CN1216793C - Catalyst for h2o transfer reaction and method of converting CO and H2O to CO2 and H2 - Google Patents
Catalyst for h2o transfer reaction and method of converting CO and H2O to CO2 and H2 Download PDFInfo
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- CN1216793C CN1216793C CN2003101001060A CN200310100106A CN1216793C CN 1216793 C CN1216793 C CN 1216793C CN 2003101001060 A CN2003101001060 A CN 2003101001060A CN 200310100106 A CN200310100106 A CN 200310100106A CN 1216793 C CN1216793 C CN 1216793C
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title abstract description 22
- 238000006276 transfer reaction Methods 0.000 title abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011787 zinc oxide Substances 0.000 claims abstract description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 10
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005751 Copper oxide Substances 0.000 claims abstract description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 7
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 28
- 235000011089 carbon dioxide Nutrition 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000906 Bronze Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000010974 bronze Substances 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 229910000423 chromium oxide Inorganic materials 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000843 powder Substances 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- 230000009466 transformation Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 206010013786 Dry skin Diseases 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention provides a catalyst used for converting carbon monoxide and water into hydrogen and carbon dioxide (water transfer reaction). The catalyst of the present invention contains a metallic oxide carrier, 0.1 to 10% of platinum and 0 to 5% of rhenium (measured by the weight of the metallic oxide carrier), wherein the platinum and the rhenium are loaded on the metallic oxide carrier; the metallic oxide carrier contains copper oxide, alanate, and one kind of metallic oxide selected from zinc oxide, chromium oxide and magnesium oxide. The present invention also discloses a method for reducing the carbon monoxide content of rich hydrogen recombination gas.
Description
Technical field
The invention relates to provides a kind of carbon monoxide and water is changed into the method (water shift reaction) of hydrogen and carbonic acid gas, especially relevant wherein employed catalyzer.
Background technology
Macromolecule membrane fuel cell (polymer electrolyte membrane fuel cell, PEMFC) very likely be used for fixation type family power generation system and electromobile, and the required fuel of supply PEMFC system is the hydrogen-rich gas (H that CO concentration is lower than 20ppm in future
2Concentration＞35%).The hydrogen-enriched recombinant gas that general hydrocarbon polymer produces via recombining reaction, its CO concentration is about 8～15%, must be via water transfer reaction (Water gas shift, be called for short WGS) as far as possible the CO concentration of hydrogen-enriched recombinant gas is reduced to below 1%, via selective oxidation the CO concentration of recombinant gas is reduced to below the 20ppm more afterwards.Tradition WGS catalyzer is Cu-ZnO/Al
2O
3, the shortcoming of its maximum be range of reaction temperature narrow, need the activation, can not ingress of air and thermo-labile.Because these shortcomings make traditional C u-ZnO/Al
2O
3The fuel reformer system that is applied to family's fixation type fuel cell generation can cause the very big inconvenience of operating aspect.
Therefore, each catalyst research unit or company there's no one who doesn't or isn't actively look on the bright side of things to send out and operate WGS catalysts easily, develop as the United States Patent (USP) (US 6,238,640) of Idemitsu Kosan Cu-MO-Al
2O
3The European patent (EP 1,161,991) of (M is Zn, Cr, Mg), PANASONIC motor company develops and Pt-M/ZrO
2The European patent (EP 1,184,445) of (M is Re, Sc, Pr), Toyota develops and Pt-M/TiO
2(M is Al, Si, P, S, V), Nextech then develop Pt/CeO
2-ZrO
2Catalyzer, they all declare these catalyzer all be not afraid of contact with oxygen and catalysis WGS reactive behavior very high.But in fact, the catalyzer of above-mentioned patent research and development respectively has its shortcoming, catalyst activity as Idemitsu Kosan research and development is not high, and the catalyzer bullion content height of Nextech, PANASONIC motor and Toyota research and development (the Pt concentration 3～12wt%) of patent working example, the synthetic cost of catalyzer is higher.
