CN1768926A - Catalyst for selective oxidation of CO in hydrogen enriched gas and its preparation method - Google Patents
Catalyst for selective oxidation of CO in hydrogen enriched gas and its preparation method Download PDFInfo
- Publication number
- CN1768926A CN1768926A CN 200510100264 CN200510100264A CN1768926A CN 1768926 A CN1768926 A CN 1768926A CN 200510100264 CN200510100264 CN 200510100264 CN 200510100264 A CN200510100264 A CN 200510100264A CN 1768926 A CN1768926 A CN 1768926A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- hydrogen
- active component
- cuo
- 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
Abstract
The invention relates to a catalyst for CO selective oxidation in hydrogen-rich gas of fuel battery electric vehicle, and its preparing process, wherein the catalyst comprises main active component of CuO, an auxiliary active component of CeO2, and another auxiliary active component comprising MgO, Li2O, Y2O3, ZnO, Fe2O3 or MnO2. The catalyst is prepared by using parallel flow co-precipitation method or sol-gal process.
Description
Technical field
The present invention relates to Catalysts and its preparation method, CO catalyst for selective oxidation and preparation method thereof in a kind of specifically hydrogen-rich gas, it can the temperature range of broad with hydrogen-rich gas in the content of CO reduce to below the 100ppm, even below the 10ppm, satisfy the actual condition demand of fuel cell.
Background technology
Proton Exchange Membrane Fuel Cells is to utilize principle of electrochemical reaction, is fuel with hydrogen or hydrogen-rich gas, the TRT of high efficiency, non-pollution discharge.Adopting liquid fuel, as methyl alcohol, gasoline etc., is the fuel cell electric vehicle fuel supplying by the reformer that carries, the inconvenience of aspects such as vehicle-mounted, storage that has solved that pure hydrogen fuel exists and transportation.The PEMFC electrode material is generally Pt at present, and the CO of trace can make its irreversible poisoning, so the content of CO must be controlled at below the 100ppm in the unstripped gas.The content of CO is higher than the patient level of PEMFC far away usually up to 0.5～2.5vol% in the hydrogen-rich gas that is obtained by reforming reactions such as methyl alcohol, aerating oxygen in hydrogen-rich gas, and optionally oxidation CO is one of present most economical effective method.
Be used for this catalyst for reaction at present and mainly contain Au catalyst, platinum group catalyst and non-precious metal catalyst three classes.Wherein the operating temperature of Au catalyst active temperature and PEMFC (80 ℃) is suitable, though have the humidity enhancement effect, to CO
2Also insensitive advantage, but catalyst particle size and reaction condition are extremely obvious to the activity influence of Au catalyst.For the more platinum group catalyst of nearest research, its performance is more stable, but low temperature active is lower, and needs the oxygen that surpasses the metering ratio far away, exists unnecessary hydrogen consumption like this.As the patent CN1397485A catalyst that to relate to a kind of Pt content be 0.05～5% (weight), at O
2During/CO=1.8, CO can be reduced to below the 100ppm, but the selectivity of oxygen is on the low side.Prior art also discloses Pt, the Ru catalyst (patent No. CN1426959A) that is carried on y-type zeolite, ZSM zeolite and the modenite, mol ratio at oxygen and CO is 1～2, reaction temperature is between 120～200 ℃, its CO conversion ratio is near 100%, but in such catalyst the content of Pt, Ru up to 3% (weight).It is reported that the noble metal conservative estimation of using in PEMFC and the fuel treatment process is 100～150g (a 50kW power vehicle), therefore there is bigger restriction in the large-scale promotion application of noble metal catalysts such as gold and platinum group on fuel cell electric vehicle.
