CN102806080A - Water gas shift reaction, water gas shift catalyst and preparation method thereof - Google Patents
Water gas shift reaction, water gas shift catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 153
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 258
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 175
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 123
- 239000000945 filler Substances 0.000 claims abstract description 39
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 35
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 76
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 73
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 73
- 229910052684 Cerium Inorganic materials 0.000 claims description 40
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 39
- 238000012546 transfer Methods 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 2
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 37
- 239000000243 solution Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 230000001186 cumulative effect Effects 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 206010013786 Dry skin Diseases 0.000 description 12
- 239000004411 aluminium Substances 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 239000003292 glue Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 8
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 7
- 239000000446 fuel Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
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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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- Catalysts (AREA)
Abstract
The invention relates to a water gas shift reaction, a water gas shift catalyst and a preparation method thereof. The water gas shift catalyst provided by the invention comprises 100 parts by weight of metal oxide carrier, wherein platinum is loaded on the surface of the metal oxide carrier, and the weight ratio of the metal oxide carrier to the platinum is between 100: 0.1 and 100: 10; and 120 to 10 parts by weight of a zirconia filler, wherein platinum is not supported on the surface of the zirconia filler, and the zirconia filler and the metal oxide carrier are dispersed and mixed, wherein the metal oxide carrier is composed of cerium oxide or cerium zirconium oxide.
Description
Technical field
The present invention relates to catalyst, more especially in regard to the used catalyst of gas shift reaction.
Background technology
Macromolecule membrane fuel cell (PEMFC) is applied to following fixation type family electricity generation system and electric automobile most probably, and its fuel is the hydrogen-rich gas that carbonomonoxide concentration is lower than 20ppm.The hydrogen-rich reformed gas that general hydrocarbon produces through reforming reaction; Its carbonomonoxide concentration is about 8～15%; Need suc as formula 1 carbonomonoxide concentration to be reduced to below 1%, with selective oxidation or methanation reaction the carbonomonoxide concentration of remnants is reduced to below the 20ppm again via gas shift reaction (WGS).
H
2O+CO → CO
2+ H
2(formula 1)
Traditional WGS catalyst is Cu-ZnO/Al
2O
3, its range of reaction temperature is narrow, needs activation, and is can not ingress of air also thermo-labile.Above-mentioned shortcoming makes this catalyst be not suitable for being applied to the fuel reformer of family's fixation type fuel cell generation, or needs extra supplementary measures, as with the steam reforming reaction design system, in order to avoid ingress of air.
Another kind of WGS catalyst is a noble metal catalyst, and its range of reaction temperature is wide, do not need activation, preferable hear resistance is arranged, and is applicable to the carbon monoxide converter of reformer.At United States Patent (USP) the 6th, 455, in No. 182, disclosed Pt/CeO
2-ZrO
2The traditional copper zinc catalyst of specific activity good.At United States Patent (USP) the 6th, 777, in No. 117, Pt-M/ZrO is disclosed
2(M can be Re, Se or Pr).At United States Patent (USP) the 6th, 723, in No. 298, PtPdFe/CeO is disclosed
2/ Al
2O
3Antigravity system.At US 6,790, in 432, Pt/SnO is disclosed
2/ CeO
2Catalyst, and declare SnO
2Can suppress methanation reaction.At European patent the 1st, 184, in No. 445, Pt-M/TiO is disclosed
2(M can be Al, Si, P, S or V).In fact, above-mentioned catalyst all has its shortcoming.For instance, the bullion content of most catalyst is higher, and this will raise the cost.United States Patent (USP) the 6th, 455, No. 182 disclosed Pt/CeO
2-ZrO
2Being known as the zirconia cerium can provide oxygen and quicken carbon monoxide and convert carbon dioxide into, therefore can reduce noble metal dosage.But Pt/CeO
2-ZrO
2After long-time the use, the carbon monoxide conversion ratio of catalyst has the problem of slow decline.At Catalysttoday, 104, the 18 pages; 2005, Applied catalysis:Environ., 56, the 69 pages; 2005, reach Applied catalysis:Environ., 93, the 250 pages; Mention in 2010 periodicals such as grade that ceria can change cerous carbonate into when starting reaction and stopping to react, therefore lose the effect of oxygen supply.Long-time reaction its carbon monoxide conversion ratio down will descend.
Summary of the invention
One embodiment of the invention provides a kind of water-gas transfer catalyst, comprises 100 parts by weight of metal oxide carriers, and the area load of this metal oxide carrier has platinum, and the weight ratio of metal oxide carrier and platinum is between 100: 0.1 to 100: 10; And the zirconia filler of 120 to 10 weight portions, the not load of surface of this zirconia filler has platinum, and this zirconia filler and this metal oxide carrier dispersing and mixing, and wherein this metal oxide carrier is made up of cerium oxide or zirconia cerium.
