CN102189003A - Preparation method of methanation catalyst carrier - Google Patents
Preparation method of methanation catalyst carrier Download PDFInfo
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- CN102189003A CN102189003A CN 201010127833 CN201010127833A CN102189003A CN 102189003 A CN102189003 A CN 102189003A CN 201010127833 CN201010127833 CN 201010127833 CN 201010127833 A CN201010127833 A CN 201010127833A CN 102189003 A CN102189003 A CN 102189003A
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Abstract
The invention belongs to the technical field of catalysis and relates to a preparation method of a methanation catalyst carrier. The method comprises the following steps of: dissolving aluminium nitrate, aluminium sulphate, magnesium nitrate or magnesium sulphate into water to prepare a mixed solution; neutralizing and precipitating by using sodium hydroxide, sodium carbonate or sodium hydrogen carbonate to obtain a precipitate; washing, filtering, drying, granulating, tabletting and roasting to obtain a rare-earth modified methanation catalyst carrier; and adding rare-earth metal nitrates into preparation process. The methanation catalyst carrier which is prepared by the method is good in hydro-thermal stability, low in surface acidity of the carrier, and applicable to preparation of a methanation catalyst of coal-based synthesis gas; and the carbon deposit of the catalyst with higher content of carbon oxide (CO) is difficult to occur at a higher reaction temperature.
Description
Technical field: the invention belongs to catalysis technical field, relate to a kind of preparation method of methanation catalyst carrier.
Background technology: natural gas is a kind of clear energy sources.Come into operation along with many natural gases " main artery " such as capital, China Shan line, transfering natural gas from the west to the east line build up in succession, natural gas has been used in increasing city, has improved urban environment greatly, has also significantly increased the demand of natural gas.
China is the country of " rich coal, oil-poor, weak breath ", utilize the coal resources of China's abundant, methanation production substitute natural gas by coal based synthetic gas has good economic benefit in the soaring oil prices epoch, to solving the problem of complex utilization of coal resources, alleviate the present situation of Chinese petroleum resources shortage, safeguard the energy security of China, realize CO
2Reduce discharging, protect environment all significant.
Usually contain more CO in the coal gas that coal gasification produces
X, in the presence of methanation catalyst, can be with CO
XAll be converted into methane, use as substitute natural gas.With gas reforming is the process (namely for methane course of reaction) of methane, and contingent reaction comprises in the methanation:
CO+3H
2→CH
4+H
2O+206.2KJ/mol (1)
CO
2+4H
2→CH
4+2H
2O+165KJ/mol (2)
CO+H
2O→H
2+CO
2+41KJ/mol (3)
CO→C+CO
2 (4)
Wherein, reaction (1) and (2) is the methanation main reaction, and the exothermic heat of reaction amount is very big.Typical coal based synthetic gas methanation reaction is operated in 250 ℃～650 ℃ scopes, because CO content is higher in the unstripped gas, and operating temperature height, use traditional methanation catalyst react easily (4) cause the catalyst surface carbon deposit, the covering catalyst surface, the blocking catalyst duct causes catalyst activity to reduce.
The methanation catalyst great majority are Ni/Al
2O
3System, as the disclosed methanation catalyst of Chinese patent CN 1043639A with Al
2O
3Be carrier, nickel is active constituent, with rare earth metal, or alkaline-earth metal, or alkali metal is co-catalyst.U.S. Pat 3933883 disclosed methanation catalysts are carrier with the high purity aluminium oxide, supported active component nickel oxide and cobalt oxide.These catalyst are carrier with the aluminium oxide, at trace amounts of CO
XMethanation reaction in use, reaction temperature is not high, steam partial pressure is lower in the reacting gas, catalyst has good stable.In the coal based synthetic gas methanation reaction, CO content is higher in the unstripped gas, use above-mentioned catalyst by reaction (4) the CO disproportionated reaction to take place easily, the carbon that generates is deposited on the catalyst surfaces externally and internally, covering catalyst surface and blocking catalyst duct cause catalyst activity reduction and bed resistance to increase.
Summary of the invention: the object of the invention is to provide a kind of preparation method of methanation catalyst carrier, the methanation catalyst surface acidity of this preparing carriers hangs down to use under higher CO content and higher reaction temperature and is difficult for carbon distribution, and this carrier is suitable for preparing the coal based synthetic gas methanation catalyst.
Methanation catalyst carrier provided by the invention prepares by the following method: with the mixing salt solution of aluminium, magnesium, rare earth metal, neutralize with alkali, the precipitation that obtains is through washing heat treatment, filtration, drying, granulation, compression molding, and roasting obtains rare earth modified methanation catalyst carrier.