Summary of the invention
A purpose of the present invention be to provide a kind of catalyzer its can be used for carbon monoxide and water are changed into the method (water shift reaction) of hydrogen and carbonic acid gas, this catalyzer has high conversion and advantage of low manufacturing cost.
Another object of the present invention is to provide a kind of method that carbon monoxide and water is changed into hydrogen and carbonic acid gas.
Another purpose of the present invention is to provide a kind of method with reduction of the carbon monoxide content in the hydrogen-enriched recombinant gas and hydrogen richness increase.
A kind of catalyzer that carbon monoxide and water is changed into hydrogen and carbonic acid gas that is applicable in order to realize that the foregoing invention purpose is finished according to content of the present invention comprises a metal oxide carrier, and this metal oxide carrier comprises copper oxide; Aluminum oxide; And be selected from zinc oxide, one metal oxide of chromated oxide and magnesium oxide, it is characterized in that comprising 0.1～10% platinum (Pt) that is carried on this metal oxide carrier, 0.5 preferable～5%Pt, and 0～5% rhenium (Re), being preferably 0.1～3%Re, is benchmark with the weight of this metal oxide carrier.
The present invention discloses simultaneously and a kind of carbon monoxide and water is changed into the method for hydrogen and carbonic acid gas, comprises a rich hydrogen charging that will contain carbon monoxide and water vapor and contacts at 200～500 ℃ with the invention described above catalyzer.
Preferable, the metal oxide carrier in the catalyzer of the present invention comprises copper oxide; Aluminum oxide; And zinc oxide, wherein this metal oxide carrier comprises 25～55% bronze medals, is benchmark with the weight of this metal oxide carrier.
Preferable, the inventive method is employed should the hydrogen-enriched recombinant gas of richness hydrogen charging for forming by the hydrocarbon of recombinating.
Preferable, the inventive method is employed should the charging of richness hydrogen to contain the above hydrogen of 30 moles of %, and H
2O is 2～10 to the mol ratio of CO.
Description of drawings
Fig. 1 is at H
2The O/CO mol ratio is the mapping of the CO transformation efficiency of 3 o'clock catalyzer to the reaction gas inlet temperature, and wherein the embodiment of the invention 1 catalyzer is represented with bullet, and comparative example 1 catalyzer is with the open circles representative of punctuating, and comparative example 2 catalyzer are represented with solid diamond point.
Fig. 2 is at H
2The O/CO mol ratio is the mapping of the CO transformation efficiency of 6 o'clock catalyzer to the reaction gas inlet temperature, wherein the embodiment of the invention 1 catalyzer is represented with open diamonds point, embodiment 2 catalyzer are represented with bullet, embodiment 3 catalyzer are with the open circles representative of punctuating, and comparative example 3 catalyzer are represented with the triangle form point.
Fig. 3 is in H
2The O/CO mol ratio is the mapping of the CO transformation efficiency of 4 o'clock catalyzer to the reaction gas inlet temperature, wherein the catalyzer of the embodiment of the invention 2 is represented with bullet before unaged, (400 ℃ of aging backs, 20 hours) with the open circles representative of punctuating, represent with black triangle point before comparison three catalyzer are unaged, aging back (400 ℃, 20 hours) is represented with hollow triangle point.
Fig. 4 is at H
2The O/CO mol ratio is the mapping of the CO transformation efficiency of 6 o'clock catalyzer to the reaction gas inlet temperature, and wherein the embodiment of the invention 2 catalyzer are represented with bullet, and comparative example 4 catalyzer are with the representative of triangle form point, and comparative example 5 catalyzer are represented with square dot.