Another embodiment of the present invention provides a kind of gas shift reaction, and comprising provides water-gas, water-gas to comprise water and carbon monoxide, and the mol ratio of water and carbon monoxide is between 3: 1 to 10: 1; And water-gas fed above-mentioned water-gas transfer catalyst, make carbon monoxide and water reaction in the water-gas form carbon dioxide and hydrogen.
Further embodiment of this invention provides a kind of preparation method of water-gas transfer catalyst, comprises the surface that platinum is deposited on metal oxide carrier; And the metal oxide carrier and the zirconia filler dispersing and mixing that area load are had platinum; Form the water-gas transfer catalyst; Wherein metal oxide carrier is cerium oxide or zirconia cerium; The weight ratio of burning carrier and platinum is between 100: 0.1 to 100: 10, and the weight ratio of metal oxide carrier and zirconia filler is between 100: 120 to 100: 10.
Description of drawings
Fig. 1 is the carbon monoxide conversion ratio curve map of catalyst under different temperatures of embodiment of the invention 1-5 and comparative example 1-2;
Fig. 2 be the embodiment of the invention 1 with the catalyst of comparative example 1-2 in the time of 350 ℃, the carbon monoxide conversion ratio curve map after reaction a period of time;
Fig. 3 be the catalyst of the embodiment of the invention 2 in the time of 350 ℃, the carbon monoxide conversion ratio curve map after reaction a period of time;
Fig. 4 be the catalyst of the embodiment of the invention 5 in the time of 330 ℃, the carbon monoxide conversion ratio curve map after reaction a period of time;
Fig. 5 is the carbon monoxide conversion ratio curve map of catalyst under different temperatures of embodiment of the invention 6-9 and comparative example 2;
Fig. 6 be the catalyst of embodiment of the invention 6-9 and comparative example 2 in the time of 350 ℃, the carbon monoxide conversion ratio curve map after reaction a period of time; And
Fig. 7 be the embodiment of the invention 10 with the catalyst of comparative example 3-5 in the time of 350 ℃, the carbon monoxide conversion ratio curve map after reaction a period of time.
The specific embodiment
The present invention provides the preparation method of water-gas transfer catalyst in a plurality of embodiment.At first platinum is deposited on the surface of metal oxide carrier, and deposition process can be equi-volume impregnating (just wet infusion process).For instance, can metal oxide be added platinum solution such as platinum nitrate, platinum chloride or platinum acetate after, heated solution can let platinum be adsorbed on the surface of metal oxide to remove solvent again, adds thermal bake-out again.In an embodiment of the present invention, metal oxide carrier can be cerium oxide or zirconia cerium.The part by weight of metal oxide carrier and platinum is between 100: 0.1 to 100: 10.If the consumption of platinum is too high, the carbon monoxide conversion ratio is not had obvious help and raises the cost.If the consumption of platinum is low excessively, can't let the water-gas transfer catalyst have enough carbon monoxide conversion ratios.
Then area load there are the metal oxide carrier and the zirconia filler dispersing and mixing of platinum, form the water-gas transfer catalyst.In an embodiment of the present invention, the weight ratio of metal oxide carrier and zirconia filler is between 100: 120 to 100: 10.If the consumption of zirconia filler is low excessively, can't improve the water-gas transfer catalyst in the long-time problem of using the back inactivation.If the consumption of zirconia filler is too high, then can't let the water-gas transfer catalyst have enough carbon monoxide conversion ratios.
In an embodiment of the present invention; Area load has metal oxide carrier and the zirconia filler of platinum when coating the honeycomb carrier; Need via grinding to form slurry, metal oxide carrier after the grinding and zirconia filler particle diameter are approximately between 1 μ m to 10 μ m.
In an embodiment of the present invention, can the aluminium glue powder be added above-mentioned water-gas transfer catalyst and water and after grinding, be modulated into slurry, again this slurry is coated on the carrier.After drying to be heated and the roasting, can let the water-gas transfer catalyst be coated on the carrier.Above-mentioned carrier can be ceramic honeycomb shape carrier, honeycomb metal shape carrier or alumina balls carrier.
In another embodiment of the present invention, can further improve the carbon monoxide conversion ratio of catalyst with dressing agent such as sodium, potassium or above-mentioned combination.The weight ratio of metal oxide carrier and dressing agent is approximately between 100: 0.5 to 100: 5.If the weight ratio of dressing agent is too high, then catalyst can rise to the initiation temperature of reaction of carbon monoxide.If the weight ratio of dressing agent is low excessively, then catalyst does not have obvious lifting to the carbon monoxide conversion ratio.
