CN1868586A - Imbedding type ruthenium system transformation reaction catalyst and its preparing method - Google Patents
Imbedding type ruthenium system transformation reaction catalyst and its preparing method Download PDFInfo
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- CN1868586A CN1868586A CNA200610085942XA CN200610085942A CN1868586A CN 1868586 A CN1868586 A CN 1868586A CN A200610085942X A CNA200610085942X A CN A200610085942XA CN 200610085942 A CN200610085942 A CN 200610085942A CN 1868586 A CN1868586 A CN 1868586A
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
An embedded Ru-system catalyst with high catalytic activity and long service life for the CO conversion reaction is prepared through preparing the catalytic nano-RuO2 sol from Mg-Al spinel, RuO2 and water-soluble high-molecular compound by sol method, mixing it with the solution of water-soluble high-molecular compound, magnesium nitrate and aluminum nitrate, regulating pH value to obtain gel, adding alkali metal or alkali-earth metal or RE metal, drying and calcining.
Description
Technical field
The present invention relates to a kind of CO catalyst for water-gas shift reaction and preparation method thereof, being specifically related to a kind of ruthenium is embedding bury type CO catalyst for water-gas shift reaction and preparation method thereof.This catalyst is applicable to the occasion of all CO transformationreations, and the semiwater gas shift conversion step as synthesis ammonia system is converted into CO with the CO in the semiwater gas in the presence of steam
2And H
2, play and remove CO, improve hydrogen yield.Because characteristics such as it is little that this imbedding type ruthenium system transformation reaction catalyst has proportion, and light-off temperature is low, being particularly suitable for alcohol is the fuel cell of raw material, is used for removing that pure reformation hydrogen production process produces that battery electrode is had the CO of poisoning effect.
Background technology
Iron-the chromium of conversion process that is used for the semiwater gas CO of synthesis ammonia system is the existing so far nearly 90 years history of high temperature conversion catalyst.This catalyst has characteristics such as mechanical strength is big, catalytic activity is high, good heat resistance, long service life, thereby uses so far always.But the chromium in this catalyst has been confirmed as carcinogen, and except that Catalyst Production person's human body is produced the harm, spent catalyst is also very serious to the pollution of environment.
Conventional iron-chromium is that transformation catalyst mainly adopts the preparation of precipitation mixing method.The salting liquid that specifically is iron, chromium and other material that will prepare makes catalyst through operations such as washing, separation, oven dry, batch mixing, moulding then with ammoniacal liquor or soda ash solution precipitation.This catalyst does not have carrier, all is made of active component.Catalyst bulk density is usually at 1.5～1.6t/m
3Between, chromium oxide content is between 10～15wt%.The present iron of China-chrome catalysts year consumption year consumes chromium and is about 600t about 6000t, and its harm to environment is not allowed to ignore.
In addition, because energy crisis and to the demand of environmental protection, adopting fuel cell is that power is one of approach that addresses these problems.A lot of fuel cells are raw material with alcohol, obtain the used H of fuel cell reaction after reforming
2But the CO that produces during pure reformation hydrogen production has poisoning effect to the battery platinum electrode, utilizes transformationreation to convert CO to H
2And CO
2, can effectively reduce the concentration of CO, improve H simultaneously
2Content.This shows, development catalytic activity height, can the transformation catalyst that light-off temperature is low be successfully develop one of key of this types of fuel cells.
Summary of the invention
The invention provides a kind of imbedding type ruthenium system transformation reaction catalyst and preparation method thereof, its objective is and will develop a kind of environment-friendly type, catalytic activity height, CO catalyst for water-gas shift reaction that light-off temperature is low, is high temperature conversion catalyst to replace conventional iron-chromium.
For achieving the above object, the technical scheme that catalyst of the present invention adopts is: a kind of imbedding type ruthenium system transformation reaction catalyst, mainly to form by effective active composition and carrier, and the component and the weight percentage of its effective active composition and carrier are respectively:
(1), effective active composition
Ruthenic oxide, molecular formula are RuO
20.5～5.0%;
Metal oxide, general formula are MO 1.0～5.0%;
Potassium oxide, molecular formula are K
2O 0.25～10.0%;
Wherein, metal oxide is selected one of following three kinds of compositions or wherein both mixtures or three's mixture:
Lanthanum sesquioxide, molecular formula are La
2O
3
Samarium sesquioxide, molecular formula are Sm
2O
3
Ceria, molecular formula are CeO
2
(2), carrier
Magnesium aluminate spinel, molecular formula are MgAl
2O
4Surplus.