At a lower temperature, copper catalyst has than better activity of platinum catalyst and selectivity.Add active transition metal oxide (as CuO) in the cerium oxide of fluorite structure after, the raising of its oxidation activity is not simple addition, but a kind of synergy.Patent WO0160738 A2 (August 23 calendar year 2001) provides the Cu of series reaction temperature between 25～300 ℃
xCe
1-xO
2-yCatalyst (x, y are mol ratio for x=0.01～0.3, y 〉=x), but this catalyst can not reduce to the CO that contains in the simulation gas of 1vol%CO below the 100ppm, do not study the performance of catalyst in the actual reformed gas that steam exists simultaneously.At Applied Catalysis A:(General) 232 (2002), in 107-120 one literary composition, the author adopts infusion process to make the CuO/CeO of samaria doped
2Catalyst is H at gas mixing ratio
2: O
2: CO=97: demonstrate CO catalytic performance preferably under 2: 1 the condition,, still can not reflect the actual condition of fuel cell because the gas of experimental study and reformed gas discrepancy are very big.People such as Ratnasamy were published in Journal of Catalysis 221 (2004), the CuO-CeO that mentions in the paper of 455-465 in 2004
2-ZrO
2Catalyst is 175 ℃ in temperature, O
2/ CO is under 1.25 the condition, the CO of 0.49vol% in the hydrogen-rich gas is reduced to 140ppm, but the CO conversion ratio of this catalyst and selectivity is all on the low side, and the temperature range less than used of catalyst is 25 ℃ simultaneously.Apply for a patent (patent No. CN92111005.7) of China Petrochemical Corporation related to a kind of non-noble metal oxide CO combustion adjuvant, and its active component is: Cu-M
1-M
2-O (M
1Refer to transition metal, as Mn, Co; M
2It is rare earth metal, as Ce), suitable with industrial precious metals pt or Pd combustion adjuvant performance, in reaction temperature is 550～650 ℃, under the oxygen concentration condition suitable with CO concentration, show good catalytic activity and hydrothermal stability, but do not report that can this catalyst at the catalytic performance under lower temperature and the rich hydrogen condition.
Summary of the invention
The objective of the invention is to shortcoming at the prior art existence, CO catalyst for selective oxidation in a kind of hydrogen-rich gas is provided, the reaction temperature interval, high selectivity and the stability that have broad at catalyst, and efficient advantages of being cheap, can satisfy the requirement of fuel cell electric vehicle preferably to hydrogen-rich gas.
Another object of the present invention is to provide described Preparation of catalysts method.
The CO catalyst for selective oxidation helps active component CeO by main active component CuO, in the hydrogen-rich gas of the present invention
2, another helps active component MgO, Li
2O, Y
2O
3, ZnO, Fe
2O
3Or MnO
2Form, each composition weight umber is as follows:
CuO 5～30
CeO
2 55～90
MgO, Li
2O, Y
2O
3, ZnO, Fe
2O
3Or MnO
25～15.
The optimum weight umber is composed as follows:
CuO 5～10
CeO
2 80～90
MgO, Li
2O, Y
2O
3, ZnO, Fe
2O
3Or MnO
25～10.
The CO catalyst for selective oxidation can adopt existing method to prepare in the hydrogen-rich gas of the present invention, for example adopts and flow coprecipitation method to prepare perhaps sol-gel process preparation.
When employing and stream coprecipitation method prepare,, it is 70～90 ℃ in temperature with the nitrate and the precipitant solution of each component of catalyst, react under pH value 8～10 conditions, and drip is gone in the stillpot aging 2-4 hour of the precipitation of generation, after washing, drying, 400～700 ℃ of following roastings 3～5 hours.
Described precipitating reagent can be general precipitating reagent, and its consumption does not have strict restriction, with reach be precipitated as fully suitable, preferred NaOH, Na
2CO
3, NaHCO
3Or (NH
4)
2CO
3PH value preferred 9～10.
When adopting the sol-gel process method to prepare, the salting liquid of each component of catalyst is mixed with the ligand solution of the total amount of substance twice of metal, with nitric acid regulator solution pH value is 1～4, mixed solution is at 70～90 ℃ of water-bath heating evaporations, obtain transparent gel, after after 110 ℃ of oven dry, in 400～600 ℃ of roasting temperatures 3～5 hours.
Described part is the general part of sol-gel process, optimization citric acid, oxalic acid or urea.
Described PH preferred 1.5～3.
The CO catalyst for selective oxidation compared with prior art has following advantage in the hydrogen-rich gas of the present invention:
1. have good CO oxidation activity, the CO of 1vol% in the reformation gas can be reduced to below the 100ppm, even below the 10ppm;
2. have the performance that stronger anti-steam is poisoned, under the situation of the steam that contains 9vol%, still can satisfy actual requirement;
3. at the reaction temperature interval of broad (140～200 ℃) and gas space velocity (5000～25000h
-1) under have higher conversion ratio, be fit to the PEMFC electric motor car and change and requirement during frequent startup in load;
4. utilize the cheap base metal and the rare earth metal of China's abundant, low price is applicable in the hydrogen-feeding system of Proton Exchange Membrane Fuel Cells electric motor car.
