CN1280953A - Catalyst for preparing hydrogen by reforming methanol and water vapour and its application - Google Patents
Catalyst for preparing hydrogen by reforming methanol and water vapour and its application Download PDFInfo
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- CN1280953A CN1280953A CN00121570A CN00121570A CN1280953A CN 1280953 A CN1280953 A CN 1280953A CN 00121570 A CN00121570 A CN 00121570A CN 00121570 A CN00121570 A CN 00121570A CN 1280953 A CN1280953 A CN 1280953A
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- methanol
- preparing hydrogen
- water vapour
- hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A catalyst for preparing hydrogen by reforming the aqueous vapour of methanol uses the aqueous solution of methanol as raw material in mole ratio of 1-3 for water to methanol; the catalyst is suitable for the conditions of 230-260 deg.c, 1.0 MPa and 1-2.5/h of space speed, and contains CuO (38-65 wt%), ZnO (15-50), Al2O3 (5-10) and Fe2O3 (0.5-15). Its advantages include low reaction temp., high transform rate of methanol (98% or more), little by-product and high stability.
Description
The invention belongs to a kind of catalyst for preparing hydrogen by reforming methanol and water vapour and using method thereof.
Along with producing and the developing rapidly of science and technology, the purposes of hydrogen more and more widely from refining of petroleum, chemical industry, control the metal working industry, all is used widely to industries such as electronics, electric power, building materials, meteorology, space flight.The demand of hydrogen is than one of fastest-rising gas of other industrial gasses.Hydrogen is a kind of functional materials, also is a kind of energy and material.In upcoming next century, the mankind face energy dilemma and problem of environmental pollution is increasingly serious, tap a new source of energy, and seeking fuel substitute is the task of top priority.And be the fuel cell of fuel with hydrogen, be a kind of movably, propulsion source efficiently, have that starting is convenient, specific power is big, pollute advantages such as little, demonstrate great application prospect.
At present, the method of industrial hydrogen manufacturing mainly contains: water electrolysis method, hydro carbons steam reforming method, ammonia decomposition method, water-gas conversion method, methanol decomposition method etc., wherein methanol steam reforming reaction, it is the highest reaction of hydrogen richness in the methanol decomposition silicol process, characteristics such as have that cost is low, mild condition, no burn into product component are few, easily separated can satisfy the requirement to hydrogen source of fuel cell and other hydrogen users.Particularly when fuel cell is used for hospital, airport, Data centre, military applications and Motor vehicles and independently provides power supply, have more the market competitiveness with hydrogen production from methanol-steam reforming.At present, the catalyst for preparing hydrogen by reforming methanol and water vapour of domestic use, be the Cu-Zn-Al catalyzer that synthesizing methanol is used mostly, their use temperature is all than higher, as the MWC-610 catalyzer of the Lanzhou Chemistry and Physics Institute of recent bibliographical information exploitation, the QMH-01 dual-function catalyst of Qilu Petrochemical institute exploitation, its use temperature is all at 260-300 ℃.
The object of the present invention is to provide low catalyst for preparing hydrogen by reforming methanol and water vapour of a kind of use temperature and using method thereof.
Catalyst weight per-cent of the present invention consists of:
CuO?38-65?ZnO?15-50?Al
2O
3?5-10?Fe
2O
3?0．5-15
Preparation of catalysts method of the present invention:
(1) coprecipitation method: be about to mixing solutions and the sodium carbonate solution or the ammoniacal liquor of certain density cupric nitrate, zinc nitrate, iron nitrate, aluminium hydroxide, under 80 ℃ of constant temperature, agitation condition, adopt and the stream coprecipitation method, with both mixed precipitation.In the precipitation process, the pH value is controlled at about 10.5, treat that precipitation finishes after, aging 2 hours.The catalyst pulp that precipitation is good filters, and to there not being chlorion, 120 ℃ of dryings are calcined after 2 hours, made catalyzer for 350 ℃ with 60 ℃ distilled water washs;
(2) the co-precipitation method that combines with dipping: be about to mixing solutions and the sodium carbonate solution or the ammoniacal liquor of certain density cupric nitrate, zinc nitrate, aluminium hydroxide, under 80 ℃ of constant temperature, agitation condition, adopt also stream coprecipitation method, with both mixed precipitation.In the precipitation process, the pH value is controlled at about 10.5, treat that precipitation finishes after, aging 2 hours.The catalyst pulp that precipitation is good filters, and to there not being chlorion, 120 ℃ of dryings are calcined after 2 hours, made the catalytic materials carrier for 350 ℃ with 60 ℃ distilled water washs.Certain density iron nitrate is immersed on the catalytic materials carrier, obtains catalyzer.
Catalyzer of the present invention is under less than 1MPa pressure, is raw material with the methanol aqueous solution of water alcohol mol ratio 1-3, and air speed is 1-2.5h
-1, react under 230-260 ℃ the condition.
The present invention compared with prior art has following advantage:
1. the methanol steam reforming temperature of reaction is low, and range of reaction temperature is 230-260 ℃, and in the time of 240 ℃, conversion of methanol is more than 98%.
2. byproduct of reaction is few, good stability.