Above-mentioned water-gas transfer catalyst can let carbon monoxide and the water reaction in the water-gas form hydrogen and carbon dioxide, shown in 1.The temperature of above-mentioned gas shift reaction is approximately between 200 ℃ to 500 ℃.If it is low that reaction temperature is spent, then carbon monoxide can not react with aqueous vapor, or reaction rate is too slow, needs to strengthen catalyst volume.If reaction temperature is too high, because of the gas shift reaction equilibrium relation, then the carbon monoxide conversion ratio descends.In an embodiment of the present invention, the mol ratio of water and carbon monoxide is between 3: 1 to 10: 1.If the mol ratio of water and carbon monoxide is low excessively, is unfavorable for the carbon monoxide balanced reaction thereby reduces the carbon monoxide conversion ratio.If the mol ratio of water and carbon monoxide is too high, then feed water is too many, is unfavorable for the thermal efficiency of fuel reformer.
Because the present invention adopts zirconia as filler, can promote the carbon monoxide conversion ratio of water-gas transfer catalyst and prolong catalyst life.On the other hand, the zirconia filler can reduce the consumption of platinum, and then reduces the catalyst cost.
For let state on the present invention with other purpose, characteristic and advantage can be more obviously understandable, the hereinafter spy enumerates a plurality of embodiment and cooperates Figure of description, elaborates as follows:
Embodiment
Embodiment 1
The zirconia cerium of 20g is added platinum solution (Pt (NO
2)
2(NH
3)
2Solution contains 0.3g platinum), keep 5 hours after being heated to 120 ℃ to remove solvent, be heated to 500 ℃ of roasts again 2 hours, promptly get the surperficial zirconia cerium catalyst that is covered with platinum, wherein the weight ratio of zirconia cerium and platinum is 100: 1.5.
Get the zirconia cerium catalyst that the 6.25g surface is covered with platinum; Mix with the Zirconium oxide powder of 4.25g; Add 2g aluminium glue powder again, about solid content to 49%, grind and form slurry with 13g water adjustment said mixture; Between adjustment slurry viscosity to 10～100cP (slurry viscosity uses rotary viscosimeter to measure), slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length
2) the hole surface of ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes) on, afterwards above-mentioned honeycomb carrier was heated to 120 ℃ of dryings 12 hours, be heated to 450 ℃ of roastings 2 hours again.Thus, area load has the zirconia cerium carrier of platinum and the zirconia filler that not load of surface has platinum, is coated on the hole surface of honeycomb carrier evenly mixing.Calculate the weight that catalyst is attached to the honeycomb carrier, the weight that the catalyst adhesion amount is coated with catalyst honeycomb carrier for the hole surface deducts the weight of honeycomb carrier.The catalyst adhesion amount is about 2.4g/, and platinum accounts for 0.75 weight % in the catalyst coating of honeycomb carrier surface.
Similar with embodiment 1, unique difference is that platinum solution contains 0.4g platinum, makes the surface be covered with that the weight ratio of zirconia cerium and platinum is 100: 2 in the zirconia cerium catalyst of platinum.Be coated at last in the lip-deep catalyst of hole of honeycomb carrier, platinum accounts for 1.0 weight % in the catalyst coating of honeycomb carrier surface.
Embodiment 3
Similar with embodiment 1, unique difference is that platinum solution contains 0.5g platinum, makes the surface be covered with that the weight ratio of zirconia cerium and platinum is 100: 2.5 in the zirconia cerium catalyst of platinum.Be coated at last in the lip-deep catalyst of hole of honeycomb carrier, platinum accounts for 1.25 weight % in the catalyst coating of honeycomb carrier surface.
Embodiment 4
Similar with embodiment 1, unique difference is that platinum solution contains 0.6g platinum, makes the surface be covered with that the weight ratio of zirconia cerium and platinum is 100: 3 in the zirconia cerium catalyst of platinum.Be coated at last in the lip-deep catalyst of hole of honeycomb carrier, platinum accounts for 1.5 weight % in the catalyst coating of honeycomb carrier surface.
Similar with embodiment 1, difference is that platinum solution contains 0.5g platinum, makes the surface be covered with that the weight ratio of zirconia cerium and platinum is 100: 2.5 in the zirconia cerium catalyst of platinum.