The specific embodiment
Embodiment 1
Adopt and flow coprecipitation and prepare catalyst, take by weighing copper nitrate 0.49g respectively, cerous nitrate 8g, zinc nitrate 0.61g is made into mixed solution 1, the sodium carbonate liquor of preparation 0.5M is a solution 2, solution 1 and solution 2 constant speed and drip under vigorous stirring are gone in the stillpot, and temperature is controlled at 70 ℃ in the precipitation process, and keeping pH value is 10, treat to filter, wash to neutrality with deionized water behind the complete also ageing 3h of precipitation, at 110 ℃ of following oven dry 12h, and in 600 ℃ roasting 5h, promptly obtain catalyst of the present invention.
Get 40～60 order catalyst 0.3g of this example preparation, with same granularity quartz sand dilution, in the crystal reaction tube of the internal diameter 7mm that packs into, first 300 ℃ with 50ml/min air-activated 2 hours, switch to hydrogen-rich gas then, gas composition is 65%H
2, 25%CO
2, 1%CO, 9%H
2O.When reaction temperature is 160 ℃, oxygen input O
2/ CO=1.5, GHSV=25000h
-1The time, the concentration of CO can be reduced to below the 76ppm, the selectivity of CO is 57.7%.
Embodiment 2
Take by weighing copper nitrate 0.49g respectively, cerous nitrate 8g, yttrium nitrate 1.18g is made into mixed solution 1, and the sal volatile of preparation 0.4M is a solution 2, and solution 1 and solution 2 constant speed and drip under vigorous stirring are gone in the stillpot, temperature is controlled at 90 ℃ in the precipitation process, the maintenance pH value is 9, treats to filter, wash to neutrality with deionized water behind the complete also ageing 3h of precipitation, oven dry 12h under 110 ℃, and in 700 ℃ roasting 4h, promptly get catalyst of the present invention.
Get 40～60 order catalyst 0.3g of this example preparation, with same granularity quartz sand dilution, in the crystal reaction tube of the internal diameter 7mm that packs into, first 300 ℃ with 50ml/min air-activated 2 hours, switch to hydrogen-rich gas then, gas composition is 65%H
2, 25%CO
2, 1%CO, 9%H
2O.When reaction temperature is 200 ℃, oxygen input O
2/ CO=1.5, GHSV=10000h
-1The time, the concentration of CO can be reduced to below the 97ppm, the selectivity of CO is 64.3%.
Embodiment 3
Take by weighing copper nitrate 0.49g respectively, cerous nitrate 8g, magnesium nitrate 0.59g is made into mixed solution 1, and the sodium carbonate liquor of preparation 0.5M is a solution 2, and solution 1 and solution 2 constant speed and drip under vigorous stirring are gone in the stillpot, temperature is controlled at 70 ℃ in the precipitation process, the maintenance pH value is 10, treats to filter, wash to neutrality with deionized water behind the complete also ageing 3h of precipitation, oven dry 12h under 110 ℃, and in 600 ℃ roasting 4h, promptly obtain catalyst of the present invention.
Get 40～60 order catalyst 0.3g of this example preparation, with same granularity quartz sand dilution, in the crystal reaction tube of the internal diameter 7mm that packs into, first 300 ℃ with 50ml/min air-activated 2 hours, switch to hydrogen-rich gas then, gas composition is 65%H
2, 25%CO
2, 1%CO, 9%H
2O.In reaction temperature is 160 ℃, oxygen input O
2/ CO=1.0, GHSV=15000h
-1Condition under, the concentration of CO can be reduced to below the 28ppm, the selectivity of CO is 65.7%.
Embodiment 4
Take by weighing copper nitrate 0.49g respectively, cerous nitrate 8g, 50% manganese nitrate solution 0.75ml is made into mixed solution 1, and the sodium bicarbonate solution of preparation 0.5M is a solution 2, and solution 1 and solution 2 constant speed and drip under vigorous stirring are gone in the stillpot, temperature is controlled at 80 ℃ in the precipitation process, the maintenance pH value is 10, treats to filter, wash to neutrality with deionized water behind the complete also ageing 3h of precipitation, oven dry 12h under 110 ℃, and in 500 ℃ roasting 4h, promptly obtain catalyst of the present invention.