Embodiment 1
(1) cupric nitrate, zinc nitrate, iron nitrate, aluminium hydroxide are dissolved in the solution that distilled water is made into 1.0g/ml respectively, CuO 65% by weight percentage, and ZnO 15.5%, Al
2O
34.5%, Fe
2O
3After 15% ratio takes by weighing each component, be made into the mixed solution of 600ml cupric nitrate, zinc nitrate, iron nitrate, aluminium hydroxide;
(2) anhydrous sodium carbonate is dissolved in the solution that distilled water is made into 1.0g/ml;
(3) under 80 ℃ of constant temperature, stirring, adopt also stream coprecipitation method, with (1), (2) solution mixed precipitation.During precipitation, the pH value is controlled at about 10.5, wait precipitation to finish after, aging 2 hours;
(4) catalyst pulp that above-mentioned precipitation is good filters, and to there not being chlorion, 120 ℃ of dryings 12 hours were calcined 2 hours, and made catalyst A for 350 ℃ with 60 ℃ of distilled water washs.
Embodiment 2
Cupric nitrate, zinc nitrate, iron nitrate, aluminium hydroxide are dissolved in the solution that distilled water is made into 1.0g/ml respectively, press CuO 38%, ZnO 47.2%, Al
2O
39.8%, Fe
2O
3After 5% ratio takes by weighing each component, be made into the mixed solution of 600ml cupric nitrate, zinc nitrate, iron nitrate, aluminium hydroxide, all the other make catalyst B with embodiment 1.
Embodiment 3
(1) cupric nitrate, zinc nitrate, iron nitrate, aluminium hydroxide are dissolved in the solution that distilled water is made into 1.0g/ml respectively, press CuO 55%, ZnO 39%, Al
2O
35%, Fe
2O
3After 0.8% ratio takes by weighing each component, be made into the mixed solution of 600ml cupric nitrate, zinc nitrate, aluminium hydroxide;
(2), (3), (4) step make support of the catalyst with embodiment 1;
(5) iron nitrate solution that will take by weighing according to the above ratio is immersed on the above-mentioned support of the catalyst for preparing, and floods after 12 hours, and oven dry was calcined 2 hours, and made catalyzer C for 350 ℃.
The evaluating catalyst that each embodiment makes:
The catalyst activity evaluation is to carry out reaction conditions such as table 1 in the fixed bed current system: before the reaction with hydrogen at 350 ℃ of following reductase 12s hour, face hydrogen and be cooled to 200 ℃, switch methanol aqueous solution and be warming up to 240 ℃, react after 1 hour sampling analysis.Reaction end gas carries out on-line analysis at the carbon molecular sieve post through the TCD detector after cold well cryostat, reaction back liquid is analyzed reaction result such as table 1 with fid detector on the GDX-103 post:
Table 1
| Reaction conditions | Catalyzer | Methanol conversion % | Gas composition (%) | |||
| ????H 2 | ????CO 2 | ????CO | ||||
| 240 ℃ of water alcohol of temperature of reaction are than=1.5 air speed 2h -1 | A | ?99．91 | ?76．92 | ?22．31 | ?0．69 | |
| B | ?98．98 | ?76．10 | ?23．41 | ?0．49 | ||
| C | ?98．85 | ?75．70 | ?23．57 | ?0．72 | ||
| 240 ℃ of water alcohol of temperature of reaction are than=3.0 air speed 1.5h -1 | A | ?99．89 | ?75．92 | ?23．28 | ?0．79 | |
| B | ?99．25 | ?75．21 | ?24．09 | ?0．68 | ||
| C | ?98．79 | ?75．80 | ?23．59 | ?0．62 | ||
Claims (2)
1. a catalyst for preparing hydrogen by reforming methanol and water vapour is characterized in that weight percent consists of: CuO 38-65 ZnO 15-50 Al
2O
35-10 Fe
2O
30.5-15.
2. the application method of a kind of catalyst for preparing hydrogen by reforming methanol and water vapour according to claim 1 is characterized in that it being under less than 1.0MPa pressure, is raw material with the methanol aqueous solution of water alcohol mol ratio 1-3, and air speed is 1-2.5h
-1, react under 230-260 ℃ the condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00121570A CN1112242C (en) | 2000-08-14 | 2000-08-14 | Catalyst for preparing hydrogen by reforming methanol and water vapour and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00121570A CN1112242C (en) | 2000-08-14 | 2000-08-14 | Catalyst for preparing hydrogen by reforming methanol and water vapour and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1280953A true CN1280953A (en) | 2001-01-24 |
| CN1112242C CN1112242C (en) | 2003-06-25 |
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|---|---|---|---|
| CN00121570A Expired - Fee Related CN1112242C (en) | 2000-08-14 | 2000-08-14 | Catalyst for preparing hydrogen by reforming methanol and water vapour and its application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857965A (en) * | 2015-05-28 | 2015-08-26 | 常州大学 | Preparation method and application process of catalyst for producing hydrogen by methanol steam reformation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051745C (en) * | 1996-01-22 | 2000-04-26 | 中国石化齐鲁石油化工公司 | Process and apparatus for converting methanol vapor into hydrogen |
| JP4161147B2 (en) * | 1998-03-27 | 2008-10-08 | 大阪瓦斯株式会社 | Hydrogen production equipment |
-
2000
- 2000-08-14 CN CN00121570A patent/CN1112242C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857965A (en) * | 2015-05-28 | 2015-08-26 | 常州大学 | Preparation method and application process of catalyst for producing hydrogen by methanol steam reformation |
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| CN1112242C (en) | 2003-06-25 |
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Granted publication date: 20030625 Termination date: 20170814 |
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