In addition, after roasting, the sodium nitrate aqueous solution that further will contain 6.1 weight % imports in the honeycomb carrier, tentatively dries up the honeycomb carrier with air again at the honeycomb carrier.Then the honeycomb carrier is heated to 120 ℃ of dryings 12 hours, was heated to 450 ℃ of roasts again 2 hours.Thus, sodium will be modified embodiment 1 described catalyst mixture surface.Be coated at last in the lip-deep catalyst of hole of honeycomb carrier, platinum accounts for 1.25 weight % in the catalyst coating of honeycomb carrier surface, and sodium accounts for 1.6 weight %.
Comparative example 1
The zirconia cerium of 20g is added platinum solution (Pt (NO
2)
2(NH
3)
2Solution contains 0.17g platinum), keep 5 hours after being heated to 120 ℃ to remove solvent, be heated to 500 ℃ of roastings 2 hours again, promptly get the surperficial zirconia cerium catalyst that is covered with platinum, wherein the weight ratio of zirconia cerium and platinum is 100: 0.85.
Get the zirconia cerium catalyst that the 11.44g surface is covered with platinum, add the 1.56g aluminium glue.About solid content to 50%, grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length with 13g water adjustment said mixture
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes), afterwards above-mentioned honeycomb carrier was heated to 120 ℃ of dryings 12 hours, be heated to 450 ℃ of roastings 2 hours again.The catalyst adhesion amount is about 2.4g/, and platinum accounts for 0.75 weight % in the catalyst coating of honeycomb carrier surface.
Comparative example 2
The zirconia cerium of 20g is added platinum solution (Pt (NO
2)
2(NH
3)
2Solution contains 0.3g platinum), keep 5 hours after being heated to 120 ℃ to remove solvent, be heated to 500 ℃ of roasts again 2 hours, promptly get the surperficial zirconia cerium catalyst that is covered with platinum, wherein the weight ratio of zirconia cerium and platinum is 100: 1.5.
Get the zirconia cerium catalyst that the 11.44g surface is covered with platinum; Add the 1.56g aluminium glue; About the solid content to 50% of adjustment said mixture; Grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes).Afterwards above-mentioned honeycomb carrier is heated to 120 ℃ of dryings 12 hours, is heated to 450 ℃ of roastings 2 hours again.Thus, area load has the zirconia cerium carrier of platinum, and with dispersing and mixing and be coated on the hole surface of honeycomb carrier, the catalyst adhesion amount is about 2.4g/, and platinum accounts for 1.32 weight % in the catalyst coating of honeycomb carrier surface.
In embodiment 1-5 and comparative example 1-2, the honeycomb carrier that the hole surface is coated with catalyst places the crystal reaction tube of 2 centimetres of internal diameters.Water-gas is imported crystal reaction tube carry out water-gas shift reaction, and control the inlet temperature of water-gas with electrothermal furnace.The carbon dioxide of the hydrogen that consists of 46.0 moles of % of water-gas, the carbon monoxide of 6.1 moles of %, 9.2 moles of %, and the water of 38.7 moles of %.The flow velocity of water-gas is 102.4 liters of/hour (space flow speed GHSV=8150hr
-1).Fig. 1 is the carbon monoxide conversion ratio curve map of catalyst under different temperatures of embodiment 1-5 and comparative example 1-2.Can know with the curve ratio of comparative example 1 by embodiment 1, under identical platinum consumption, adopt zirconia can under lower reaction temperature (as 330 ℃), have higher carbon monoxide conversion ratio as filler.In general, the platinum catalyst consumption is high more, and the carbon monoxide conversion ratio is high more, sees embodiment 1-4.Can know with the curve ratio of comparative example 2 by embodiment 3; Though the platinum catalyst ratio (1.25%) of embodiment 3 is less than the platinum catalyst ratio (1.32%) of comparative example 2, the carbon monoxide conversion ratio of embodiment 3 under any temperature all is higher than the carbon monoxide conversion ratio of comparative example 2.Curve by embodiment 5 can know, can effectively promote carbon monoxide conversion ratio to 90% at relatively low reaction temperature (as 310 ℃) with the practice of sodium modified catalyst.
In embodiment 1 and comparative example 1-2, the hole surface is coated with the honeycomb carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes) of catalyst, places the crystal reaction tube of 2 centimetres of internal diameters.Water-gas is imported crystal reaction tube carry out water-gas shift reaction, and be fixed in 350 ℃ with the inlet temperature of electrothermal furnace control water-gas.The carbon dioxide of the hydrogen that consists of 46.0 moles of % of water-gas, the carbon monoxide of 6.1 moles of %, 9.2 moles of %, and the water of 38.7 moles of %.The flow velocity of water-gas is 102.4 liters of/hour (space flow speed GHSV=8150hr
-1).Fig. 2 be embodiment 1 with the catalyst of comparative example 1-2 in the time of 350 ℃, the carbon monoxide conversion ratio curve map after reaction a period of time.After 16 hours, can find out obviously that the carbon monoxide conversion ratio of the catalyst of embodiment 1 still maintains more than 85%, but the carbon monoxide conversion ratio of the catalyst of comparative example 1-2 then drops to respectively below 70% and 80% below.From the above, can effectively promote life of catalyst with zirconia as the practice of filler.
In embodiment 2, the hole surface is coated with the honeycomb carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes) of catalyst, places the crystal reaction tube of 2 centimetres of internal diameters.Water-gas is imported crystal reaction tube carry out water-gas shift reaction, and be fixed in 350 ℃ with the inlet temperature of electrothermal furnace control water-gas.The carbon dioxide of the hydrogen that consists of 46.0 moles of % of water-gas, the carbon monoxide of 6.1 moles of %, 9.2 moles of %, and the water of 38.7 moles of %.The flow velocity of water-gas is 102.4 liters of/hour (space flow speed GHSV=8150hr
-1).Fig. 3 be the catalyst of embodiment 2 in the time of 350 ℃, the carbon monoxide conversion ratio curve map after reaction a period of time.Can know that by Fig. 3 after 500 hours, the carbon monoxide conversion ratio of catalyst is still up to 85%.
In embodiment 5, the hole surface is coated with the honeycomb carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes) of catalyst, places the crystal reaction tube of 2 centimetres of internal diameters.Water-gas is imported crystal reaction tube carry out water-gas shift reaction, and be fixed in 330 ℃ with the inlet temperature of electrothermal furnace control water-gas.The carbon dioxide of the hydrogen that consists of 46.0 moles of % of water-gas, the carbon monoxide of 6.1 moles of %, 9.2 moles of %, and the water of 38.7 moles of %.The flow velocity of water-gas is 102.4 liters of/hour (space flow speed GHSV=8150hr
-1).Fig. 4 be the catalyst of embodiment 5 in the time of 330 ℃, the carbon monoxide conversion ratio curve map after reaction a period of time.Can know that by Fig. 4 after 500 hours, the carbon monoxide conversion ratio of catalyst is still up to 89%.
The zirconia cerium of 20g is added platinum solution (Pt (NO
2)
2(NH
3)
2Solution contains 0.3g platinum), keep 5 hours after being heated to 120 ℃ to remove solvent, be heated to 500 ℃ of roasts again 2 hours, promptly get the surperficial zirconia cerium catalyst that is covered with platinum, wherein the weight ratio of zirconia cerium and platinum is 100: 1.5.
Get the zirconia cerium catalyst that the 4g surface is covered with platinum, mix, add the 1.6g aluminium glue again with the Zirconium oxide powder of 4.4g.About solid content to 50%, grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length with 10g water adjustment said mixture
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes).Afterwards above-mentioned honeycomb carrier is heated to 120 ℃ of dryings 12 hours, is heated to 450 ℃ of roastings 2 hours again.Thus; Area load has the zirconia cerium carrier of platinum and the zirconia filler that not load of surface has platinum; With dispersing and mixing and be coated on the hole surface of honeycomb carrier; The catalyst adhesion amount is about 2.4g/, and wherein platinum accounts for 0.6 weight % in the catalyst coating of honeycomb carrier surface.
Embodiment 7
Get the zirconia cerium catalyst that the surface is covered with platinum among the 5g embodiment 6, mix, add the 1.6g aluminium glue again with the Zirconium oxide powder of 3.4g.About solid content to 50%, grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length with 10g water adjustment said mixture
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes).Afterwards above-mentioned honeycomb carrier is heated to 120 ℃ of dryings 12 hours, is heated to 450 ℃ of roastings 2 hours again.Thus; Area load has the zirconia cerium carrier of platinum and the zirconia filler that not load of surface has platinum; With dispersing and mixing and be coated on the hole surface of honeycomb carrier; The catalyst adhesion amount is about 2.4g/, and wherein platinum accounts for 0.75 weight % in the catalyst coating of honeycomb carrier surface.
Get the zirconia cerium catalyst that the surface is covered with platinum among the 6g embodiment 6, mix, add the 1.6g aluminium glue again with the Zirconium oxide powder of 2.4g.About solid content to 50%, grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length with 10g water adjustment said mixture
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes).Afterwards above-mentioned honeycomb carrier is heated to 120 ℃ of dryings 12 hours, is heated to 450 ℃ of roastings 2 hours again.Thus; Area load has the zirconia cerium carrier of platinum and the zirconia filler that not load of surface has platinum; With dispersing and mixing and be coated on the hole surface of honeycomb carrier; The catalyst adhesion amount is about 2.4g/, and wherein platinum accounts for 0.9 weight % in the catalyst coating of honeycomb carrier surface.
