CN101934229A - Catalyst for oxidative removal of CO in hydrogen-rich gas and preparation and application thereof - Google Patents
Catalyst for oxidative removal of CO in hydrogen-rich gas and preparation and application thereof Download PDFInfo
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- CN101934229A CN101934229A CN 201010166529 CN201010166529A CN101934229A CN 101934229 A CN101934229 A CN 101934229A CN 201010166529 CN201010166529 CN 201010166529 CN 201010166529 A CN201010166529 A CN 201010166529A CN 101934229 A CN101934229 A CN 101934229A
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Abstract
The invention discloses a catalyst for oxidative removal of CO in hydrogen-rich gas. In the catalyst, active carbon is taken as a carrier, and an nCoO-mNiO composite oxide formed by non-noble metals such as cobalt and nickel is taken as an active ingredient so that the cost of the catalyst is greatly reduced, and the catalyst has high CO catalytic oxidative activity and selectivity in a low and wide reaction temperature range and can keep more than 99.5 percent of CO conversion rate at a high reaction air speed, effectively reduce the CO concentration in the hydrogen-rich gas to be below 50ppm and meet the standard of a hydrogen fuel for a fuel cell. The invention also discloses a preparation method for the catalyst, which comprises the following steps of: loading a cobalt salt and a nickel salt on the active carbon by a wet immersion method, and then preparing the nCoO-mNiO composite oxide containing low-valence cobalt by high-temperature roasting. The method has the advantages of simple process, mild and easily controlled conditions and good repeatability. The invention discloses application of the catalyst at the same time, which has simple and convenient operation and easy implementation and is very suitable for industrialized popularization.
Description
Technical field
The present invention relates to a kind of catalyst that the hydrogen rich gas co selective oxidation removes that is used for, particularly a kind ofly be used for non-precious metal catalyst and preparation and the application that the hydrogen rich gas co selective oxidation removes.
Background technology
Fuel cell be a kind of novel be the TRT of fuel with hydrogen, energy transformation ratio can reach 90% in theory, and generating efficiency is far above corresponding internal combustion engine, and water is unique product of reaction, can avoid environmental pollution effectively, be a kind of clean energy resource truly.The fuel cell These characteristics receives much attention its application in different field, and its correlative study also becomes the focus of research in recent ten years.The Proton Exchange Membrane Fuel Cells (PEMFC) that with hydrogen is fuel is a kind of fuel cell with long-range future that is used for industries such as energy generating, auto industry, shipping industry, Aero-Space, domestic power supply, mobile communication.
The hydrogen source is very wide, can produce by fossil fuels such as oil, natural gas, coals, can be made by conventional fuel alcohol, hydro carbons, also can produce by living beings (as, bacterium hydrogen manufacturing, ferment for hydrogen production etc.).There is bigger problem in the on-board storage of pure hydrogen, comparatively desirable solution is exactly at reforming unit of fuel cell system configuration, vehicle-mounted " charcoal-hydrogen " (hydro carbons) is converted into hydrogen-rich gas through processes such as steam reforming, self-heating recapitalization, steam transforming or partial oxidations, and this hydrogen-rich gas can be used as fuel-cell fuel after treatment.But the CO (carbon monoxide) that contains 0.5-2vol.% in this hydrogen-rich fuel usually, and the electrode pair CO of fuel cell has high sensitiveness, require the concentration of CO in the unstrpped gas must be for the Pt electrode, promptly use alloy electrode to require also that CO concentration is no more than 100ppm in the unstripped gas less than 10ppm.In order to reach this purpose, in research process, adopted all multi-methods, with the best results of a spot of CO in the selective oxidation removal hydrogen rich gas, and become one of the heat subject in catalyticing research field, the world today for the research of CO oxidation removal in the hydrogen rich gas.