Get 40～60 order catalyst 0.3g of this example preparation, with same granularity quartz sand dilution, in the crystal reaction tube of the internal diameter 7mm that packs into, first 300 ℃ with 50ml/min air-activated 2 hours, switch to hydrogen-rich gas then, gas composition is 65%H
2, 25%CO
2, 1%CO, 9%H
2O.At 160 ℃, oxygen input O
2/ CO=2.0, GHSV=10000h
-1Condition under, the concentration of CO can be reduced to below the 13ppm, the selectivity of CO is 42.4%.
Embodiment 5
Take by weighing copper nitrate 0.49g respectively, cerous nitrate 8g, lithium nitrate 0.24g is made into mixed solution 1, and the sodium carbonate liquor of preparation 0.5M is a solution 2, and solution 1 and solution 2 constant speed and drip under vigorous stirring are gone in the stillpot, temperature is controlled at 70 ℃ in the precipitation process, the maintenance pH value is 10, treats to filter, wash to neutrality with deionized water behind the complete also ageing 3h of precipitation, oven dry 12h under 110 ℃, and in 500 ℃ roasting 4h, promptly obtain catalyst of the present invention.
Get 40～60 order catalyst 0.3g of this example preparation, with same granularity quartz sand dilution, in the crystal reaction tube of the internal diameter 7mm that packs into, first 300 ℃ with 50ml/min air-activated 2 hours, switch to hydrogen-rich gas then, gas composition is 65%H
2, 25%CO
2, 1%CO, 9%H
2O.At 160 ℃, oxygen input O
2/ CO=1.5, GHSV=10000h
-1Condition under, the concentration of CO can be reduced to below the 24ppm, the selectivity of CO is 45.6%.
Embodiment 6
Take by weighing copper nitrate 0.49g respectively, cerous nitrate 8g, ferric nitrate 0.83g is made into mixed solution 1, gets the urea that doubles the total amount of substance of metal and is made into 0.3M solution 2, under vigorous stirring solution 1 and solution 2 is mixed, be 2.0 with nitric acid regulator solution pH value then, mixed solution obtains transparent gel at 80 ℃ of water-bath heating evaporations, behind 110 ℃ of oven dry 12h, and in 600 ℃ of air atmospheres roasting 3h, promptly obtain catalyst of the present invention.
Get 40～60 order catalyst 0.3g of this example preparation, with same granularity quartz sand dilution, in the crystal reaction tube of the internal diameter 7mm that packs into, first 300 ℃ with 50ml/min air-activated 2 hours, switch to hydrogen-rich gas then, gas composition is 65%H
2, 25%CO
2, 1%CO, 9%H
2O.When reaction temperature is 160 ℃, oxygen input O
2/ CO=1.5, GHSV=25000h
-1The time, the concentration of CO can be reduced to below the 59ppm, the selectivity of CO is 46.7%.
Embodiment 7
Take by weighing copper nitrate 0.49g respectively, cerous nitrate 8g, ferric nitrate 0.83g is made into mixed solution 1, gets the oxalic acid that doubles the total amount of substance of metal and is made into 0.4M solution 2, under vigorous stirring solution 1 and solution 2 is mixed, be 3.5 with nitric acid regulator solution pH value then, mixed solution obtains transparent gel at 80 ℃ of water-bath heating evaporations, behind 110 ℃ of oven dry 12h, and in 500 ℃ of air atmospheres roasting 5h, promptly obtain catalyst of the present invention.
Get 40～60 order catalyst 0.3g of this example preparation, with same granularity quartz sand dilution, in the crystal reaction tube of the internal diameter 7mm that packs into, first 300 ℃ with 50ml/min air-activated 2 hours, switch to hydrogen-rich gas then, gas composition is 65%H
2, 25%CO
2, 1%CO, 9%H
2O.When reaction temperature is 160 ℃, oxygen input O
2/ CO=2.0, GHSV=5000h
-1The time, the concentration of CO can be reduced to below the 8ppm, the selectivity of CO is 35.3%.
