CN1288854A - Catalyst for steam reformation of methanol to produce hydrogen - Google Patents
Catalyst for steam reformation of methanol to produce hydrogen Download PDFInfo
- 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
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cuo
- zno
- methanol
- produce hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
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
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.
Priority Applications (1)
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 |
Applications Claiming Priority (1)
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 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1288854A true CN1288854A (en) | 2001-03-28 |
CN1111446C CN1111446C (en) | 2003-06-18 |
Family
ID=4589223
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN00122375A Expired - Fee Related CN1111446C (en) | 2000-09-07 | 2000-09-07 | Catalyst for steam reformation of methanol to produce hydrogen |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1111446C (en) |
Cited By (6)
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)
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 |
-
2000
- 2000-09-07 CN CN00122375A patent/CN1111446C/en not_active Expired - Fee Related
Cited By (7)
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 |
Also Published As
Publication number | Publication date |
---|---|
CN1111446C (en) | 2003-06-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102407121B (en) | Preparation method of hydrogenation catalyst with X/Ni/A1 hydrotalcite as precursor | |
CN110787822A (en) | Cobaltosic oxide catalyst, preparation method and application thereof | |
CN1111446C (en) | Catalyst for steam reformation of methanol to produce hydrogen | |
CN104148086B (en) | Prepare the catalyst and method of ethanol | |
CN102583242A (en) | Method for preparing hydrogen gas through catalytic cracking of methane | |
CN101255115A (en) | Method for synthesizing long-chain alkyl carbonate by transesterification | |
CN102451695A (en) | Preparation method of copper base catalyst for methanol synthesis | |
CN103801282B (en) | A kind of solid base catalyst and Synthesis and applications thereof | |
CN114853567B (en) | Catalyst for preparing low-carbon alcohol by converting carbon dioxide, and preparation method and application thereof | |
CN1291784C (en) | Copper base catalyst in use for preparing hydrogen by reforming vapor of methanol and preparation method | |
CN102463121A (en) | High-stability Cu-based catalyst and preparation method thereof | |
CN1139427C (en) | Nano CuZnAl catalyst for synthesizing methanol and dimethylether and its preparing process | |
CN102029166B (en) | Catalyst for preparing low-carbon mixed alcohol by using synthesis gas and preparation method thereof | |
CN112221509B (en) | Preparation method of high-stability methanol synthesis catalyst | |
CN102304021A (en) | Method for preparing neopentyl glycol | |
CN101264447A (en) | Nickel-boehmite composite catalyst for ethylene glycol liquid phase reforming reaction and preparation thereof | |
CN1911507A (en) | Nanometer copper base catalyst for preparing 1,3-propanediol by hydrogenation of 3-hydroxy methyl propionate and its preparation method | |
CN1680027A (en) | Copper-base catalyst of methanol steam reintegrating hydrogen manufacturing and preparation thereof | |
CN103613483A (en) | Application of layered loading catalyst in preparation of lower alcohol by using synthesis gas | |
CN1099907C (en) | Catalyst for dehydrogenation of saturated hydrocarbon and its preparation | |
CN108636423A (en) | A kind of preparation method of load type nano gold catalyst and application | |
CN101294093A (en) | Integrated preparation method for biological diesel oil and isolated plant | |
CN105363454B (en) | Hydrogenation catalyst | |
CN105363459B (en) | Ester through hydrogenation copper catalyst | |
CN114950478A (en) | Catalyst for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid, and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |