CN1541936A - Catalyst for vehicle mounted methanol steam reform hydrogen production plant - Google Patents
Catalyst for vehicle mounted methanol steam reform hydrogen production plant Download PDFInfo
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- CN1541936A CN1541936A CNA2003101120619A CN200310112061A CN1541936A CN 1541936 A CN1541936 A CN 1541936A CN A2003101120619 A CNA2003101120619 A CN A2003101120619A CN 200310112061 A CN200310112061 A CN 200310112061A CN 1541936 A CN1541936 A CN 1541936A
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Abstract
The catalyst consists of main active component CuO, assistant active components ZnO and oxide of Ce or Zr, and carrier Al2O3. The preparation process of the catalyst includes reaction of the nitrate solution and carbonate solution containing the catalyst components at 60-90 deg.c and pH 7-9; dropping the reaction product into co-precipitator to produce precipitate; and ageing for 2-5 hr, washing, drying, roasting at 300-700 deg.c for 3-8 hr. The produced catalyst has high activity at low temperature, high selectivity, excellent stability, high efficiency and low cost, and is used in vehicular methane reformer of fuel cell vehicle.
Description
Technical field
The present invention relates to catalyst field, specifically relate to a kind of vehicle-mounted methanol steam reformation hydrogen production catalyzer.The invention still further relates to this Preparation of catalysts method.
Background technology
Compare with traditional internal-combustion engines vehicle, the fuel cell electric vehicle of efficient " zero release " is owing to have the advantage of environmental protection and energy-conservation two aspects, classified as first of the big high and new technology of 21 centurys ten by U.S.'s Time, and be the future of automotive industry.And be Proton Exchange Membrane Fuel Cells (PEMFC) power truck of fuel through the hydrogen manufacturing of vehicle-mounted methanol reformer with methyl alcohol, thought one of fuel cell electric vehicle scheme of most possibly dropping into commercial applications by the various countries expert is consistent at present.
The catalyzer that methanol vapor reformation to produce hydrogen reaction is at present used mainly contains nickel catalyst, palladium series catalyst and Cu-series catalyst three classes.Wherein nickel catalyst has good stability, and applicable elements is wide, be difficult for the advantage of poisoning, but reaction preference is relatively poor, particularly when temperature of reaction is lower than 300 ℃, generates more CO and a certain amount of CH
4, and CO easily makes the platinum electrode of PEMFC produce irreversible poisoning, so need the CO convertor of follow-up use comparatively large vol, this has just limited the independent use of nickel catalyst on fuel cell electric vehicle.The advantage of palladium series catalyst is active high, and selectivity and good stability are subjected to the influence of poisonous substance and heat little.As the Pd/ZnO catalyzer (CN1334141A) of Mitsui Chemicals, Inc's development, by the H of methanol steam reforming formation
2With the productive rate of CO mixed gas be 2.68mol/mlCath, and react that activity only reduces by 1.2% after 48 hours, but since in such catalyzer the consumption of precious metal palladium higher, so on fuel cell electric vehicle the bigger limitation of large-scale promotion application existence.Cu-series catalyst is cheap, and active high, selectivity is good, be the most widely used class catalyzer of present industrial methanol hydrogen manufacturing, but such catalyzer thermostability is relatively poor, and overtemperature easily causes the sintering of catalyst inactivation.In view of copper thermostability in Cu-series catalyst is not high is the major cause that causes poor catalyst stability, Dalian Chemiclophysics Inst., Chinese Academy of Sciences has developed a series of no copper non-precious metal catalyst (CN1305868A, CN1305867A), such catalyzer has the excellent high-temperature thermostability, still keeps more than 90% at 400-600 ℃ of reaction 300h methanol conversion.But such catalyzer need be in higher relatively temperature of reaction (more than 400 ℃) operation down in order to keep high reaction activity and high, and the easy like this fuel cell electric vehicle that causes is long start time, and thermal losses is excessive.
Summary of the invention
The objective of the invention is to shortcoming at the prior art existence, a kind of catalyst for methanol vapor reformation to produce hydrogen is provided, this catalyzer has low temperature high activity, highly selective, good stability and efficient advantages of being cheap, satisfies the needs of fuel cell electric vehicle vehicle-mounted methanol reformer preferably.
Another object of the present invention is to provide this Preparation of catalysts method.
A kind of vehicle-mounted methanol steam reformation hydrogen production of the present invention catalyzer by main activeconstituents CuO, help activeconstituents ZnO, to help activeconstituents be the oxide compound and the carrier A l of a kind of metal among Ce, the Zr for another
2O
3Form; Each composition weight percentage composition: CuO is 20～80%, and ZnO is 10～60%, and a kind of oxide compound of metal is 1～40% among Ce, the Zr, Al
2O
3Be 1～30%.
As preferred version, described each composition weight percentage composition: CuO of vehicle-mounted methanol steam reformation hydrogen production catalyzer is 40～60%, and ZnO is 20～40%, and a kind of oxide compound of metal is 3～20% among Ce, the Zr, Al
2O
3Be 3～15%.