Embodiment 9
Get the zirconia cerium catalyst that the surface is covered with platinum among the 7g embodiment 6, mix, add the 1.6g aluminium glue again with the Zirconium oxide powder of 1.4g.About solid content to 50%, grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length with 10g water adjustment said mixture
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes).Afterwards above-mentioned honeycomb carrier is heated to 120 ℃ of dryings 12 hours, is heated to 450 ℃ of roastings 2 hours again.Thus; Area load has the zirconia cerium carrier of platinum and the zirconia filler that not load of surface has platinum; With dispersing and mixing and be coated on the hole surface of honeycomb carrier; The catalyst adhesion amount is about 2.4g/, and wherein platinum accounts for 1.05 weight % in the catalyst coating of honeycomb carrier surface.
In embodiment 6-9 and comparative example 2, the hole surface is coated with the honeycomb carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes) of catalyst, places the crystal reaction tube of 2 centimetres of internal diameters.Water-gas is imported crystal reaction tube carry out water-gas shift reaction, and control the inlet temperature of water-gas with electrothermal furnace.The carbon dioxide of the hydrogen that consists of 46.0 moles of % of water-gas, the carbon monoxide of 6.1 moles of %, 9.2 moles of %, and the water of 38.7 moles of %.The flow velocity of water-gas is 102.4 liters of/hour (space flow speed GHSV=8150hr
-1).Fig. 5 is the carbon monoxide conversion ratio curve map of catalyst under different temperatures of embodiment 6-9 and comparative example 2.Curve ratio by embodiment 6-9 and comparative example 2 can know that even do not adopt zirconia to have higher platinum content as the catalyst of filler, its carbon monoxide conversion ratio is still low as the catalyst of filler than adopting zirconia.Comparison by embodiment 6-9 can be known, if the consumption of zirconia filler is too much, is unfavorable for its carbon monoxide conversion ratio on the contrary.Fig. 6 be the catalyst of embodiment 6-9 and comparative example 2 when 350 ℃ of constant temperature, the carbon monoxide conversion ratio curve map after reaction a period of time.At the water-gas shift reaction initial stage, the carbon monoxide conversion ratio of embodiment 6-9 and comparative example 2 is respectively 81%, 88%, 88%, 88%, reaches 89%.After reaction 20 hours, the carbon monoxide conversion ratio of embodiment 6 reduces to 75%, and the carbon monoxide conversion ratio of embodiment 7-9 maintains more than 87%, and the carbon monoxide conversion ratio of comparative example 2 reduces to 80%.Can know that by embodiment 6 too much zirconia filler will reduce the initial conversion of catalyst for carbon monoxide, and also can weaken for the degree of keeping of catalyst life.Can know by comparative example 2, if catalyst zirconia free filler even have the platinum of higher dosage, is kept its high carbon monoxide conversion ratio after still can't using in the short time.
The cerium oxide of 20g is added platinum solution (Pt (NO
2)
2(NH
3)
2Solution contains 0.3g platinum), keep 5 hours after being heated to 120 ℃ to remove solvent, be heated to 500 ℃ of roastings 2 hours again, promptly get the surperficial cerium oxide catalyst that is covered with platinum, wherein the weight ratio of cerium oxide and platinum is 100: 1.5.
Get the cerium oxide catalyst that the 6.25g surface is covered with platinum, mix, add the 2g aluminium glue again with the Zirconium oxide powder of 4.25g.About solid content to 49%, grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length with 13g water adjustment said mixture
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes).Afterwards above-mentioned honeycomb carrier is heated to 120 ℃ of dryings 12 hours, is heated to 450 ℃ of roastings 2 hours again.Thus; Area load has the cerium oxide carrier of platinum and the zirconia filler that not load of surface has platinum; With dispersing and mixing and be coated on the hole surface of honeycomb carrier; The catalyst adhesion amount is about 2.4g/, and wherein platinum accounts for 0.75 weight % in the catalyst coating of honeycomb carrier surface.
Comparative example 3
The cerium oxide of 20g is added platinum solution (Pt (NO
2)
2(NH
3)
2Solution contains 0.3g platinum), keep 5 hours after being heated to 120 ℃ to remove solvent, be heated to 500 ℃ of roastings 2 hours again, promptly get the surperficial cerium oxide catalyst that is covered with platinum, wherein the weight ratio of cerium oxide and platinum is 100: 1.5.