The catalyst that is used for hydrogen rich gas CO oxidation removal at present mainly be noble metal (as, Pt, Au, Ru, Pd and Rh etc.) catalyst, and it is less that non-precious metal catalyst is used for the research of this catalytic reaction, and mainly concentrate on CuO
x/ CeO
2The research of catalyst system.For CuO
x/ CeO
2Catalyst system, wherein Ce is a kind of thulium, and its price is still more expensive, and has certain radioactivity, and this still is that the environmental pollution angle considers it is not desirable selection from the catalyst cost.Other base metal (as, Co, Fe, Zn, Mg and Mn etc.) also just done a spot of research as catalyst carrier or promoter.
Summary of the invention
In view of this, one of purpose of the present invention provides a kind of catalyst that is used for hydrogen rich gas CO oxidation removal, and is with low cost and have higher catalytic oxidation of CO at low temperature activity and a selectivity.
The catalyst that is used for hydrogen rich gas CO oxidation removal of the present invention comprises nCoO-mNiO composite oxides and carrier active carbon.
Further, comprise the active carbon of 60-70% and the nCoO-mNiO composite oxides of 30-40% by weight percentage, in the described composite oxides, the atomic ratio n of Co and Ni: m is 4: 1-1: 4;
Further, comprise 65% active carbon and 35% nCoO-mNiO composite oxides by weight percentage, in the described composite oxides, the atomic ratio n of Co and Ni: m is 1: 1;
Further, the hydrogen volume mark is not less than 90.0% in the described hydrogen rich gas.
Two of purpose of the present invention provides a kind of method for preparing catalyst of the present invention, may further comprise the steps:
(1) amount by described Co and Ni atomic ratio takes by weighing cobalt salt and nickel salt respectively and fully is dissolved in the distilled water, getting 20-80 purpose activated carbon granule impregnated in the gained solution, in 353K evaporate to dryness moisture content, get raw material under stirring condition, gained raw material freeze-day with constant temperature 10-24h under 373K makes siccative;
Described active carbon weight is 6 with the ratio of the composite oxides theoretical weight that forms by described atomic ratio: 4-7: 3.
(2) gained siccative heating rate with 5K/min in the room temperature inert environments is warming up to 573-673K, and constant temperature calcining 2-4h makes required catalyst under 573-673K then.
Further, the described cobalt salt of step (1) is a cobalt nitrate, and described nickel salt is a nickel nitrate.
Three of purpose of the present invention provides a kind of Application of Catalyst method of the present invention, comprise the steps: the gained catalyst and the tubular fixed-bed reactor of packing into after inertia quartz sand mixes, feed rich hydrogen unstripped gas after being warmed up to reaction temperature, and at this reaction temperature and 20,000h
-1Isothermal reaction is at least 180 minutes under the reaction gas air speed condition, and reaction back gained gas removes CO through the soda lime drying
2After get final product;
Wherein, when the atomic ratio n of Co in the composite oxides and Ni: m more than or equal to 1: 4 and less than the weight ratio of 1: 1, composite oxides and active carbon more than or equal to 30% and less than 35% the time, described range of reaction temperature is 413-443K; Atomic ratio n as Co in the composite oxides and Ni: m be greater than 1: 1 and smaller or equal to the weight ratio of 4: 1, composite oxides and active carbon for greater than 35% and smaller or equal to 40% the time, described range of reaction temperature is 433-453K; Atomic ratio n as Co in the composite oxides and Ni: m is the weight ratio of 1: 1, composite oxides and active carbon when being 35%, and described range of reaction temperature is 413-463K.
The invention has the beneficial effects as follows:
Catalyst of the present invention is compared with the existing catalyst that is used for hydrogen rich gas CO selective oxidation removal has following advantage:
1, with the active carbon be carrier, the nCoO-mNiO composite oxides that form with base metal cobalt and nickel are active component, have reduced the catalyst cost significantly.
When 2, catalyst is used high reaction velocity (20,000h
-1), show good catalytic activity and selectivity in the low and wide range of reaction temperature, in the certain reaction temperature range, keep CO conversion ratio greater than 99.5%, can effectively CO concentration in the hydrogen rich gas be dropped to below the 50ppm, reach the standard of fuel cell with hydrogen fuel.
Method for preparing catalyst of the present invention is that cobalt salt and nickel salt are carried on the active carbon according to a certain percentage by wet infusion process, and then makes the nCoO-mNiO composite oxides that contain the lower valency cobalt by high-temperature roasting.By discovering, CoO has the Co of being better than
3O
4Catalytic activity and selectivity, the technology that method of the present invention prepares lower valency CoO and corresponding catalyst is simple, mild condition is easily controlled, good reproducibility.
Application of Catalyst method of the present invention is easy and simple to handle, implements easily, is fit to very much Industry Promotion.
Other advantages of the present invention, target and feature will be set forth to a certain extent in the following description, and to a certain extent, based on being conspicuous to those skilled in the art, perhaps can gain enlightenment from the practice of the present invention to hereinafter the meaning of investigating.
Description of drawings
Fig. 1 is the XRD spectra of different metal oxides load capacity catalyst;
Fig. 2 makes the XRD spectra of catalyst for roasting under the different sintering temperatures.
The specific embodiment
Below with reference to specific embodiment the present invention is described in detail.Should be appreciated that selected embodiment only for the present invention is described, rather than in order to limit protection scope of the present invention.
Among the present invention, carrier active carbon (AC) is the active carbon that Ningxia active carbon factory produces.
Experiment condition:
The X-ray powder diffraction experiment is carried out experimental condition on Philips X ' Pert ProMPD X-ray diffraction instrument: Cu K α is a radiographic source, λ=1.5418
, tube voltage 40kV, tube current 40mA, 1 °/min of scan frequency, sweep limits 20-80 °.
The concentration of CO is by being equipped with the methanation converter, being with the GC-1026 type gas-chromatography of fid detector to measure in CO and the product in the hydrogen rich gas, and testing conditions is: detector temperature 523K, and injector temperature 373K, post oven temperature, degree perseverance is 373K.
Embodiment 1
By described Co and Ni atomic ratio is respectively to take by weighing cobalt nitrate and nickel nitrate at 1: 1 and fully be dissolved in the distilled water, getting granularity impregnated in the gained solution at the activated carbon granule (active carbon weight is 6.5: 3.5 with the ratio of the composite oxides theoretical weight that forms by described atomic ratio) of 20-80 order scope, constantly under the stirring condition in 353K evaporate to dryness moisture content, get raw material, the gained raw material makes siccative in freeze-day with constant temperature 24h under the 373K (be to remove the crystallization water in the described raw material in the purpose of 373K freeze-day with constant temperature, be that 10-24h all can realize goal of the invention drying time) herein; Again the siccative heating rate with 5K/min in the room temperature inert environments that makes is warming up to 673K, constant temperature calcining 2h under 673K gets required catalyst prod again.
The gained catalyst is used for the CO oxidation removal of hydrogen rich gas, operates as follows:
Hydrogen rich gas by volume percentage comprises: CO-1.0%, O
2-0.8% and H
2-98.2%;
Operating procedure: the activity of such catalysts evaluation is carried out in internal diameter is the miniature tubular fixed-bed reactor of 8mm under normal pressure, and thermocouple is built in the reactor, reaction temperature by
The control of-708P type temperature programming controller, microreactor places tube furnace.Measure the 0.1mL catalyst and inertia quartz sand is mixed to 0.4mL, in the reflection light of the miniature tubular fixed-bed reactor of packing into after mixing, be warmed up to 413K after, feed the hydrogen rich gas of described composition, at this temperature and 20,000h
-1Constant temperature removes CO (the hydrogen rich gas flow is controlled by flowmeter) under the reaction gas air speed condition, reaction back gas through the soda lime drying, remove CO
2After, again through methanator with gas in remaining CO methanation; Gaseous mixture after the methanation is by the online detection methane content of GC-1026 type gas-chromatography of band hydrogen flame detector, and the least concentration that used hydrogen flame detector detects CO can reach 5ppm.
Embodiment 2:
Thermostat temperature is 423K in the change CO oxidation removal process, and all the other conditions are with embodiment 1.
Embodiment 3:
Roasting time is that 4h makes catalyst under 673K, and CO oxidation removal reaction temperature is 433K, and all the other conditions are with embodiment 1.
Embodiment 4
Thermostat temperature is 443K in the change CO oxidation removal process, and all the other conditions are with embodiment 1.
Embodiment 5
Roasting time is that 4h makes catalyst under 673K, and CO oxidation removal reaction temperature is 453K, and all the other conditions are with embodiment 1.
Embodiment 6
Thermostat temperature is 463K in the change CO oxidation removal process, and all the other conditions are with embodiment 1.
Embodiment 7
Thermostat temperature is 473K in the change CO oxidation removal process, and all the other conditions are with embodiment 1.
Embodiment 8
The ratio of getting activated carbon dosage and the composite oxides theoretical weight that forms by described atomic ratio is 7: 3, and all the other conditions are with embodiment 2.
Embodiment 9
Thermostat temperature is 433K in the change CO oxidation removal process, and all the other conditions are with embodiment 8.
Embodiment 10
Thermostat temperature is 443K in the change CO oxidation removal process, and all the other conditions are with embodiment 8.
Embodiment 11
Thermostat temperature is 453K in the change CO oxidation removal process, and all the other conditions are with embodiment 8.
Embodiment 12
The ratio of getting activated carbon dosage and the composite oxides theoretical weight that forms by described atomic ratio is 6: 4, and all the other conditions are with embodiment 1.
Embodiment 13
Thermostat temperature is 423K in the change CO oxidation removal process, and all the other conditions are with embodiment 12.
Embodiment 14
Thermostat temperature is 453K in the change CO oxidation removal process, and all the other conditions are with embodiment 12.
Embodiment 15
Thermostat temperature is 463K in the change CO oxidation removal process, and all the other conditions are with embodiment 12.
Embodiment 16
The atomic ratio of Co and Ni is 4: 1 in the change catalyst, and all the other conditions are with embodiment 2.
Embodiment 17
Thermostat temperature is 433K in the change CO oxidation removal process, and all the other conditions are with embodiment 16.
Embodiment 18
Thermostat temperature is 443K in the change CO oxidation removal process, and all the other conditions are with embodiment 16.
Embodiment 19
Thermostat temperature is 453K in the change CO oxidation removal process, and all the other conditions are with embodiment 16.
The atomic ratio of Co and Ni is 1: 4 in the change catalyst, and thermostat temperature is 403K in the CO oxidation removal process, and all the other conditions are with embodiment 1.
Embodiment 21:
Thermostat temperature is 413K in the change CO oxidation removal process, and all the other conditions are with embodiment 20.
Embodiment 22
Thermostat temperature is 443K in the change CO oxidation removal process, and all the other conditions are with embodiment 20.
Embodiment 23
Thermostat temperature is 453K in the change CO oxidation removal process, and all the other conditions are with embodiment 20.
Embodiment 24
Thermostat temperature is 423K in the change CO oxidation removal process, and sintering temperature is 623K, and roasting time is 2h, and all the other conditions are with embodiment 1.
Thermostat temperature is 453K in the change CO oxidation removal process, and all the other conditions are with embodiment 24.
Embodiment 26
The change sintering temperature is 573K, and roasting time is 2h, and thermostat temperature is 423K in the CO oxidation removal process, and all the other conditions are with embodiment 1.
Embodiment 27
Thermostat temperature is 453K in the change CO oxidation removal process, and all the other conditions are with embodiment 28.
Embodiment 28
Thermostat temperature is 463K in the change CO oxidation removal process, and all the other conditions are with embodiment 28.
More than the CO conversion ratio of each embodiment gained catalyst prod the results are shown in Table 1:
Table 1
Get embodiment 1, embodiment 9 and embodiment 13 gained catalyst prods (representing) and carry out XRD (X-ray diffraction) detection, get the XRD spectrum as Fig. 1 with CoO-NiO/AC; Among Fig. 1,30 represent embodiment 9 products, and composite oxide supported amount is 30% in the expression catalyst, 35 represent embodiment 1 product, composite oxide supported amount is 35%, 40 represent embodiment 13 products in the expression catalyst, represents that composite oxides mass loading amount is 40%.
By shown in Figure 1, the XRD of the CATALYST Co O-NiO/AC of the oxide carried amount of different composite spectrum is 36.6 °, 42.6 °, 62.0 °, 74.4 ° and 78.5 ° at the angle of diffraction 2 θ respectively and locates to have occurred high-intensity XRD diffraction maximum.The information that provides by the standard P DF card of CoO and NiO as can be known, CoO-PDF-43-1004:36.5 ° of { 111}, 42.4 ° of { 200}, 61.5 ° of { 220}, 73.7 ° of { 311} and 77.6 ° of { 222}; NiO-PDF-47-1049:37.2 ° of { 111}, 43.3 ° of { 200}, 62.9 ° of { 220}, 75.4 ° of { 311} and 79.4 ° of { 222}, show that promptly the XRD angle of diffraction of catalyst and CoO and NiO are closely similar, show to have formed CoO and NiO thing among the CoO-NiO/AC that under each condition, makes mutually; And in this XRD spectra, do not have other new thing phase (as, Co3O4, Co2O3 and Ni2O3 etc.) be detected, do not have simultaneously the compound generation of Co and Ni yet, show that Co and Ni do not form new compound yet in the catalyst; The XRD diffraction maximum of CoO and NiO is molten for the division at peak does not take place one among the figure, shows that CoO and NiO have formed composite oxides.
Further contrast as can be known, under same atoms ratio and the sintering temperature condition, the oxide carried amount of different composite has produced influence to the intensity of XRD diffraction maximum, and with the increase of composite oxide supported amount, peak intensity is more and more stronger, and it is more and more sharp-pointed that peak shape becomes.
Get embodiment 1, embodiment 24 and embodiment 26 products and carry out XRD (X-ray diffraction) detection, get the XRD spectrum as Fig. 2; Among Fig. 2,573 represent embodiment 26 products, and the sintering temperature during the expression preparation is 573K; 623 represent embodiment 24 products, and the sintering temperature during the expression preparation is 623K; 673 represent embodiment 1 product, and the expression sintering temperature is 673K.
As shown in Figure 2, sintering temperature has produced influence to the intensity of XRD diffraction maximum, along with the rising of sintering temperature, and CoO and NiO diffraction peak intensity grow, it is more and more sharp-pointed that peak shape becomes, and CoO and NiO grain size become big in the interpret sample, and crystallinity improves.Significantly not new thing phase peak is detected in the XRD spectrum, and the variation that does not have main thing phase in the process that sintering temperature changes in the catalyst is described, still exists with CoO and NiO.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (7)
1. a catalyst that is used for hydrogen rich gas CO oxidation removal is characterized in that: comprise nCoO-mNiO composite oxides and carrier active carbon.
2. the catalyst that is used for hydrogen rich gas CO oxidation removal according to claim 1, it is characterized in that: comprise the active carbon of 60-70% and the nCoO-mNiO composite oxides of 30-40% by weight percentage, in the described composite oxides, the atomic ratio n of Co and Ni: m is 4: 1-1: 4.
3. the catalyst that is used for hydrogen rich gas CO oxidation removal according to claim 2, it is characterized in that: comprise 65% active carbon and 35% nCoO-mNiO composite oxides by weight percentage, in the described composite oxides, the atomic ratio n of Co and Ni: m is 1: 1.
