Filter and wash with appropriate amount of deionized water. Then add water to the filter cake to re-beat, add an appropriate amount of potassium acetate aqueous solution according to the ratio of Fe / K=100 / 3, after fully ...

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PUM

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Abstract

The invention discloses an iron base catalyst used for Fischer-Tropsch synthesis and a preparation method and the application thereof. The catalyst comprises iron, reducing auxiliary agents of IB family metal Cu and / or Ag oxides, electronic auxiliary agents of IA family metal Li, Na, K or Rb, hydrogenation auxiliary agents of VIII family noble metal Ru, Rh, Pd or Pt and structural auxiliary agents of SiO2. The preparation method of the catalyst comprises the following steps: using alkaline compounds for carrying out fast coprecipitation on iron salts or a mixture of the iron salts or reducing auxiliary agents of IB family metal salt solutions; carrying out secondary pulping after precipitate washing; adding IA family metal salt solutions and silica sol, or adding IA family metal silicate in the pulp; carrying out spray drying forming on pulp; then, soaking obtained materials in VIII family noble metal salt solution; and obtaining the catalyst of the invention after drying roasting. The catalyst is applicable to the technical process for producing hydrocarbon through low-temperature Fischer-Tropsch synthesis reaction, and has high heavy hydrocarbon product yield, wherein the methane selectivity is very low, and the olefin selectivity is also obviously reduced.

Description

technical field [0001] The present invention relates to a kind of CO hydrogenation reaction catalyst and preparation method thereof, specifically, the present invention relates to a kind of iron-based catalyst for Fischer-Tropsch synthesis, its preparation method and the use of the catalyst in the method for producing hydrocarbons by Fischer-Tropsch synthesis technology application. Background technique [0002] Fischer-Tropsch synthesis was invented in Germany in the 1920s and gradually turned to industrial applications. It consists of synthesis gas (CO+H 2 ) is a method of producing liquid fuels from coal, natural gas, coal bed methane, and other carbon-containing biomass. The main active metals of Fischer-Tropsch synthesis catalysts are Group VIII metals. Among them, only four metals, Fe, Co, Ni, and Ru, have sufficiently high CO hydrogenation reactivity, and they have application value for Fischer-Tropsch synthesis, among which Ru has the highest activity, and can obta...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/745B01J23/72B01J23/89B01J23/78C07C1/04
CPCB01J23/78B01J21/08C10G2/342C10G2/333B01J23/8906B01J37/0045B01J23/8946C10G2300/4031C10G2/332B01J37/03
Inventor 吴宝山杨勇李永旺相宏伟
Owner SYNFUELS CHINA TECH CO LTD
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