Get the cerium oxide catalyst that the 11.44g surface is covered with platinum, add the 1.56g aluminium glue.About solid content to 50%, grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length with 13g water adjustment said mixture
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes).Afterwards above-mentioned honeycomb carrier is heated to 120 ℃ of dryings 12 hours, is heated to 450 ℃ of roastings 2 hours again.Thus, area load has the cerium oxide carrier of platinum will be coated on the hole surface of honeycomb carrier, and the catalyst adhesion amount is about 2.4g/, and wherein platinum accounts for 1.32 weight % in the catalyst coating of honeycomb carrier surface.
Comparative example 4
The zirconia of 20g is added platinum solution (Pt (NO
2)
2(NH
3)
2Solution contains 0.3g platinum), keep 5 hours after being heated to 120 ℃ to remove solvent, be heated to 500 ℃ of roastings 2 hours again, promptly get the surperficial zirconia catalyst that is covered with platinum, wherein the weight ratio of zirconia and platinum is 100: 1.5.
Get the zirconia catalyst that the 6.25g surface is covered with platinum, mix, add the 2g aluminium glue again with the Zirconium oxide powder of 4.25g.About solid content to 49%, grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length with 13g water adjustment said mixture
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes).Afterwards above-mentioned honeycomb carrier is heated to 120 ℃ of dryings 12 hours, is heated to 450 ℃ of roastings 2 hours again.Thus; Area load has the Zirconia carrier of platinum and the zirconia filler that not load of surface has platinum; With dispersing and mixing and be coated on the hole surface of honeycomb carrier; The catalyst adhesion amount is about 2.4g/, and wherein platinum accounts for 0.75 weight % in the catalyst coating of honeycomb carrier surface.
Comparative example 5
The zirconia of 20g is added platinum solution (Pt (NO
2)
2(NH
3)
2Solution contains 0.3g platinum), keep 5 hours after being heated to 120 ℃ to remove solvent, be heated to 500 ℃ of roastings 2 hours again, promptly get the surperficial zirconia catalyst that is covered with platinum, wherein the weight ratio of zirconia and platinum is 100: 1.5.
Get the zirconia catalyst that the 11.44g surface is covered with platinum, add the 1.56g aluminium glue.About solid content to 50%, grind and form slurry, between adjustment slurry viscosity to 10～100cP, slurry is coated on the 400 holes/square inch (cells/in of 2 centimetres of diameters, 4 centimetres of length with 13g water adjustment said mixture
2) ceramic honeycomb shape carrier (cylinder that diameter is 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes).Afterwards above-mentioned honeycomb carrier is heated to 120 ℃ of dryings 12 hours, is heated to 450 ℃ of roastings 2 hours again.Thus, area load has the Zirconia carrier of platinum will be coated on the hole surface of honeycomb carrier, and the catalyst adhesion amount is about 2.4g/, and wherein platinum accounts for 1.32 weight % in the catalyst coating of honeycomb carrier surface.
In embodiment 10 and comparative example 3-5, the hole surface is coated with the honeycomb carrier (cylinder that diameter is about 2 centimetres, 4 centimetres of length, 12.6 cubic centimetres of catalyst cumulative volumes) of catalyst, places the crystal reaction tube of 2 centimetres of internal diameters.Water-gas is imported crystal reaction tube carry out water-gas shift reaction, and control the inlet temperature of water-gas with electrothermal furnace.The carbon dioxide of the hydrogen that consists of 46.0 moles of % of water-gas, the carbon monoxide of 6.1 moles of %, 9.2 moles of %, and the water of 38.7 moles of %.The flow velocity of water-gas is 102.4 liters of/hour (space flow speed GHSV=8150hr
-1).Fig. 7 be embodiment 10 with the catalyst of comparative example 3-5 in the time of 350 ℃, the carbon monoxide conversion ratio curve map after reaction a period of time.At the water-gas shift reaction initial stage, embodiment 10 is respectively 88% and 86% with the carbon monoxide conversion ratio of comparative example 3.After reaction 40 hours, the carbon monoxide conversion ratio of embodiment 10 maintains 88%, and the carbon monoxide conversion ratio of comparative example 3 reduces to 83%.Can know by comparative example 3, if catalyst zirconia free filler even have the platinum of higher dosage, is kept its high carbon monoxide conversion ratio after still can't using in the short time.