4. the catalyst that is used for hydrogen rich gas CO oxidation removal according to claim 1 and 2 is characterized in that: the hydrogen volume mark is not less than 90.0% in the described hydrogen rich gas.
5. prepare the method for the described catalyst of claim 1, it is characterized in that: may further comprise the steps:
(1) amount by described Co and Ni atomic ratio takes by weighing cobalt salt and nickel salt respectively and fully is dissolved in the distilled water, getting 20-80 purpose activated carbon granule impregnated in the gained solution, 353K evaporate to dryness moisture content under stirring condition gets raw material again, and gained raw material freeze-day with constant temperature 10-24h under 373K makes siccative;
Described active carbon weight is 6 with the ratio of the composite oxides theoretical weight that forms by described atomic ratio: 4-7: 3.
(2) gained siccative heating rate with 5K/min in the room temperature inert environments is warming up to 573-673K, and constant temperature calcining 2-4h makes required catalyst under 573-673K then.
6. preparation method according to claim 5 is characterized in that: the described cobalt salt of step (1) is a cobalt nitrate, and described nickel salt is a nickel nitrate.
7. the described Application of Catalyst of claim 1, it is characterized in that: comprise the steps: the gained catalyst and the tubular fixed-bed reactor of packing into after inertia quartz sand mixes, feed rich hydrogen unstripped gas after being warmed up to reaction temperature, and at this reaction temperature and 20,000h
-1Reaction gas air speed condition under isothermal reaction at least 180 minutes, reaction back gained gas removes CO through the soda lime drying
2After get final product;
Wherein, when the atomic ratio n of Co in the composite oxides and Ni: m more than or equal to 1: 4 and be that described reaction temperature is 413-443K more than or equal to 30% and less than 35% the time less than the weight ratio of 1: 1, composite oxides and active carbon; Atomic ratio n as Co in the composite oxides and Ni: m greater than 1: 1 and smaller or equal to the weight ratio of 4: 1, composite oxides and active carbon greater than 35% and when being less than or equal to 40%, described range of reaction temperature is 433-453K; Atomic ratio n as Co in the composite oxides and Ni: m is the weight ratio of 1: 1, composite oxides and active carbon when being 35%, and described range of reaction temperature is 413-463K.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104512864A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Method for removing micro-scale carbon monoxide at low temperature |
| CN113666337A (en) * | 2021-07-30 | 2021-11-19 | 清华大学 | Non-pure hydrogen sectional purification treatment method and device for fuel cell |
| CN115477282A (en) * | 2021-05-31 | 2022-12-16 | 国家能源投资集团有限责任公司 | Method for removing CO from high-purity hydrogen, purified hydrogen and application of purified hydrogen |
-
2010
- 2010-05-07 CN CN2010101665292A patent/CN101934229B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 《Chemical Engineering Journal》 20051231 Guilin Zhou et al. Non-noble metal catalyst for carbon monoxide selective oxidation in excess hydrogen 第142页第2.1节、2.3节及第144页第3.4节 1-7 第109卷, 2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104512864A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Method for removing micro-scale carbon monoxide at low temperature |
| CN115477282A (en) * | 2021-05-31 | 2022-12-16 | 国家能源投资集团有限责任公司 | Method for removing CO from high-purity hydrogen, purified hydrogen and application of purified hydrogen |
| CN115477282B (en) * | 2021-05-31 | 2024-04-02 | 国家能源投资集团有限责任公司 | Method for removing CO in high-purity hydrogen, purified hydrogen and application thereof |
| CN113666337A (en) * | 2021-07-30 | 2021-11-19 | 清华大学 | Non-pure hydrogen sectional purification treatment method and device for fuel cell |
| CN113666337B (en) * | 2021-07-30 | 2023-08-15 | 清华大学 | Method and device for purifying non-pure hydrogen in segments for fuel cell |
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