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Low-temperature high-activity methanation catalyst and preparation method thereof

A methanation catalyst, high activity technology, applied in physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc. Expensive, no data and other problems, to achieve the effect of increasing surface utilization, improving low-temperature activity, and increasing nickel content

Active Publication Date: 2014-04-09
SOUTHWEST RES & DESIGN INST OF CHEM IND
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] At present, the research on low-temperature methanation catalysts at home and abroad is mainly concentrated on ruthenium (Ru)-based and nickel (Ni)-based catalysts. Although ruthenium catalysts have better low-temperature activity, they do not have industrial application value due to their high price. , so Ni-based catalysts are widely used
However, the application of low-temperature methanation catalysts with metallic nickel as the active component is still at a high hydrogen-to-carbon ratio (H 2 / (CO+CO 2 )), high activity temperature, and low reaction space velocity, and the catalyst has poor heat resistance and oxidation resistance, weak ability to resist system fluctuations, and narrow application range
For example, the domestic ammonia synthesis system uses a methanation catalyst, the reaction temperature is generally above 300 °C, and the H 2 / CO 2 ≥50, the maximum operating temperature is 450°C; although it is reported that the minimum applicable temperature of the methanation catalyst produced by the British Davy Company abroad is 230°C, no specific data has been found

Method used

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  • Low-temperature high-activity methanation catalyst and preparation method thereof
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  • Low-temperature high-activity methanation catalyst and preparation method thereof

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Effect test

Embodiment 1

[0049] In the present embodiment, the component mass percent of the low-temperature high-activity methanation catalyst is required to be:

[0050] NiO: 18%, Al 2 o 3 : 70%, MgO: 11.5%, La 2 o 3 : 0.4%, MnO 2 : 0.1%.

[0051] The specific preparation process is as follows.

[0052] a) Auxiliary precipitation: Weigh 214.33g of porous Al(OH) passing through a 300-mesh sieve 3 , and add 147.21g Mg(NO 3 ) 2 ·6H 2 O is poured into the first constant temperature reactor. Then add 3000ml of deionized water into the first constant temperature reaction kettle to form a turbid solution. When the turbid liquid in the first constant temperature reaction kettle was uniformly heated to 70°C, slowly add 9% Na 2 CO 3 The solution was stirred continuously, keeping the temperature constant, and reacted for 2 hours. When the pH value of the cloudy solution was 7.0, the carrier mixture was obtained. Then the carrier mixture was filtered, and the filtered slurry was poured into a polyt...

Embodiment 2

[0056] In the present embodiment, the component mass percent of the low-temperature high-activity methanation catalyst is required to be:

[0057] NiO: 25%, Al 2 o 3 : 40%, MgO: 30%, La 2 o 3 : 2%, MnO 2 : 3%.

[0058] The specific preparation process is as follows.

[0059] a) Precipitation of additives: Weigh 122.48g of porous Al(OH) passing through a 300-mesh sieve 3 , and add 384.05g Mg(NO 3 ) 2 ·6H 2 O, poured into the first constant temperature reactor. Then add 3000ml of deionized water into the first constant temperature reaction kettle to form a turbid solution. When the turbid liquid in the first constant temperature reaction kettle was evenly heated to 65°C, slowly add 9% Na 2 CO 3 The solution was stirred continuously, keeping the temperature constant, and reacted for 3 hours. When the pH value of the cloudy solution was 6.5, the carrier mixture was obtained. Then the carrier mixture was filtered, and the filtered slurry was poured into a polytetrafluo...

Embodiment 3

[0063] In the present embodiment, the component mass percent of the low-temperature high-activity methanation catalyst is required to be:

[0064] NiO: 35%, Al 2 o 3 : 45%, MgO: 15%, La 2 o 3 : 2%, MnO 2 : 3%.

[0065] The specific preparation process is as follows.

[0066] a) Precipitation of additives: Weigh 137.78g of porous Al(OH) passing through a 300-mesh sieve 3 , and add 192.00g Mg(NO 3 ) 2 ·6H 2 O, poured into the first constant temperature reactor. Then add 3000ml of deionized water into the first constant temperature reaction kettle to form a turbid solution. When the turbid liquid in the first constant temperature reaction kettle was evenly heated to 70°C, slowly add 9% Na 2 CO 3 The solution was stirred continuously, keeping the temperature constant, and reacted for 2 hours. When the pH value of the cloudy solution was 7.5, the carrier mixture was obtained. Then the carrier mixture was filtered, and the filtered slurry was poured into a polytetrafluo...

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Abstract

The invention discloses a low-temperature high-activity methanation catalyst and a preparation method thereof. The catalyst comprises metallic nickel as an active component, AL2O3 as a carrier and MgO as a structure auxiliary agent, and an appropriate amount of lanthanum oxide and manganese oxide are added as active auxiliary agents. The catalyst comprises the following main components in percentage by mass: 18-45% of NiO, 40-70% of Al2O3, 5-30% of MgO, 0.4-5% of La2O3 and 0.1-5% of MnO2. The catalyst disclosed by the invention has the advantages of large specific area, uniform nickel dispersity, good heat stability, strong oxidation resistance, low active temperature, adaptability to low hydrogen-carbon ratio and the like. The catalyst is applicable to preparation of LNG (liquefied natural gas) through methanation of industrial gases including coke oven gas, coal synthesis gas, semi coke exhaust gas and the like rich in CO, CO2 and H2, is particularly applicable to a methanation reaction in a low-temperature section, and can effectively improve the quality of synthetic natural gas. Meanwhile, the invention also provides the preparation method of the catalyst, and the preparation method is simple in process flow and can realize industrial production easily.

Description

technical field [0001] The invention belongs to the technical field of methanation catalysis, in particular to a low-temperature high-activity methanation catalyst and a preparation method thereof, in particular to a low-concentration CO and CO catalyst used in methane-enriched gas 2 Catalyst for hydromethanation and method for its preparation. In industry, the catalyst can be applied to coke oven gas, coal-to-synthesis gas, semi-coke tail gas and other industrial gas methanation to LNG devices to improve the quality of synthetic natural gas. Background technique [0002] In recent years, my country's natural gas market has developed rapidly, and the gap between supply and demand is getting bigger and bigger. Domestic large-scale unconventional natural gas projects such as coal-to-natural gas, coke oven gas-to-natural gas and other industrial exhaust gas to synthetic natural gas are booming, and continue to become a useful supplement to my country's natural gas industry. A...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/889B01J35/10C10L3/08
Inventor 谭建冬郭雄张新波郑珩陈俊生刘玉成张恒
Owner SOUTHWEST RES & DESIGN INST OF CHEM IND
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