CN1288854A - Catalyst for steam reformation of methanol to produce hydrogen - Google Patents

Catalyst for steam reformation of methanol to produce hydrogen Download PDF

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Publication number
CN1288854A
CN1288854A CN 00122375 CN00122375A CN1288854A CN 1288854 A CN1288854 A CN 1288854A CN 00122375 CN00122375 CN 00122375 CN 00122375 A CN00122375 A CN 00122375A CN 1288854 A CN1288854 A CN 1288854A
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China
Prior art keywords
catalyst
cuo
zno
methanol
produce hydrogen
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CN 00122375
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Chinese (zh)
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CN1111446C (en
Inventor
蔡迎春
刘淑文
徐贤伦
李树本
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The present invention discloses a hydrogen-making catalyst by reforming aqueous vapour of methyl alcohol. Said catalyst is CuO/ZnO/La2O3/Al2O3 catalyst, and is prepared by utilizing coprecipitation method. Said catalyst is low in cost, high in activity, good in selectivity and stability, under the condition of proper water-alcohol ratio and proper reaction temp. the conversion rate of methyl alcohol is greater than 87.5%, and its CO3 selectivity is greater than 96%.

Description

Catalyst for steam reformation of methanol to produce hydrogen
The present invention relates to a kind of metal oxide catalyst, be used for the methanol steam reformation and produce hydrogen.
Hydrogen is important industrial gasses, and traditional hydrogen production process mainly adopts brine electrolysis, and this method power consumption is many, and cost is higher.In recent years, along with expanding economy, the hydrogen demand amount is increasing and more and more present multi-point and wide-ranging characteristics, traditional water electrolysis hydrogen production more and more is difficult to meet the demands, closely during the last ten years, for obtaining hydrogen source easily, steam reformation of methanol to produce hydrogen more and more comes into one's own.
Industrial most widely used catalyst for steam reformation of methanol to produce hydrogen is CuO/ZnO/Al at present 2O 3Catalyst, this catalyst low-temperature activity height, selectively good, but catalyst stability is relatively poor.People such as Hao Shuren (fine chemistry industry, 1998,15 (5): 52-54) reported a kind of dual-function catalyst, this catalyzer has higher activity, but being divided into methanol decomposition-steam, this reaction transforms two steps, temperature of reaction higher (260 ℃-280 ℃), and the selectivity of reaction is relatively poor.Recently, the people such as mass troops and reported the CuO/ZnO/CeO that a kind of activity is high 2/ Al 2O 3Catalyst, this catalyst is at 260 ℃, and methanol conversion reaches more than 98%, but this result has under the condition of diluent gas argon gas to obtain, and has than big difference with actual industrial operating condition (no carrier gas).
The objective of the invention is to improve the deficiency of existing methanol steam reforming catalyst, a kind of catalyst for steam reformation of methanol to produce hydrogen with satisfactory stability and greater activity is provided.
The objective of the invention is to be achieved through the following technical solutions.
Catalyst activity component of the present invention is CuO, and carrier is Al 2O 3, co-catalyst is ZnO and La 2O 3
General formula of the present invention is CuO/ZnO/La 2O 3/ Al 2O 3, its CuO, ZnO, La 2O 3, Al 2O 3Mol ratio is 100: X: Y: 29.42, and wherein X is 78.20-99.40, Y is 1.10-5.58.
The catalyst that the present invention adopts is CuO/ZnO/La 2O 3/ Al 2O 3, by the preparation of metal nitrate coprecipitation, precipitating reagent is Na 2CO 3, concrete grammar is: press CuO, ZnO, La 2O 3, Al 2O 3The mol ratio of four components is 100: X: Y: 29.42, and wherein X is 78.20-99.40; Y is that 1.10-5.58 takes by weighing Cu (NO 3) 23H 2O, Zn (NO 3) 26H 2O, La (NO 3) 36H 2O, Al (NO 3) 39H 2O is dissolved in an amount of distilled water, slowly is added dropwise to an amount of supersaturation Na 2CO 3In the solution, precipitation fully after, leave standstill aging, washing making beating, the Na that flush away is excessive 2CO 3, after 110 ℃ of oven dry, compression molding, in Muffle furnace 300 ℃-400 ℃ roasting 3-5 hour, be crushed to predetermined order number after the cooling.
