Supported sulfur-resistant low-carbon alcohol catalyst, preparation method thereof and use thereof

A technology for catalysts and low-carbon alcohols, applied in catalyst activation/preparation, chemical instruments and methods, preparation of hydroxyl compounds, etc., can solve the problems of low selectivity of higher alcohols, harsh reaction conditions, affecting the activity and selectivity of catalysts, etc. The effect of high C2+OH selectivity, easy industrial application, and excellent sulfur resistance

Active Publication Date: 2010-06-16
SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Representative patents include EP-0034338-A2 and US Patent-4513100. Although the catalyst has high activity, the reaction conditions are harsh (the pressure is 14-20Mpa, the temperature is 350-450°C), and the selectivity of higher alcohols is low (generally less than 35 %), high water content in the product (generally 30-50%), very sensitive to sulfur
(2) Modified F-T catalyst: The French Institute of Petroleum (IFP) first developed the Cu-Co co-precipitated low-carbon alcohol catalyst, and obtained four catalyst patents before 1985 (US Patent 4122110 and 4291126 and GB Patent 2118061 and 2158730) The product synthesized by this catalyst is mainly C 1 -C 6 Linear normal alcohol, the by-product is mainly C 1 -C 6 Aliphatic hydrocarbons, mild reaction conditions (similar to low-pressure methanol synthesis catalysts), but poor stability, like the first type of catalyst, the catalyst is extremely sensitive to su

Method used

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  • Supported sulfur-resistant low-carbon alcohol catalyst, preparation method thereof and use thereof

Examples

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Example Embodiment

[0042] Example 1

[0043] powder carrier SiO 2 (80-100 mesh), calcined at 500°C for 3 hours, with water and ethanol (H 2 O / C 2 h 5 OH=1:5) mixed solution is the citric acid solution of solvent preparation 0.4mol / L, adds concentrated hydrochloric acid and is adjusted to pH=3; Fe(NO 3 ) 3 9H 2 O and (NH 4 ) 6 Mo 7 o 24 4H 2 O was added to the above solution at a Fe:Mo molar ratio of 0.125:1, wherein the molar ratio of citric acid:M (main metal and second metal) was 1:1, and a certain amount of SiO was added under stirring conditions. 2 (the loading of Mo is determined as wt.20%), then the solution is heated in a water bath at 60°C; stirring is continued for 2 hours, and the resulting product is treated at 100°C for 12 hours to obtain FeMo / SiO 2 The precursor was cooled to room temperature, then placed in a muffle furnace for 3 h at 500°C, and then cooled to room temperature and taken out. After the precursor was ground to 60-80 mesh, 1.0 g was taken and placed in a q...

Example Embodiment

[0044] Example 2

[0045] powder carrier SiO 2 (80-100 mesh), roasted at 600°C for 3 hours, at 60°C, under stirring conditions, with water and methanol (H 2 O / CH 3 OH=1:5) mixed solution is the citric acid solution of solvent preparation 0.4mol / L, adds concentrated hydrochloric acid and is adjusted to pH=3; Fe(NO 3 ) 3 9H 2 O and (NH 4 ) 6 Mo 7 o 24 4H 2 O was added to the above solution at a Fe:Mo molar ratio of 0.25:1, wherein the molar ratio of citric acid:M (main metal and second metal) was 1:1, and a certain amount of SiO was added under stirring conditions. 2 (The loading of Mo is determined as wt.17%), and then the solution is heated in a water bath at 60°C; stirring is continued for 2 hours, and the resulting product is treated at 100°C for 12 hours to obtain FeMo / SiO 2 The precursor was cooled to room temperature, then placed in a muffle furnace for 3 h at 600°C, and then cooled to room temperature and taken out. After the precursor was ground to 60-80 mesh...

Example Embodiment

[0046] Example 3

[0047] powder carrier Al 2 o 3 (80-100 mesh), roasted at 700°C for 3 hours, at 50°C, under stirring conditions, mixed with water and ethanol (H 2 O / C 2 h 5 OH=1:5) mixed solution is the citric acid solution of solvent preparation 0.6mol / L, adds concentrated hydrochloric acid 1.5ml, is adjusted to pH=2.0; Co(NO 3 ) 2 ·6H 2 O and (NH 4 ) 6 Mo 7 o 24 4H 2 O was added to the above solution at a Co:Mo molar ratio of 0.1:1, wherein the molar ratio of citric acid:M (main metal and second metal) was 1:6, and a certain amount of Al was added under stirring conditions. 2 o 3 (The loading of Mo is determined to be wt.23%), and then the solution is heated in a water bath at 60°C; stirring is continued for 12 hours, and the resulting product is treated at 100°C for 12 hours to obtain CoMo / Al 2 o 3 The precursor was cooled to room temperature, then placed in a muffle furnace for 3 h at 600°C, and then cooled to room temperature and taken out. After the prec...

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Abstract

The invention discloses a supported sulfur-resistant low-carbon alcohol catalyst, which is expressed as MC-M1-M2/S, wherein the carbide of a metal M is used as an active ingredient; metals M1 and M2 are used as assistants; the active ingredient of the catalyst is supported by an oxide carrier S; the M supporting capacity of the carrier is 15 to 50 weight percent based on the weight of S; the molar ratio of the M1 to M2 to M is 0.01-0.5:0.1-1:1; M is one or more of Mo, W, and V; M1 is one or more of Fe, Co, Ni, Cr, Mn, La, Y and Ce; M2 is one or more of K, Na, Be and Mg; and S is one or more of SiO2, ZrO2, Al2O3, MgO and TiO2. The catalyst has the advantages of high sulfur resistance, high stability, high activity, high C2+ alcohol selectivity and long service life.

Description

technical field [0001] The invention relates to a catalyst and its preparation method and application, in particular to a sulfur-resistant catalyst for preparing low-carbon alcohols from synthesis gas, its preparation method and application. Background technique [0002] The industrial application of coal-based carbon-chemicals based on CO hydrogenation synthetic fuels and chemicals reduces the dependence on limited petroleum resources, and is of great significance to economic development, environmental protection, and especially the guarantee of national energy security. . Low-carbon mixed alcohols (C1-C6 alcohol mixtures, Higher Alcohols, Mixed Alcohols) produced from syngas based on coal and natural gas can be used as high-efficiency and high-quality fuel additives, fuels, and chemical raw materials. It has the characteristics of clean combustion, explosion-proof, shock-proof and high-octane number, and is an effective way to optimize the use of energy and resources. ...

Claims

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Application Information

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IPC IPC(8): B01J27/22B01J37/00C07C29/153C07C29/156C07C31/04C07C31/08
CPCY02P20/52
Inventor 孙予罕姜东李德宝冉宏峰
Owner SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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