Embodiment
The present invention discloses a kind of WGS catalyst for reaction, and it both can avoid traditional C u-ZnO/Al
2O
3Shortcoming, and catalyst WGS reactive activity is better than or can be suitable with aforementioned PANASONIC motor, Nextech and the developer of Toyota institute.The precious metal concentration of catalyzer of the present invention must reduce in addition, to reduce the synthetic cost of catalyzer.The comparative result of a preferred embodiment of the embodiment of case and this case invention before following table is listed:
| Toyota EP?1184445 | The motor EP of Panasonic 1161991 | Idemitsu?Kosan US?6238640 | The present invention | |
| Catalyzer is formed | Pt-M/TiO 2M:Al, Si, P, S and V | Pt-M/ZrO 2M：Re，Sc， Pr | Cu-M/Al 2O 3M：Zn，Cr，Mg | Pt-Re/Cu-Zn-Al |
| Your gold content | 3-12 weight % | 3 weight % | --- | 1-4 weight % |
| Reactive | High | High | In | High |
| Can contact oxygen | Can | Can | Can | Can |
| Synthetic cost | High | High | Low | In |
The present invention can further be understood by following examples, and this embodiment but not is used to limit the scope of the invention as illustrative purposes only.
Embodiment 1
Take by weighing 34.2g Cu (NO
3)
2.3H
2O, 92.7g Al (NO
3)
3.9H
2O and 30.6g Zn (NO
3)
2.6H
2O is dissolved in the deionized water of 1500ml, and under stirring at room, splashing into 28% ammoniacal liquor to pH value of solution value is 7.5.After at room temperature stirring 2 hours, filter out the jelly and the washing that are formed in the solution,, promptly get Cu/Al through 12 hours, 500 ℃ roastings of 120 ℃ of dryings 5 hours
2O
3-ZnO, and its weight proportion of composing is Cu: Al
2O
3: ZnO=30: 42: 28.
With the Pt (NH that contain 0.2 g Pt of just wet impregnation method with a proper volume
3)
2(NO
2)
2Solution adds the Cu/Al of 20 grams
2O
3-ZnO powder mixes, and through 12 hours, 400 ℃ roastings of 120 ℃ of dryings 2 hours, promptly gets Pt/Cu/Al
2O
3-ZnO catalyst, wherein the concentration of platinum is 1 weight %.
Get the Pt/Cu/Al of preparation
2O
3-ZnO powder mixes with alumina gel (alumina sol), the weight ratio of mixture is 9 to 1, and add the suitable water yield and adjust solid content, through adjusting the viscosity of slurry after grinding again, then slurry is coated in the 400 holes/square inch (cells/in of 2 centimeters of diameters, 2 centimeters of length therebetween
2) ceramic honeycomb shape carrier, make a monolithic honeycomb catalyzer (monolith honeycomb catalyst) through 120 ℃ of dryings (12 hours), 450 ℃ of roastings (2 hours) afterwards.The catalyzer adhesion amount of each monolithic honeycomb catalyzer is about 1～2 gram.
Comparative example 1
The step that repeats embodiment 1 prepares a monolithic honeycomb catalyzer, but not contain the Cu/Al of Pt among the embodiment 1
2O
3-ZnO powder replaces this Pt/Cu/Al
2O
3-ZnO powder carries out this coating step.
Comparative example 2
Take by weighing 114g Cu (NO
3)
2.3H
2O, 102g Al (NO
3)
3.9H
2O and 309g Zn (NO
3)
2.6H
2O is dissolved in the deionized water of 3000ml, and under stirring at room, splashing into 28% ammoniacal liquor to pH value of solution value is 7.5.After at room temperature stirring 2 hours, filter out the throw out and the washing that are formed in the solution,, promptly get Cu/Al through 12 hours, 500 ℃ roastings of 120 ℃ of dryings 5 hours
2O
3-ZnO catalyst, and its weight proportion of composing is Cu: Al
2O
3: ZnO=23.4: 10.8: 65.8.Then with this Cu/Al
2O
3-ZnO powder repeats the lining step of embodiment 1, makes a monolithic honeycomb catalyzer.