Catalyzer of the present invention is at H 2O and CH 3The OH mol ratio is 3, and temperature of reaction is 230 ℃-260 ℃, under the normal pressure, can realize CH effectively 3The steam reforming reaction of OH.
Little reaction evaluating device is adopted in experiment, and reactor is the stainless steel reaction pipe of internal diameter 8mm, and the catalyzer loading amount is 10ml, the micro-sampling pump control that raw material is produced by Shanghai atom the subject of knowledge and the object of knowledge, and product is by gc analysis.
Catalyzer CH of the present invention 3The OH transformation efficiency is greater than 87.5%, CO 2Selectivity is higher than 96%.
For further setting forth the present invention, the spy provides following example.Obviously, embodiments of the present invention are not limited to following example.
Embodiment 1
Take by weighing respectively 54.36 gram Cu (NO 3) 23H 2O, 66.94 gram Zn (NO 3) 26H 2O, 3.19 gram La (NO 3) 36H 2O, 50.02 gram Al (NO 3) 39H 2O is mixed with respectively the solution of 1M, under constantly stirring, slowly splash in the lump excessive 10% and temperature constant be 65 ℃-70 ℃ supersaturation Na 2CO 3In the solution to precipitation fully, filtering and washing, repeatedly making beating, move in the Muffle furnace 300 ℃ roasting 3-4 hour, it is for subsequent use to be crushed to the 20-60 order after the cooling.
Get 10ml (9.1 gram) catalyzer and put into stainless steel reactor, H 2O and CH 3The OH mol ratio is 3: 1, and temperature of reaction is 240 ℃, CH 3The OH transformation efficiency is 98.5%, CO 2Selectivity is 99.7%.
Embodiment 2
Take by weighing respectively 54.36 gram Cu (NO 3) 23H 2O, 62.48 gram Zn (NO 3) 26H 2O, 6.38 gram La (NO 3) 36H 2O, 50.02 gram Al (NO 3) 39H 2O is mixed with respectively the solution of 1M, under constantly stirring, slowly splash in the lump excessive 10% and temperature constant be 65 ℃-70 ℃ supersaturation Na 2CO 3In the solution to precipitation fully, filtering and washing, repeatedly making beating, move in the Muffle furnace 300 ℃ roasting 3-4 hour, it is for subsequent use to be crushed to the 20-60 order after the cooling.
The evaluation of catalyst is with example 1, CH 3The OH conversion ratio is 97.5%, CO 2Selectively be 99.7%.
Embodiment 3
Take by weighing respectively 54.36 gram Cu (NO 3) 23H 2O, 58.01 gram Zn (NO 3) 26H 2O, 9.57 gram La (NO 3) 36H 2O, 50.02 gram Al (NO 3) 39H 2O is mixed with respectively the solution of 1M, under constantly stirring, slowly splash in the lump excessive 10% and temperature constant be 65 ℃-70 ℃ supersaturation Na 2CO 3In the solution to precipitation fully, filtering and washing, repeatedly making beating, move in the Muffle furnace 300 ℃ roasting 3-4 hour, it is for subsequent use to be crushed to the 20-60 order after the cooling.
The evaluation of catalyst is with example 1, CH 3The OH conversion ratio is 90.6%, CO 2Selectively be 99.8%.
Embodiment 4
Method for preparing catalyst is with example 1.
Take by weighing 10ml (9.1 gram) catalyzer and put into stainless steel reactor, H 2O and CH 3The OH mol ratio is 3: 1, and catalyzer is through the working fluid in-situ reducing, and originally temperature of reaction is 230 ℃, and the liquid air speed is 1.0h -1, this moment CH 3The OH transformation efficiency is 98.5%, CO 2Selectivity is that 99.8%30 hours afterreaction temperature are upgraded to 250 ℃, liquid air speed 0.7h -1, this moment CH 3The OH transformation efficiency is 87.6%, CO 2Selectivity is 99.1%.CH after 300 hours 3The OH conversion ratio is 90.5%, CO 2Selectively be 98.7%; CH after 600 hours 3The OH conversion ratio is 90.3%, CO 2Selectively be 99.7%.