The inventive method is achieved like this: the preparation of carrier may further comprise the steps: 1. with aluminum nitrate or the water-soluble mixed solution that is mixed with of aluminum sulfate, magnesium nitrate or magnesium sulfate, carry out neutralization precipitation with NaOH, sodium carbonate or sodium acid carbonate under 50 ℃～80 ℃; 2. with deionized water with washing of precipitate, in closed reaction kettle, be warmed up to 150 ℃～200 ℃ then and handle 1h～2h, cool to 50 ℃～80 ℃ again; 3. precipitate through concentrating and separating overwhelming majority water and make slurry, spray-drying then, the particle that obtains adds stearic acid and water, and compressing tablet becomes cylindrical pellet, and roasting 1h～4h obtains rare earth modified methanation catalyst carrier under 500 ℃～1000 ℃ roastings again.
In above-mentioned preparation process, also need to add the nitrate of rare earth metal, can join in the mixed solution in 1. in step, also can add in the slurry in 3. in step.
Rare-earth metal nitrate usually of the present invention is a kind of in lanthanum nitrate, cerous nitrate or the neodymium nitrate.
The neutralization precipitation of described catalyst carrier preparation process adopts the method for neutralization fast, and whole N-process is finished in 3min～5min.
Preferred 600 ℃～900 ℃ of the sintering temperature of the carrier in the described catalyst carrier preparation process.
Adopt the carrier of the inventive method preparation, the mixed precipitation for preparing magnesium, aluminium by the precipitation method, through heat treatment in the closed reactor and the roasting after the moulding, obtain rare earth modified methanation catalyst carrier, this carrier has good hydrothermal stability, the rare earth that adds is inhibited to the carrier surface acid site, and the methanation catalyst that is used to prepare has anti-carbon performance preferably.
The specific embodiment:
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1: take by weighing aluminum nitrate, magnesium nitrate water-soluble be mixed with contain Al 108g, contain Mg 48.6g, mixed solution A; Mixed solution A is used the sodium carbonate liquor neutralization precipitation down at 50 ℃～80 ℃, the precipitation that obtains spends deionised water earlier, in closed reaction kettle, be warmed up to 150 ℃～170 ℃ then and handle 1h～2h, make slurry through concentrating and separating overwhelming majority water again, add the lanthanum nitrate making beating and mix.The spray-dried particle that obtains of slurry adds stearic acid and water, and compressing tablet becomes cylindrical pellet, puts in the Muffle furnace and obtains rare earth modified methanation catalyst carrier i in 600 ℃～700 ℃ following roasting 1h～4h.
Embodiment 2: take by weighing water-soluble being mixed with of aluminum sulfate, magnesium sulfate, lanthanum nitrate and contain Al 108g, contain Mg 48.6g, contain the mixed solution A of La 35g; Mixed solution A is used the sodium hydroxide solution neutralization precipitation down at 50 ℃～80 ℃, the precipitation that obtains spends deionised water earlier, in closed reaction kettle, be warmed up to 180 ℃～200 ℃ then and handle 1h～2h, make slurry through concentrating and separating overwhelming majority water again, add the lanthanum nitrate making beating and mix.The spray-dried particle that obtains of slurry adds stearic acid and water, and compressing tablet becomes cylindrical pellet, puts in the Muffle furnace and obtains rare earth modified methanation catalyst carrier ii in 800 ℃～900 ℃ following roasting 1h～4h.
Embodiment 3: respectively with carrier i, ii and spherical γ-Al
2O
3Carrier floods nickel with infusion process, obtains nickel content and be 20% methanation catalyst I, II, III.
Embodiment 4: methanation catalyst I, II, III are seated in respectively in the tubular reactor at 3.0MPa, H
2O/H
2=10,500 ℃ of following operation 100h measure respectively with rear catalyst thing phase with x-ray diffractometer behind the end of run, and the result has found AlOOH thing phase in rear catalyst III, and all do not detect AlOOH thing phase in the catalyst I after usefulness, II.
Embodiment 5: methanation catalyst I, II, III are seated in respectively in the tubular reactor under 500 ℃ of pressure 3.0MPa, temperature, with CO content 10%, CO
2Content 3%, H
2Content 45%, surplus be CH
4Unstripped gas reaction 100h, having with rear catalyst III surface obviously has the carbon distribution phenomenon, and catalyst I, II surface all do not detect carbon.
According to the foregoing description, this traditional methanation catalyst of methanation catalyst of the present invention's preparation has better anti-phase transformation, anti-carbon performance, can under higher CO, vapour content, use, be suitable for the methanation reaction process of coal based synthetic gas system substitute natural gas.