Embodiment 8
Take by weighing copper nitrate 0.53g respectively, cerous nitrate 8.42g, 50% manganese nitrate solution 0.5ml is made into mixed solution 1, gets the citric acid that doubles the total amount of substance of metal and is made into 0.4M solution 2, under vigorous stirring solution 1 and solution 2 is mixed, be 1.0 with nitric acid regulator solution pH value then, mixed solution obtains transparent gel at 90 ℃ of water-bath heating evaporations, behind 110 ℃ of oven dry 12h, and in 400 ℃ of air atmospheres roasting 5h, promptly obtain catalyst of the present invention.
Get 40～60 order catalyst 0.3g of this example preparation, with same granularity quartz sand dilution, in the crystal reaction tube of the internal diameter 7mm that packs into, first 300 ℃ with 50ml/min air-activated 2 hours, switch to hydrogen-rich gas then, gas composition is 65%H
2, 25%CO
2, 1%CO, 9%H
2O.When reaction temperature is 160 ℃, oxygen input O
2/ CO=1.5, GHSV=15000h
-1The time, the concentration of CO can be reduced to below the 47ppm, the selectivity of CO is 50.3%.
Claims (8)
1, CO catalyst for selective oxidation in a kind of hydrogen-rich gas is characterized in that helping active component CeO by main active component CuO,
2, another helps active component MgO, Li
2O, Y
2O
3, ZnO, Fe
2O
3Or MnO
2Form, each composition weight umber is as follows:
CuO 5～30
CeO
2 55～90
MgO, Li
2O, Y
2O
3, ZnO, Fe
2O
3Or MnO
25～15.
2, catalyst according to claim 1 is characterized in that parts by weight are composed as follows:
CuO 5～10
CeO
2 80～90
MgO, Li
2O, Y
2O
3, ZnO, Fe
2O
3Or MnO
25～10.
3, claim 1 or 2 described Preparation of catalysts methods, it is characterized in that nitrate and precipitant solution with each component of catalyst, in temperature is 70～90 ℃, react under pH value 8～10 conditions, and drip is gone in the stillpot, aging 2～4 hours of the precipitation that generates is after washing, drying, 400～700 ℃ of following roastings 3～5 hours.
4, method according to claim 3 is characterized in that described precipitating reagent is NaOH, Na
2CO
3, NaHCO
3Or (NH
4)
2CO
3
5,, it is characterized in that described pH value is 7～10 according to claim 3 or 4 described methods.
6, claim 1 or 2 described methods, it is characterized in that the salting liquid of each component of catalyst is mixed with the ligand solution of the total amount of substance twice of metal, with nitric acid regulator solution pH value is 1～4, mixed solution is at 70～90 ℃ of water-bath heating evaporations, obtain transparent gel, after after 110 ℃ of oven dry, in 400～600 ℃ of roasting temperatures 3～5 hours.
7, method according to claim 6 is characterized in that described part is citric acid, oxalic acid or urea.
8,, it is characterized in that described PH is 1.5～3 according to claim 6 or 7 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101002645A CN100479915C (en) | 2005-10-13 | 2005-10-13 | Catalyst for selective oxidation of CO in hydrogen enriched gas and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101002645A CN100479915C (en) | 2005-10-13 | 2005-10-13 | Catalyst for selective oxidation of CO in hydrogen enriched gas and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1768926A true CN1768926A (en) | 2006-05-10 |
| CN100479915C CN100479915C (en) | 2009-04-22 |
Family
ID=36750612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101002645A Expired - Fee Related CN100479915C (en) | 2005-10-13 | 2005-10-13 | Catalyst for selective oxidation of CO in hydrogen enriched gas and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100479915C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752311A (en) * | 2013-11-25 | 2014-04-30 | 邵建军 | Preparation and catalytic application of Au/ZnO/CeO2 catalyst |
| CN104475114A (en) * | 2014-11-19 | 2015-04-01 | 上海化工研究院 | Copper-zinc-cerium-based catalyst for low-temperature deep removal of carbon monoxide and preparation method and application of catalyst |
| CN103362613B (en) * | 2012-03-30 | 2015-10-28 | 通用汽车环球科技运作有限责任公司 | Carbon monoxide selective oxidizing catalyst |
| CN107537515A (en) * | 2017-09-11 | 2018-01-05 | 中国科学技术大学 | A kind of application of carried copper Mn catalyst and preparation method thereof and CO catalytic oxidation under low temperature |