Described vehicle-mounted methanol steam reformation hydrogen production Preparation of catalysts method may further comprise the steps: the nitrate solution and the carbonate solution that will contain each component of catalyzer, in temperature of reaction is 60～90 ℃, under pH value 7～9 conditions, and drip is gone in the co-precipitation groove, aging 2-5 hour of the precipitation that generates, after washing, drying, 300～700 ℃ of roastings 3～8 hours.
As preferred version, temperature of reaction is 70～80 ℃, and maturing temperature is 400～600 ℃.
The present invention compared with prior art has following beneficial effect:
(1) catalyzer of the present invention when being used for the methanol vapor reformation to produce hydrogen reaction, has low temperature high activity and highly selective.Promptly 240～270 ℃ of temperature of reaction, normal pressure, water/methyl alcohol (mol ratio)=0.7～2.0/1, WHSV=1.0～7.0h
-1When (methanol solution is to the mass space velocity of unit catalyzer), the methanol steam reforming transformation efficiency is 90～99%, and hydrogen selective is 90～100%;
(2) catalyzer of the present invention has good reaction stability, sustained reaction 100h, and methanol conversion and hydrogen yield remain unchanged substantially;
(3) catalyzer of the present invention, its preparation cost of material is cheap, is easy to obtain, and is fit to produce in enormous quantities.
Embodiment
Embodiment 1
Take by weighing cupric nitrate 14.1g, zinc nitrate 7.0g, zirconium nitrate 2.9g, aluminum nitrate 4.3g is with getting solution 1 behind an amount of dissolved in distilled water; The sodium carbonate solution of preparation 0.6M is a solution 2.With solution 1 and solution 2 under vigorous stirring simultaneously constant speed and drip go in the settling bath, add 50ml distilled water in the groove in advance, temperature is controlled at 70 ℃ in the precipitation process, pH value is controlled at 9.Precipitation is aging 3 hours of back fully, and washing is to neutral, drying, and 450 ℃ of roastings 6 hours promptly get Cu quality percentage composition and are 60% CuZnZrAlO catalyzer.
Get the 20-40 order catalyzer 0.2g of this example preparation, get again same granularity quartz sand mixed evenly after, the crystal reaction tube constant temperature zone of the internal diameter 7mm that packs into, earlier at 300 ℃ with 10% (vol%) H
2-N
2Gas mixture reduction 5h switches to the mixture (water/methyl alcohol mol ratio=1.3: 1) of methyl alcohol and water then.When temperature of reaction is 250 ℃, normal pressure, WHSV=3.56h
-1The time, methanol conversion＞90%, hydrogen selective＞94%, reaction continues 100 hours, and catalyst activity does not have reduction.
Embodiment 2
Take by weighing cupric nitrate 9.83g, zinc nitrate 8.81g, zirconium nitrate 7.60g, aluminum nitrate 4.49g is with getting solution 1 behind an amount of dissolved in distilled water; The sodium carbonate solution of preparation 1.2M is a solution 2.With solution 1 and solution 2 under vigorous stirring and drip go in the settling bath, temperature is controlled at 80 ℃ in the precipitation process, pH value is controlled at 7.Precipitation is aging about 5 hours of back, washing, drying fully, and 600 ℃ of roastings 3 hours promptly get the copper mass percentage composition and be 40% CuZnZrAlO catalyzer.
Get the 20-40 order catalyzer 0.5g of this example preparation, adopt experimental installation and the catalyst reduction method identical with example 1,250 ℃ of temperature of reaction, normal pressure, water/methyl alcohol mol ratio=1.0: 1, WHSV=2.97h
-1React under the condition, methanol conversion is near 99%, hydrogen selective＞90%.
Embodiment 3
Take by weighing cupric nitrate 4.32g, zinc nitrate 18.18g, cerous nitrate 0.48g, aluminum nitrate 2.14g is with getting solution 1 behind an amount of dissolved in distilled water; The sodium carbonate solution of preparation 0.8M is a solution 2.With solution 1 and solution 2 under vigorous stirring and drip go in the settling bath, temperature is controlled at 60 ℃ in the precipitation process, pH value is controlled at 8.Precipitation is aging about 2 hours of back, washing, drying fully, and 400 ℃ of roastings 8 hours promptly get the copper mass percentage composition and be 20% CuZnCeAlO catalyzer.
Embodiment 4
Take by weighing cupric nitrate 12.1g, zinc nitrate 8.4g, cerous nitrate 0.96g, aluminum nitrate 3.9g is with getting solution 1 behind an amount of dissolved in distilled water; The sodium carbonate solution of preparation 0.5M is a solution 2.With solution 1 and solution 2 under vigorous stirring and drip go in the settling bath, temperature is controlled at 70 ℃ in the precipitation process, pH value is controlled at 8.Precipitation is aging about 3 hours of back, washing, drying fully, and 500 ℃ of roastings 5 hours promptly get the copper mass percentage composition and be 60% CuZnCeAlO catalyzer.
