Catalyst for methanating coke oven gas and preparation method thereof

A coke oven gas and catalyst technology, applied in physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problems of increased equipment investment, large catalyst consumption, and lack of provision, etc. problems, to achieve high activity, improved thermal stability, and high operating space velocity

Inactive Publication Date: 2012-06-27
DALIAN CATALYTIC ENG TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, it does not provide stability data at higher temperatures (above 400°C) and activity data at lower temperatures (below 350°C). Generally speaking, the operating temperature in the adiabatic non-circulating methanation process will be above 500°C. The operating temperature in the heat exchange reactor methanation process is below 300°C, and only the operating temperature of the cyclic adiabatic methanation process is between 400-500°C, which leads to the fact that the methanation catalyst disclosed in this patent may only be suitable for cyclic adiabatic methanation process; in addition, its volumetric space velocity is low - 4000h -1 , the low volumetric space velocity means that the amount of catalyst is large, and the volume of the methanation reactor is also increased, resulting in an increase in catalyst procurement cost and equipment investment.

Method used

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  • Catalyst for methanating coke oven gas and preparation method thereof
  • Catalyst for methanating coke oven gas and preparation method thereof
  • Catalyst for methanating coke oven gas and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] 90g Na 2 CO 3 Dissolve in 350ml deionized water for later use. 198g Ni(NO 3 ) 2 ·6H 2 O, 31g La(NO 3 ) 3 ·6H 2 O was dissolved in 400ml deionized water and stirred evenly to form a solution 1, 78gMn(NO 3 ) 2 (50% content), 19g Zr(NO 3 ) 2 ·5H 2 O was dissolved in 200ml deionized water and stirred uniformly to form solution 2. 114g Al 2 o 3 Slowly add the powder to solution 1 and stir well. To this solution was added solution 2 followed by Na 2 CO 3 The solution allowed sufficient precipitation of the metal ions, and stirring was continued for 30 minutes. After washing and drying, the precipitate was dried at 120°C for 8 hours, and then the precipitate was calcined in a muffle furnace at 600°C for 4 hours, and a φ3×3mm cylindrical catalyst was obtained through a tableting process. The catalyst was reduced at 400° C. for 4 hours under a hydrogen atmosphere to obtain a final coke oven gas methanation catalyst.

[0026] Activity test results: CO conversio...

Embodiment 2

[0028] 103g Na 2 CO 3 Dissolve in 350ml deionized water for later use. 200g Ni(NO 3 ) 2 ·6H 2 O was dissolved in 400ml deionized water and stirred evenly to form solution 1, 20g La(NO 3 ) 3 ·6H 2 O, 10g Sr(NO 3 ) 2 4H 2 O, 15g Zr(NO 3 ) 2 ·5H 2 O was dissolved in 100ml deionized water and stirred uniformly to form solution 2. 120g Al 2 o 3Slowly add the powder into solution 1 and stir evenly, add Na to the solution at the same time 2 CO 3 Solution and additive solution 2 fully precipitate metal ions, and continue to stir for 30 minutes. After washing and drying, the precipitate was dried at 120°C for 8 hours, and then the precipitate was calcined in a muffle furnace at 600°C for 4 hours, and a φ3×3mm cylindrical catalyst was obtained through a tableting process. The catalyst was reduced at 400° C. for 4 hours under a hydrogen atmosphere to obtain a final coke oven gas methanation catalyst.

[0029] Activity test results: CO conversion rate is 84.17%, CH 4 T...

Embodiment 3

[0031] Dissolve 70g NaOH in 350ml deionized water for later use. 200g Ni(NO 3 ) 2 ·6H 2 O, 10g La(NO 3 ) 3 ·6H 2 O, 10g Zr(NO 3 ) 2 ·5H 2 O, 7g Ce(NO 3 ) 3 ·6H 2 O was dissolved in 400ml deionized water and stirred well. Slowly add 132g Al with stirring 2 o 3 Mix the powder well. NaOH solution was added to the solution to fully precipitate metal ions, and stirring was continued for 30 minutes. After washing and drying, the precipitate was dried at 120°C for 8 hours, and then the precipitate was calcined in a muffle furnace at 600°C for 4 hours, and a φ3×3mm cylindrical catalyst was obtained through a tableting process. The catalyst was reduced at 400° C. for 4 hours under a hydrogen atmosphere to obtain a final coke oven gas methanation catalyst.

[0032] Activity test results: CO conversion rate is 80.35%, CH 4 The selectivity is 77.56%; the conversion rate of CO under this condition is theoretically calculated to be 87.93%, and the CH 4 The selectivity is: ...

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Abstract

The invention relates to a technology for manufacturing artificial natural gas by methanating oxycarbide and provides a catalyst for methanating coke oven gas and a preparation method thereof. The catalyst is a gamma-aluminum oxide or a TiO2 carrier for carrying an active component and an addition agent, wherein the active component is Ni and the addition agent is composed of a first addition agent and a second addition agent; the first addition agent is a rare-earth element and the second addition agent is one or combination of more of Sr, Mn, V, Zr, Ce and Cr. The catalyst provided by the invention has good coke oven gas methanation activity and selectivity, and has the advantages of good high-temperature resistance, low-temperature activity and higher use space velocity; and the catalyst can be applied to various coke oven gas methanation processes including heat-insulating circulation, heat-insulating non-circulation, heat-exchange reactors and the like, and operation space velocities in the processes are more than 5000 per hour.

Description

technical field [0001] The invention relates to the technology of producing artificial natural gas through methanation of carbon oxides, and provides a coke oven gas methanation catalyst and a preparation method thereof. technical background [0002] The comprehensive utilization of coking gas has always been a major issue in the coking industry, which produces a large amount of coke oven gas (calorific value 16.746MJ / Nm 3 ). About 400m by-product per ton of coke 3 Calculation of coke oven gas, independent coking enterprises produce 89.4 billion cubic meters of coke oven gas every year 3 about. At present, the industrial use of coke oven gas mainly includes: as city gas; power generation; hydrogen extraction from coke oven gas; production of methanol, dimethyl ether or synthetic ammonia after deep purification. However, some of these utilization methods have low efficiency and energy utilization rate, and some have poor markets and poor economic benefits. The coke oven ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/889B01J23/83C07C9/04C07C1/04C10L3/08
Inventor 刘振峰杜霞茹李楠邱国文任宪平李锋张东辉宋跃奇肖菲刘金刚
Owner DALIAN CATALYTIC ENG TECH
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