-
2005
- 2005-10-13 CN CNB2005101002645A patent/CN100479915C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103362613B (en) * | 2012-03-30 | 2015-10-28 | 通用汽车环球科技运作有限责任公司 | Carbon monoxide selective oxidizing catalyst |
| CN103752311A (en) * | 2013-11-25 | 2014-04-30 | 邵建军 | Preparation and catalytic application of Au/ZnO/CeO2 catalyst |
| CN104475114A (en) * | 2014-11-19 | 2015-04-01 | 上海化工研究院 | Copper-zinc-cerium-based catalyst for low-temperature deep removal of carbon monoxide and preparation method and application of catalyst |
| CN107537515A (en) * | 2017-09-11 | 2018-01-05 | 中国科学技术大学 | A kind of application of carried copper Mn catalyst and preparation method thereof and CO catalytic oxidation under low temperature |
| CN107537515B (en) * | 2017-09-11 | 2020-04-17 | 中国科学技术大学 | Supported copper-manganese catalyst, preparation method thereof and application of supported copper-manganese catalyst in low-temperature catalytic oxidation of CO |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100479915C (en) | 2009-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Luengnaruemitchai et al. | Selective catalytic oxidation of CO in the presence of H2 over gold catalyst | |
| KR101426110B1 (en) | Desulfurizing agent for kerosene, desulfurization method and fuel cell system using the desulfurizing agent for kerosene | |
| CN101947456B (en) | Integral automobile exhaust purification catalyst and preparation method thereof | |
| US6576217B1 (en) | Methanol reforming catalyst, method of manufacturing methanol reforming catalyst and method of reforming methanol | |
| CN101944620B (en) | Fuel cell catalyst taking multi-element compound as carrier and preparation method thereof | |
| CN101181683B (en) | Method for preparing cu-ce composite oxidation catalyst | |
| CN1672789A (en) | Catalyst for autothermal reformation of methanol to prepared hydrogen and its prepn process and application | |
| KR20190102532A (en) | Method for Manufacturing High Purity Electrolyte for Vandium Redox Flow Battery by using Catalytic Reaction | |
| CN100479915C (en) | Catalyst for selective oxidation of CO in hydrogen enriched gas and preparation method thereof | |
| CN103143364A (en) | High-dispersion nano-composite catalyst, and preparation method and applications thereof | |
| CN109772165A (en) | A kind of tail gas clean-up reactor and preparation method thereof reacts pile with tail gas clean-up | |
| CN101607201A (en) | Be difficult for water gas converting catalyst of spontaneous combustion and its production and application | |
| CN101580225B (en) | Method for preparing low platinum modified carbon-loaded ruthenium nano particles and application thereof | |
| CN105148930A (en) | Modified Co-Ce core-shell structure catalyst for carbon monoxide (CO) low-temperature oxidation | |
| CN101306365A (en) | Composite anode electrocatalyst for direct methanol fuel cell | |
| CN1698956A (en) | Method for preparing catalyst(CuxCeO2-x) for low-temperature selective oxidation removal of CO | |
| CN101733128A (en) | Preparation method of catalyst for selectively oxidizing CO in hydrogen-rich gas | |
| JP2003144930A (en) | Desulfurization catalyst for hydrocarbon, desulfurization method and fuel cell system | |
| US20040156771A1 (en) | Method of reducing carbon monoxide concentration | |
| JP3796745B2 (en) | CO selective oxidation catalyst in hydrogen gas, method for producing the same, and method for removing CO in hydrogen gas | |
| CN110038565B (en) | High-airspeed catalyst for hydrogen production from methanol water and preparation method and application thereof | |
| CN1258397C (en) | Nano cerium and zirconium based oxide with transition elements added and its preparation | |
| CN1489232A (en) | Method for preparing carbon-carried platinum/rare earth oxide composite electro catalyst for fuel cell | |
| CN112403463A (en) | Pt-based perovskite catalyst and preparation method thereof | |
| CN100466346C (en) | Low-temperature fuel cell platinum-tin base anode catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090422 Termination date: 20111013 |