Claims (2)

1. catalyst for steam reformation of methanol to produce hydrogen, the active component that it is characterized in that catalyst is CuO, carrier is Al 2O 3, co-catalyst is ZnO and La 2O 3, the catalyst general formula is CuO/ZnO/La 2O 3/ Al 2O 3, CuO, ZnO, La 2O 3, Al 2O 3Mol ratio be 100: X: Y: 29.42, wherein X is 78.20-99.40, Y is 1.10-5.58.
2. the preparation method of catalyst as claimed in claim is characterized in that by CuO ZnO, La 2O 3, Al 2O 3The mol ratio of four components is 100: X: Y: 29.42, and wherein X is 78.20-99.40, Y is that 1.10-5.58 takes by weighing Cu (NO 3) 23H 2O, Zn (NO 3) 26H 2O, La (NO 3) 36H 2O, Al (NO 3) 39H 2O is dissolved in an amount of distilled water, slowly is added dropwise to an amount of supersaturation Na 2CO 3In the solution, precipitation fully after, leave standstill aging, washing making beating, the Na that flush away is excessive 2CO 3, after 110 ℃ of oven dry, compression molding, in Muffle furnace 300 ℃-400 ℃ roasting 3-5 hour, be crushed to predetermined number after the cooling.
CN00122375A 2000-09-07 2000-09-07 Catalyst for steam reformation of methanol to produce hydrogen Expired - Fee Related CN1111446C (en)

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Application Number Priority Date Filing Date Title
CN00122375A CN1111446C (en) 2000-09-07 2000-09-07 Catalyst for steam reformation of methanol to produce hydrogen

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Application Number Priority Date Filing Date Title
CN00122375A CN1111446C (en) 2000-09-07 2000-09-07 Catalyst for steam reformation of methanol to produce hydrogen

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CN1111446C CN1111446C (en) 2003-06-18

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1326608C (en) * 2005-01-13 2007-07-18 南京大学 Dimethoxym ethane renormalized hydrogen production catalyst and preparation method and purpose thereof
CN100341619C (en) * 2004-10-14 2007-10-10 中国科学院大连化学物理研究所 Catalyst in use for preparing hydrogen through reforming oxidized methyl alcohol, and preparation method
CN102614882A (en) * 2012-03-07 2012-08-01 中国科学院山西煤炭化学研究所 Low temperature methanol cracking catalyst for methanol-fueled automobiles as well as preparation method thereof and application thereof
CN104689823A (en) * 2015-02-12 2015-06-10 上海摩醇动力技术有限公司 Process for preparing copper-based catalyst by using formed foil as carrier
CN104741132A (en) * 2015-02-12 2015-07-01 上海摩醇动力技术有限公司 Process for preparing noble-metal catalyst by adopting formed foil as carrier
CN112827483A (en) * 2020-12-29 2021-05-25 宁波申江科技股份有限公司 Hydrogen production catalyst and preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3259020B2 (en) * 1991-08-21 2002-02-18 智行 乾 Oxide-based catalyst, method for producing the same, and method for catalytic hydrogenation of CO2 using the catalyst
JP3339655B2 (en) * 1993-10-04 2002-10-28 花王株式会社 Catalyst precursor for hydrogenation reaction, method for producing the same, and method for producing alcohol
US5703133A (en) * 1995-12-08 1997-12-30 Exxon Research And Engineering Company Isoalcohol synthesis

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100341619C (en) * 2004-10-14 2007-10-10 中国科学院大连化学物理研究所 Catalyst in use for preparing hydrogen through reforming oxidized methyl alcohol, and preparation method
CN1326608C (en) * 2005-01-13 2007-07-18 南京大学 Dimethoxym ethane renormalized hydrogen production catalyst and preparation method and purpose thereof
CN102614882A (en) * 2012-03-07 2012-08-01 中国科学院山西煤炭化学研究所 Low temperature methanol cracking catalyst for methanol-fueled automobiles as well as preparation method thereof and application thereof
CN102614882B (en) * 2012-03-07 2013-10-30 中国科学院山西煤炭化学研究所 Low temperature methanol cracking catalyst for methanol-fueled automobiles as well as preparation method thereof and application thereof
CN104689823A (en) * 2015-02-12 2015-06-10 上海摩醇动力技术有限公司 Process for preparing copper-based catalyst by using formed foil as carrier
CN104741132A (en) * 2015-02-12 2015-07-01 上海摩醇动力技术有限公司 Process for preparing noble-metal catalyst by adopting formed foil as carrier
CN112827483A (en) * 2020-12-29 2021-05-25 宁波申江科技股份有限公司 Hydrogen production catalyst and preparation method and application thereof

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