Claims (4)
1. the preparation method of a methanation catalyst carrier, it is characterized in that realizing: 1., under 50 ℃～80 ℃, carry out neutralization precipitation with NaOH, sodium carbonate or sodium acid carbonate with aluminum nitrate or the water-soluble mixed solution that is mixed with of aluminum sulfate, magnesium nitrate or magnesium sulfate by following steps; 2. with deionized water with washing of precipitate, in closed reaction kettle, be warmed up to 150 ℃～200 ℃ then and handle 1h～2h, cool to 50 ℃～80 ℃ again; 3. precipitate through concentrating and separating overwhelming majority water and make slurry, spray-drying then, the particle that obtains adds stearic acid and water, and compressing tablet becomes cylindrical pellet, and roasting 1h～4h obtains rare earth modified methanation catalyst carrier under 500 ℃～1000 ℃ roastings again; 1. add the nitrate of rare earth metal or in the step 3. in preparation process.
2. the preparation method of catalyst carrier according to claim 1 is characterized in that rare-earth metal nitrate is a kind of in lanthanum nitrate, cerous nitrate or the neodymium nitrate.
3. the preparation method of catalyst carrier as claimed in claim 1 or 2 is characterized in that neutralization precipitation adopts the method for neutralization fast, and whole N-process is finished in 3min～5min.
4. the preparation method of catalyst carrier as claimed in claim 1 or 2 is characterized in that 600 ℃～900 ℃ of the sintering temperatures of carrier.
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| CN2010101278336A CN102189003B (en) | 2010-03-19 | 2010-03-19 | Preparation method of methanation catalyst carrier |
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| CN102189003B CN102189003B (en) | 2012-11-28 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389808A (en) * | 2011-10-17 | 2012-03-28 | 西南化工研究设计院 | Sulfur-resistant methanation catalyst and preparation method thereof |
| WO2013166653A1 (en) * | 2012-05-08 | 2013-11-14 | 中国科学院过程工程研究所 | Method for preparing ni-mg/al2o3 catalyst |
| CN103418442A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method of precious metal-containing low-carbon alkane dehydrogenation catalyst carrier |
| CN104028276A (en) * | 2014-06-10 | 2014-09-10 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing composite wide-temperature methanation catalyst |
| CN106748609A (en) * | 2016-12-09 | 2017-05-31 | 西安元创化工科技股份有限公司 | A kind of preparation method of methanation catalyst carrier |
| CN107880680A (en) * | 2017-12-19 | 2018-04-06 | 衢州职业技术学院 | High rigidity shock resistance body of a motor car paint and preparation method thereof |
| CN108043413A (en) * | 2017-11-15 | 2018-05-18 | 华东理工大学 | Catalyst for being combined to natural gas for coal methylmethane and preparation method thereof |
| CN113713845A (en) * | 2021-09-03 | 2021-11-30 | 成都龙飞科技有限公司 | Preparation method of CO methanation catalyst in hydrogen-rich environment and catalyst prepared by method |
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| US20080167180A1 (en) * | 2006-10-27 | 2008-07-10 | Peter John Van Den Brink | Method of manufacturing a catalyst |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389808A (en) * | 2011-10-17 | 2012-03-28 | 西南化工研究设计院 | Sulfur-resistant methanation catalyst and preparation method thereof |
| CN102389808B (en) * | 2011-10-17 | 2013-05-08 | 西南化工研究设计院 | Sulfur-resistant methanation catalyst and preparation method thereof |
| WO2013166653A1 (en) * | 2012-05-08 | 2013-11-14 | 中国科学院过程工程研究所 | Method for preparing ni-mg/al2o3 catalyst |
| CN103418442A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method of precious metal-containing low-carbon alkane dehydrogenation catalyst carrier |
| CN103418442B (en) * | 2012-05-16 | 2017-04-19 | 中国石油化工股份有限公司 | Preparation method of precious metal-containing low-carbon alkane dehydrogenation catalyst carrier |
| CN104028276A (en) * | 2014-06-10 | 2014-09-10 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing composite wide-temperature methanation catalyst |
| CN104028276B (en) * | 2014-06-10 | 2016-03-30 | 中国华能集团清洁能源技术研究院有限公司 | A kind of preparation method of compound molded breadth temperature methanation catalyst |
| CN106748609A (en) * | 2016-12-09 | 2017-05-31 | 西安元创化工科技股份有限公司 | A kind of preparation method of methanation catalyst carrier |
| CN106748609B (en) * | 2016-12-09 | 2019-07-30 | 西安元创化工科技股份有限公司 | A kind of preparation method of methanation catalyst carrier |
| CN108043413A (en) * | 2017-11-15 | 2018-05-18 | 华东理工大学 | Catalyst for being combined to natural gas for coal methylmethane and preparation method thereof |
| CN107880680A (en) * | 2017-12-19 | 2018-04-06 | 衢州职业技术学院 | High rigidity shock resistance body of a motor car paint and preparation method thereof |
| CN113713845A (en) * | 2021-09-03 | 2021-11-30 | 成都龙飞科技有限公司 | Preparation method of CO methanation catalyst in hydrogen-rich environment and catalyst prepared by method |
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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
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