Sulfur-tolerant low-carbon alcohol catalyst and preparing method and application 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, and high water content of products, and achieve high C2+ OH selectivity, easy industrial application, the effect of simplifying the preparation process

Active Publication Date: 2010-06-16
SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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Problems solved by technology

Representative patents include patent EP-0034338-A2 and US Patent-4513100. Although the catalyst has high activity, the reaction conditions are harsh (the pressure is 14-20Mpa, and 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 sulfur
(3) Rh-based catalysts (such as US Patent 4014913 and 4096164): After adding 1-2 kinds of transition metal or metal oxide additives in the supported Rh catalyst, it has higher activity and selectivity for the synthesis of low-carbon alcohols, especially Yes to C 2 + The selectivity of alcohol is high, and the product is mainly ethanol, but the Rh compound is expensive, and the catalyst is easily destroyed by CO 2 Poisoning, due to the above limitations restricting its industrial development, so the reports in the current literature are gradually decreasing
There are two main problems with this catalyst: one is the H 2 / CO ratio is demanding (H 2 / CO molar ratio 1.0-1.1), the second is that the catalyst additive element Co is very easy to form carbonyl compounds with CO, resulting in the loss of additive elements, affecting the activity and selectivity of the catalyst, resulting in limited catalyst stability and life

Method used

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  • Sulfur-tolerant low-carbon alcohol catalyst and preparing method and application thereof

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Experimental program
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Effect test

Embodiment 1

[0039] At 60°C, with stirring, 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 adjusts pH=3; Fe(NO 3 ) 3 9H 2 O and (NH 4 ) 6 Mo 7 o 24 4H 2 O is added respectively in the above-mentioned solution with Fe:Mo molar ratio 0.125:1, wherein citric acid: (M 1 +M 2 ) molar ratio is 1:1, and then the solution is heated in a water bath at 60°C; stirring is continued for 2 hours, and the obtained product is treated at 100°C for 12 hours to obtain a FeMo precursor, cooled to room temperature, and placed in a muffle Roast in the furnace at 500°C for 3h, cool to room temperature and take out. After the precursor was ground to 60-80 mesh, 1.0 g was taken and placed in a quartz tube reactor, and Ar was passed into the reactor at a flow rate of 100 ml / min. Using temperature programming control, the temperature rises from room temperature to 400°C at a rate of 5°C / min, and ...

Embodiment 2

[0041] At 60°C, with stirring, 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 adjusts pH=3; Fe(NO 3 ) 3 9H 2 O and (NH 4 ) 6 Mo 7 o 24 4H 2 O is added in the above-mentioned solution respectively with Fe:Mo molar ratio 0.25:1, wherein citric acid: (M 1 +M 2 ) molar ratio is 1:1, and then the solution is heated in a water bath at 60°C; stirring is continued for 2 hours, and the obtained product is treated at 100°C for 12 hours to obtain a FeMo precursor, cooled to room temperature, and placed in a muffle Roast in the furnace at 600°C for 3h, cool to room temperature and take out. After the precursor was ground to 60-80 mesh, 1.0 g was taken and placed in a quartz tube reactor, and Ar was passed into the reactor at a flow rate of 100 ml / min. Using temperature programming control, the temperature rises from room temperature to 400°C at a rate of 5°C / min, and the ...

Embodiment 3

[0043] At 50°C, with stirring, 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; Co(NO 3 ) 2 ·6H 2 O and (NH 4 ) 6 Mo 7 o 24 4H 2 O was added to the above solution with a Co:Mo molar ratio of 0.1:1, wherein citric acid: (M 1 +M 2 ) with a molar ratio of 1:6 and then place the solution in a 60°C water bath and heat it; continue to stir for 12 hours, and treat the resulting product at 100°C for 12 hours to obtain a CoMo precursor, cool it to room temperature, and then place it in a muffle furnace Calcined at 600°C for 3h, 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 quartz tube reactor, and Ar was passed into the reactor at a flow rate of 100 ml / min. Using temperature programming control, the temperature rises from room temperature to 400°C at a rate of 5°C / min, and the temperature ris...

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Abstract

The invention relates to sulfur-tolerant low-carbon alcohol catalyst which has the expression of MC-M1-M2. The sulfur-tolerant low-carbon alcohol catalyst takes the M metal carbide as the active component, and M1 metal element and M2 metal element are added to the M metal carbide so as to be used as the auxiliary agents. The molar ratio of the M1 to the M2 to the M is 0.01-0.5:0.1-1:1. The M is one or some of the Mo, the W and the V, the M1 is one or some of the Fe, the Co, the Ni, the Cr, the Mn, the La, the Y and the Ce, and the M2 is one or some of the K, the Na, the Be and the Mg. The sulfur-tolerant low-carbon alcohol catalyst has the advantages of good sulfur tolerance, good stability and high activity.

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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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/22B01J37/00C07C29/153C07C29/156C07C31/04C07C31/08
CPCY02P20/52
Inventor 孙予罕冉宏峰姜东李德宝房克功林明桂
Owner SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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