Utilize conventional fixed bed reactive system detecting catalyst catalysis WGS reactive activity, get above-mentioned honeycomb catalyzer and insert in the crystal reaction tube of 2.2 centimeters of internal diameters, utilize the temperature in of electrothermal oven control reactant gases, reactant gases is: H
250.2%, CO9.4%, CO
212.2%, H
2O28.2%, H
2The O/CO mol ratio is 3, and reactant gases space flow speed (GHSV) is 7000 hours
-1Fig. 1 is to use the transformation efficiency of catalyzer catalysis WGS reaction under differing temps of embodiment 1 and comparative example 1 and 2.The experimental data of Fig. 1 shows that fully adding platinum can significantly promote Cu/Al
2O
3-ZnO catalyst improves the CO transformation efficiency to the catalytic capability of WGS reaction.
Embodiment 2:
Take by weighing 151.02g Cu (NO
3)
2.3H
2O, 214.31g Al (NO
3)
3.9H
2O and 71.0gZn (NO
3)
2.6H
2O is dissolved in the deionized water of 3000ml, and under stirring at room, splashing into 28% ammoniacal liquor to pH value of solution value is 7.5.After at room temperature stirring 2 hours, filter out the throw out and the washing that are formed in the solution, through 12 hours, 500 ℃ roastings of 120 ℃ of dryings 5 hours, promptly getting part by weight was Cu: Al
2O
3: ZnO=45: 33: 22 Cu/Al
2O
3-ZnO.With Cu/Al
2O
3After-ZnO pulverizes, with the Pt (NH that contain 0.2 gram Pt of just wet impregnation method with proper volume
3)
2(NO
2)
2The NH of solution and 0.2 gram Re
4ReO
4Solution dilution becomes to add the Cu/Al of 20 grams
2O
3Mix in-the ZnO powder,, promptly get Pt-Re/Cu/Al through 12 hours, 400 ℃ roastings of 120 ℃ of dryings 2 hours
2O
3-ZnO catalyst, wherein the concentration of platinum is that the concentration of 1 weight %, rhenium is 1 weight %.Then with this Pt-Re/Cu/Al
2O
3-ZnO powder repeats the lining step among the embodiment 1 and makes a monolithic honeycomb catalyzer.The catalyzer adhesion amount of each monolithic honeycomb catalyzer is about 2 grams.
Embodiment 3
The step that repeats embodiment 1 prepares a monolithic honeycomb catalyzer, but Pt-Re/Cu/Al
2O
3-ZnO powder contains 3 weight %Pt and 1 weight % rhenium.The catalyzer adhesion amount of each monolithic honeycomb catalyzer is about 2 grams.
Comparative example 3
Take by weighing 151.02g Cu (NO
3)
2.3H
2O, 214.31g Al (NO
3)
3.9H
2O and 71.0gZn (NO
3)
2.6H
2O is dissolved in the deionized water of 3000ml, and under stirring at room, splashing into 28% ammoniacal liquor to pH value of solution value is 7.5.After at room temperature stirring 2 hours, filter out the throw out and the washing that are formed in the solution, through 12 hours, 500 ℃ roastings of 120 ℃ of dryings 5 hours, promptly getting part by weight was Cu: Al
2O
3: ZnO=45: 33: 22 Cu/Al
2O
3-ZnO.Then with this Cu/Al
2O
3-ZnO powder repeats the lining step of embodiment 1, makes a monolithic honeycomb catalyzer.
Utilize conventional fixed bed reactive system detecting catalyst catalysis WGS reactive activity equally, get above-mentioned honeycomb catalyzer and insert in the crystal reaction tube of 2.2 centimeters of internal diameters, utilize the temperature in of electrothermal oven control reactant gases, reactant gases is: H
233.8%, CO5.4%, CO
210.2%, H
2O32.4%, H
2The O/CO mol ratio is 6, and reactant gases space flow speed (GHSV) is 6000 hours
-1Fig. 2 is the transformation efficiency of catalyzer catalysis WGS reaction under differing temps of embodiment 1, embodiment 2, embodiment 3 and comparative example 3.The experimental data of Fig. 2 shows that fully adding rhenium can promote Pt/Cu/Al
2O
3-ZnO catalyst improves the CO transformation efficiency to the catalytic capability of WGS reaction, and Pt-Re/Cu/Al
2O
3-ZnO catalyst catalysis WGS reaction surmounts Cu/Al more significantly for the transformation efficiency of CO
2O
3-ZnO.