The 20-40 order catalyzer 1.0g that gets the preparation of this example estimates, and experimental installation and catalyst reduction method are with example 1.When temperature of reaction is 260 ℃, normal pressure, water/methyl alcohol mol ratio=1.0: 1, WHSV=4.4h
-1The time, methanol conversion＞97%, hydrogen selective is near 100%.Reaction continues 100 hours, and catalyst activity does not have to reduce substantially.
Claims (4)
1, a kind of vehicle-mounted methanol steam reformation hydrogen production catalyzer, it is characterized in that by main activeconstituents CuO, help activeconstituents ZnO, to help activeconstituents be the oxide compound and the carrier A l of a kind of metal among Ce, the Zr for another
2O
3Form; Each composition weight percentage composition: CuO is 20～80%, and ZnO is 10～60%, and a kind of oxide compound of metal is 1～40% among Ce, the Zr, Al
2O
3Be 1～30%.
2, vehicle-mounted methanol steam reformation hydrogen production catalyzer according to claim 1 is characterized in that being that each composition weight percentage composition: CuO is 40～60%, and ZnO is 20～40%, and a kind of oxide compound of metal is 3～20% among Ce, the Zr, Al
2O
3Be 3～15%.
3, claim 1 or 2 described vehicle-mounted methanol steam reformation hydrogen production Preparation of catalysts methods, it is characterized in that may further comprise the steps: the nitrate solution and the carbonate solution that will contain each component of catalyzer, in temperature of reaction is 60～90 ℃, under pH value 7～9 conditions, and drip is gone in the co-precipitation groove, aging 2-5 hour of the precipitation that generates is after washing, drying, 300～700 ℃ of roastings 3～8 hours.
4, vehicle-mounted methanol steam reformation hydrogen production Preparation of catalysts method according to claim 3 is characterized in that temperature of reaction is 70～80 ℃, and maturing temperature is 400～600 ℃.
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| CNA2003101120619A CN1541936A (en) | 2003-11-07 | 2003-11-07 | Catalyst for vehicle mounted methanol steam reform hydrogen production plant |
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|---|---|---|---|
| CNA2003101120619A CN1541936A (en) | 2003-11-07 | 2003-11-07 | Catalyst for vehicle mounted methanol steam reform hydrogen production plant |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104741128A (en) * | 2015-02-12 | 2015-07-01 | 上海摩醇动力技术有限公司 | Copper-based catalyst for preparing hydrogen by methanol-steam reforming and method for preparing hydrogen thereby |
| CN107349956A (en) * | 2017-08-01 | 2017-11-17 | 晋城市阿邦迪能源有限公司 | Hydrogen production by ethanol steam reforming catalyst and preparation method thereof |
| CN111282575A (en) * | 2020-04-03 | 2020-06-16 | 中国科学院上海高等研究院 | Catalyst for methanol steam reforming hydrogen production and preparation method and application thereof |
| CN113336555A (en) * | 2021-06-24 | 2021-09-03 | 浙江大学 | Photocuring type 3D printing manufacturing method of integral SiC-based microreactor |
| CN115041174A (en) * | 2022-06-20 | 2022-09-13 | 西南化工研究设计院有限公司 | Preparation method of copper-based catalyst for large-scale methanol hydrogen production device |
-
2003
- 2003-11-07 CN CNA2003101120619A patent/CN1541936A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104741128A (en) * | 2015-02-12 | 2015-07-01 | 上海摩醇动力技术有限公司 | Copper-based catalyst for preparing hydrogen by methanol-steam reforming and method for preparing hydrogen thereby |
| CN107349956A (en) * | 2017-08-01 | 2017-11-17 | 晋城市阿邦迪能源有限公司 | Hydrogen production by ethanol steam reforming catalyst and preparation method thereof |
| CN107349956B (en) * | 2017-08-01 | 2020-08-11 | 晋城市阿邦迪能源有限公司 | Catalyst for hydrogen production by reforming ethanol steam and preparation method thereof |
| CN111282575A (en) * | 2020-04-03 | 2020-06-16 | 中国科学院上海高等研究院 | Catalyst for methanol steam reforming hydrogen production and preparation method and application thereof |
| CN113336555A (en) * | 2021-06-24 | 2021-09-03 | 浙江大学 | Photocuring type 3D printing manufacturing method of integral SiC-based microreactor |
| CN115041174A (en) * | 2022-06-20 | 2022-09-13 | 西南化工研究设计院有限公司 | Preparation method of copper-based catalyst for large-scale methanol hydrogen production device |
| CN115041174B (en) * | 2022-06-20 | 2023-09-29 | 西南化工研究设计院有限公司 | Preparation method of copper-based catalyst of large-scale methanol hydrogen production device |
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