Load type sulfur-tolerant methanation catalyst and preparation method and application thereof

A technology for sulfur-resistant methanation and catalyst, which is applied in physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc. The effect of improving utilization and high activity

Active Publication Date: 2010-06-23
SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This type of molybdenum-based sulfur-resistant catalyst is molybdenum oxide before the reaction, and it must be used with a ...

Method used

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  • Load type sulfur-tolerant methanation catalyst and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Formula: citric acid / (Ni+Mo) molar ratio is 1:0.5, Ni:Mo:TiO 2 The mass ratio is 1:10:30

[0038] TiO 2 The carrier was calcined at 400°C for 2 hours, and the preparation of the catalyst was carried out according to the formula as follows:

[0039] Under stirring conditions at 35°C, prepare citric acid, water / ethanol mixed solution (H 2 O / C 2 h 5 OH=1:10w / w), adjust the solution pH=1.5 with concentrated nitric acid; add Ni(NO 3 ) 3 ·6H 2 O solution and (NH 4 ) 6 Mo 7 o 24 4H 2 O solution, continue to stir for 14 hours, add the TiO after roasting treatment 2 Continue to stir for 5 hours, continue to evaporate the solvent at 60°C to a viscous solution, and dry the obtained product at 140°C for 4 hours to obtain Ni-Mo / TiO 2 Precursor. Grind the obtained precursor to a particle size of less than 0.25mm and place it in a quartz reaction tube, blow it with argon gas at a flow rate of 120mL / min, and use two-stage temperature program control to increase the temper...

Embodiment 2

[0041] Formula: citric acid / (Ni+Mo) molar ratio is 1:0.5, Fe:Mo:SiO 2 The mass ratio is 1:5:30

[0042] SiO 2 The carrier was calcined at 800°C for 24 hours, and the preparation of the catalyst was carried out according to the formula as follows:

[0043] Under stirring conditions at 20°C, prepare citric acid, water / ethanol mixed solution (H 2 O / C 2 h 5 OH=10:1w / w), adjust the solution pH=1.5 with concentrated nitric acid; add Fe(NO 3 ) 3 9H 2 O solution and (NH 4 ) 6 Mo 7 o 24 4H 2 O solution, continue to stir for 24 hours, add the calcined SiO 2 Continue to stir for 24 hours, continue to evaporate the solvent at 90°C to a viscous solution, and dry the obtained product at 140°C for 24 hours to obtain Fe-Mo / SiO 2 Precursor. Grind the obtained precursor to a particle size of less than 0.25mm and place it in a quartz reaction tube, and pass in argon gas at a flow rate of 150mL / min, and use two-stage temperature program control to increase the temperature from room ...

Embodiment 3

[0045] Formula: tartaric acid / (Co+Mo) molar ratio is 1:0.2, Co:Mo:Al 2 o 3 The mass ratio is 0.01:30:90

[0046] Al first 2 o 3 The carrier was roasted at 500°C for 12 hours, and the preparation of the catalyst was carried out according to the formula as follows:

[0047] Under the condition of stirring at 60°C, prepare a mixed solution of tartaric acid and water, adjust the pH of the solution to 1.5 with acetic acid; add Co(NO 3 ) 3 ·6H 2 O solution and (NH 4 ) 6 Mo 7 o 24 4H 2 O solution, continue to stir for 1 hour, add the Al after roasting treatment 2 o 3 Continue to stir for 1 hour, continue to evaporate the solvent at 60°C to a viscous solution, and dry the obtained product at 60°C for 24 hours to obtain Co-Mo / Al 2 o 3 Precursor. Grind the obtained precursor to a particle size of less than 0.25 mm and place it in a quartz reaction tube, blow nitrogen gas at a flow rate of 60 mL / min, and use two-stage temperature program control to increase the temperature...

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Abstract

The invention discloses a load type sulfur-tolerant methanation catalyst, which is characterized by taking a main metal M as an active component, a second metal M1 as an auxiliary agent and S as a carrier, and consisting of the metal M, the metal M1 and the carrier S, wherein the mass ratio of the M1 to the M to the S is 0.01-39:1-30:0.01-90; the main metal M is one or more of Mo, W and V; the second metal M1 is one or more of Fe, Co, Ni, Cr, Mn, La, Y or Ce; and the carrier S is SiO2, ZrO2, Al2O3, MgO or TiO2. The load type sulfur-tolerant methanation catalyst is prepared by a sol-gel method. The metallic carbide catalyst prepared by the method has the advantages of low cost, high specific area, small particles, high methane selectivity and better sulfur tolerance when used for CO hydrogenation methanation reaction, and the like.

Description

technical field [0001] The invention relates to a methanation catalyst and its preparation method and application, in particular to a sulfur-resistant methanation catalyst and its preparation method and application. Background technique [0002] Coal, oil and natural gas are the three pillars of the world's energy supply in the 21st century. At present, in the world's energy consumption structure, oil accounts for 39.7% and natural gas accounts for 23.2%. The proportion is only about 2.5%, far lower than the world average and the Asian average of 10.1%. Natural gas is not only a high-quality fuel, but also an important raw material for the chemical industry. With the continuous discovery and exploitation of natural gas resources, the scope of utilization of natural gas has gradually expanded, and it has played an important role in my country's economic construction. Experts predict that the proportion of natural gas in China's energy consumption structure will reach 6 per...

Claims

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Application Information

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IPC IPC(8): B01J23/883B01J23/881B01J23/882B01J23/889B01J23/34B01J23/847B01J23/888C07C9/04C07C1/04
Inventor 孙予罕赵立红姜东李德宝侯博王俊刚
Owner SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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