Utilize the aging rear catalyst catalysis WGS reactive activity of conventional fixed bed reactive system test equally.With the monolithic honeycomb catalyzer of embodiment 2 and comparative example 3 in 400 ℃ aging 20 hours, insert again in the crystal reaction tube of 2.2 centimeters of internal diameters and carry out the WGS reaction, utilize the temperature in of electrothermal oven control reactant gases, reactant gases is: H
247.3%, CO8.1%, CO
212.2%, H
2O32.4%, H
2The O/CO mol ratio is 4, and reactant gases space flow speed (GHSV) is 6000 hours
-1Fig. 3 is under above-mentioned reaction conditions, without the transformation efficiency of the embodiment 2 after aging and aging with monolithic honeycomb catalyzer catalysis WGS reaction under differing temps of comparative example 3.Fig. 3 experimental data shows Pt-Re/Cu/Al
2O
3-ZnO catalyst still can be maintained at a top grade in 400 ℃ of transformation efficiencys for CO after aging 20 hours, and obviously than Cu/Al
2O
3-ZnO height shows that adding Pt-Re can effectively promote Cu/Al
2O
3-ZnO is for the catalysis characteristics of WGS reaction.
Comparative example 4
Taking by weighing an amount of Zirconium oxide powder and add 3 weight %Pt and 1 weight %Re with first wet impregnation method, is benchmark with the weight of Zirconium oxide powder, and through 120 ℃ of dryings 12 hours, and 400 ℃ of roastings made Pt-Re/ZrO after 2 hours
2Powder.With Pt-Re/ZrO
2Powder mixes with the alumina gel cakingagent, its weight ratio of mixture is 9 to 1, and add suitable water yield adjustment solid content, through adjusting the viscosity of slurry after grinding again, then slurry is coated in the 400 holes/square inch (cells/in of 2 centimeters of diameters, 2 centimeters of length
2) ceramic honeycomb shape carrier, through 120 ℃ of dryings 12 hours, 400 ℃ of roastings made a monolithic honeycomb catalyzer in 2 hours.The Pt-Re/ZrO of each monolithic honeycomb catalyzer
2Adhesion amount is about 2 grams.
Comparative example 5
Take by weighing the Pt/CeO that buys from Nextech company in right amount
2-ZrO
2Powder (contains 2 weight %Pt, with CeO
2-ZrO
2The weight of powder is benchmark) mix with alumina gel (alumina sol) cakingagent of 10 weight %, and the suitable water yield of adding is adjusted solid content, through adjusting the viscosity of slurry after grinding again, then slurry is coated in the 400 holes/square inch (cells/in of 2 centimeters of diameters, 2 centimeters of length
2) ceramic honeycomb shape carrier, through 120 ℃ of dryings 12 hours, 400 ℃ of roastings made a monolithic honeycomb catalyzer in 2 hours.The Pt/CeO of each monolithic honeycomb catalyzer
2-ZrO
2Adhesion amount is about 2 grams.
Equally, utilize conventional fixed bed reactive system detecting catalyst catalysis WGS reactive activity, get the foregoing description 2 and insert in the crystal reaction tube of 2.2 centimeters of internal diameters with the honeycomb catalyzer of comparative example 4 and 5, utilize the temperature in of electrothermal oven control reactant gases, reactant gases is: H
233.8%, CO5.4%, CO
210.2%, N
218.2%, H
2O32.4%, H
2The O/CO mol ratio is 6, and reactant gases space flow speed (GHSV) is 6000 hours
-1Fig. 4 is embodiment 2 and the transformation efficiency of comparative example 4 with the catalysis WGS reaction under differing temps of comparative example 5 catalyzer.Fig. 4 experimental data shows Pt-Re/Cu/Al
2O
3-ZnO catalyst is suitable with 5 catalyzer for peak rate of conversion and the comparative example 4 of CO, but Pt-Re/Cu/Al
2O
3-ZnO catalyst temperature of reaction is lower and its bullion content is lower than comparative example 4 and 5 catalyzer, and this experimental data fully manifests Pt-Re/Cu/Al
2O
3The superiority of-ZnO catalysis WGS reaction.