And the carbon monoxide conversion ratio of comparative example 4-5 is respectively 32% and 63%.After reaction 40 hours, the carbon monoxide conversion ratio of comparative example 4 reduces to 26%, and the carbon monoxide conversion ratio of comparative example 5 reduces to 47%.Can know that by comparative example 4-5 if catalyst non-oxidation cerium provides oxygen to help to carry out gas shift reaction, the carbon monoxide conversion ratio of comparative example 5 has only 63%.Even comparative example 4 adds the zirconium dioxide filler, still can't improve the carbon monoxide conversion ratio, catalyst contains the platinum amount to be reduced, and the carbon monoxide conversion ratio is lower.
Though the present invention with a plurality of preferred embodiments openly as above; Right its is not that any those skilled in the art are not breaking away from the spirit and scope of the present invention in order to qualification the present invention; Can change arbitrarily and retouching, so protection scope of the present invention is as the criterion with what claims defined.
Claims (8)
1. water-gas transfer catalyst comprises:
100 parts by weight of metal oxide carriers, the area load of this metal oxide carrier has platinum, and the weight ratio of metal oxide carrier and platinum is between 100: 0.1 to 100: 10; And
The zirconia filler of 120 to 10 weight portions, the not load of surface of this zirconia filler has platinum, and this zirconia filler and this metal oxide carrier dispersing and mixing,
Wherein this metal oxide carrier is made up of cerium oxide or zirconia cerium.
2. water-gas transfer catalyst according to claim 1 can comprise the dressing agent of 0.5 to 5 weight portion, and this dressing agent comprises sodium, potassium or above-mentioned combination.
3. gas shift reaction method comprises:
Water-gas is provided, and this water-gas comprises water and carbon monoxide, and the mol ratio of water and carbon monoxide is between 3: 1 to 10: 1; And
This water-gas is fed the described water-gas transfer catalyst of claim 1, make carbon monoxide and water reaction in this water-gas form carbon dioxide and hydrogen.
4. gas shift reaction method according to claim 3 wherein makes reaction temperature that carbon monoxide and the water reaction in this water-gas forms carbon dioxide and hydrogen between 200 ℃ to 500 ℃.
5. the preparation method of a water-gas transfer catalyst comprises:
Platinum is deposited on the surface of metal oxide carrier; And
Area load there are this metal oxide carrier and the zirconia filler dispersing and mixing of platinum, form the water-gas transfer catalyst,
Wherein this metal oxide carrier is cerium oxide or zirconia cerium; The weight ratio of this burning carrier and platinum is between 100: 0.1 to 100: 10, and the weight ratio of this metal oxide carrier and this zirconia filler is between 100: 120 to 100: 10.
6. the preparation method of water-gas transfer catalyst according to claim 5 also comprises gel added to grind behind this water-gas transfer catalyst forming slurry, this slurry is coated on the carrier surface again.
7. the preparation method of water-gas transfer catalyst according to claim 5 can comprise that sodium with 0.5 to 5 weight portion, potassium or above-mentioned combination modify the surface of this metal oxide carrier and this zirconia filler.
8. the preparation method of water-gas transfer catalyst according to claim 5, wherein the particle diameter of this metal oxide carrier is between 1 μ m to 10 μ m, and the particle diameter of this zirconia filler is between 1 μ m to 10 μ m.
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| TW100119172 | 2011-06-01 |
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| CN104716342A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Fuel cell catalyst slurry and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0870543A2 (en) * | 1997-04-09 | 1998-10-14 | Degussa Aktiengesellschaft | Oxygen storage material having high temperature stability based on cerium oxide and process for preparing such a material |
| EP1872851A2 (en) * | 2006-06-30 | 2008-01-02 | Daiichi Kigenso Kagaku Co., Ltd. | Cerium oxide-zirconium oxide-based mixed oxide and methode for producing thereof |
| US8298984B2 (en) * | 2007-12-28 | 2012-10-30 | Samsung Electronics Co., Ltd. | Non-pyrophoric catalyst for water-gas shift reaction and method of preparing the same |
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| US7824455B2 (en) * | 2003-07-10 | 2010-11-02 | General Motors Corporation | High activity water gas shift catalysts based on platinum group metals and cerium-containing oxides |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0870543A2 (en) * | 1997-04-09 | 1998-10-14 | Degussa Aktiengesellschaft | Oxygen storage material having high temperature stability based on cerium oxide and process for preparing such a material |
| EP1872851A2 (en) * | 2006-06-30 | 2008-01-02 | Daiichi Kigenso Kagaku Co., Ltd. | Cerium oxide-zirconium oxide-based mixed oxide and methode for producing thereof |
| US8298984B2 (en) * | 2007-12-28 | 2012-10-30 | Samsung Electronics Co., Ltd. | Non-pyrophoric catalyst for water-gas shift reaction and method of preparing the same |
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|---|---|---|---|---|
| CN104716342A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Fuel cell catalyst slurry and application thereof |
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