Claims (10)
1. one kind is applicable to the catalyzer that carbon monoxide and water is changed into hydrogen and carbonic acid gas, comprises a metal oxide carrier, and this metal oxide carrier comprises copper oxide; Aluminum oxide; And being selected from zinc oxide, a metal oxide of chromated oxide and magnesium oxide is characterized in that comprising 0.1～10% platinum and 0.1～5% rhenium that is carried on this metal oxide carrier, is benchmark with the weight of this metal oxide carrier.
2. catalyzer as claimed in claim 1, wherein this metal oxide carrier comprises copper oxide; Aluminum oxide; And zinc oxide, wherein this metal oxide carrier comprises 25～55% bronze medals, is benchmark with the weight of this metal oxide carrier.
3. catalyzer as claimed in claim 1 or 2, wherein this catalyzer comprises 0.5～5% platinum, is benchmark with the weight of this metal oxide carrier.
4. catalyzer as claimed in claim 3, wherein this catalyzer comprises 0.1～3% rhenium, is benchmark with the weight of this metal oxide carrier.
5. one kind changes into the method for hydrogen and carbonic acid gas with carbon monoxide and water, comprises a rich hydrogen charging that will contain carbon monoxide and water vapor and contacts in 200～500 ℃ with catalyzer;
Described catalyzer is to comprise a metal oxide carrier, and this metal oxide carrier comprises copper oxide; Aluminum oxide; And being selected from zinc oxide, a metal oxide of chromated oxide and magnesium oxide also comprises 0.1～10% platinum and 0.1～5% rhenium that is carried on this metal oxide carrier, is benchmark with the weight of this metal oxide carrier.
6. method as claimed in claim 5 wherein should the hydrogen-enriched recombinant gas of richness hydrogen charging for forming by the hydrocarbon of recombinating.
7. as claim 5 or 6 described methods, wherein should the charging of richness hydrogen contain the above hydrogen of 30 moles of %, and H
2O is 2～10 to the mol ratio of CO.
8. method as claimed in claim 5, wherein the metal oxide carrier of this catalyzer comprises copper oxide; Aluminum oxide; And zinc oxide, wherein this metal oxide carrier comprises 25～55% bronze medals, is benchmark with the weight of this metal oxide carrier.
9. as claim 5 or 8 described methods, wherein this catalyzer comprises 0.5～5% platinum, is benchmark with the weight of this metal oxide carrier.
10. method as claimed in claim 9, wherein this catalyzer comprises 0.1～3% rhenium, is benchmark with the weight of this metal oxide carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2003101001060A CN1216793C (en) | 2002-12-02 | 2003-10-08 | Catalyst for h2o transfer reaction and method of converting CO and H2O to CO2 and H2 |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02153818.2 | 2002-12-02 | ||
| CN2002153818.2.2 | 2002-12-02 | ||
| CN02153818 | 2002-12-02 | ||
| CN2003101001060A CN1216793C (en) | 2002-12-02 | 2003-10-08 | Catalyst for h2o transfer reaction and method of converting CO and H2O to CO2 and H2 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1504402A CN1504402A (en) | 2004-06-16 |
| CN1216793C true CN1216793C (en) | 2005-08-31 |
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ID=34276098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2003101001060A Expired - Lifetime CN1216793C (en) | 2002-12-02 | 2003-10-08 | Catalyst for h2o transfer reaction and method of converting CO and H2O to CO2 and H2 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1216793C (en) |
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2003
- 2003-10-08 CN CN2003101001060A patent/CN1216793C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1504402A (en) | 2004-06-16 |
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