Related content in the technique scheme is explained as follows:
1, in the such scheme, in order further to improve effect, the content of described each effective active components is respectively:
Ruthenic oxide 1.7～2.0%;
Metal oxide 1.5～2.0%;
Potassium oxide 2.0～4.5%.
2, in the such scheme, described effective active components also comprises:
Calcium oxide, molecular formula are CaO 0.5～2.0%.
3, in the described metal oxide of such scheme, both and three's weight mixing ratio can be arranged in pairs or groups arbitrarily, but both weight mixing ratio the bests are 10～5: 1～0.1, and weight mixing ratio the best of three is La
2O
3: Sm
2O
3: CeO
2=10～5: 1～0.1: 1～0.5.
For achieving the above object, the technical scheme that method for preparing catalyst of the present invention adopts is: a kind of preparation method of imbedding type ruthenium system transformation reaction catalyst:
(1), RuO
2The preparation of colloidal sol
With ruthenium trichloride, molecular formula RuCI
3Be raw material, water and ethanol are solvent, in the presence of water-soluble high-molecular compound, with alkaline aqueous solution regulator solution pH value to 7～10, are heated to 40～60 ℃ and stir 2～5 hours, obtain nanometer RuO
2Colloidal sol; Repeatedly dialyse through deionized water with dialysis again until RuO
2There is not Cl in the colloidal sol
-Till ion detects;
Wherein:
Water-soluble high-molecular compound is selected a kind of in three kinds of the daiamid type branch molecules of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), 3-8, and the mol ratio of ruthenium trichloride and water-soluble high-molecular compound (by monomer) is controlled at 1: between the 50-1;
Alkaline aqueous solution adopts NH
4HCO
3Or ammoniacal liquor (5～8%);
(2), Preparation of catalysts
Magnesium nitrate, aluminum nitrate are mixed with the aqueous solution by 1: 2 mol ratio, add described water-soluble high-molecular compound, the mol ratio of magnesium nitrate and aluminum nitrate and water-soluble high-molecular compound (by monomer) is controlled at 10: between the 100-1, after between 10～25% ammoniacal liquor regulator solution pH value to 6～7, by the proportioning adding nanometer RuO of above-mentioned catalyst effective active composition
2Colloidal sol and metal oxide and potassium oxide effective active composition solution stir, and add 20～25% concentrated ammonia liquors again system pH is transferred to 10～11, obtain containing the catalytic active component gel, and reduction vaporization removes and desolvates then; Then will be except that the oven dry of the gel after desolvating, 400～600 ℃ of following roastings 4～8 hours, after post processing gets goods.
Related content in the technique scheme is explained as follows:
1, such scheme is at RuO
2In the preparation of colloidal sol, the volume ratio of aqueous solvent and etoh solvent=0.5～1.5.
2, such scheme is at RuO
2In the preparation of colloidal sol, the mol ratio that changes ruthenium trichloride and water-soluble high-molecular compound can be regulated nanometer RuO
2The particle size of particle, the ratio of ruthenium trichloride and water-soluble high-molecular compound is high more, and the particle diameter of nano particle is big more, otherwise more little.RuO
2Grain diameter is about 5nm.
3, such scheme is in Preparation of catalysts, removes gel after desolvating 110～120 ℃ of oven dry.
4, such scheme is in Preparation of catalysts, and the main finger pressure sheet of described post processing is pulverized, and gets subsequent treatment such as 15-20 order particle.
Operation principle of the present invention is: be carrier with the magnesium aluminate spinel, with ruthenic oxide RuO
2Deng metal oxide is the active component presoma, by selecting suitable water-soluble high-molecular compound, with it is stabilizing agent, prepared metal Ru oxide nano-particles with catalytic activity with sol method, then with the nanometer ruthenium oxide particles with after magnesium nitrate that is added with the suitable quantity of water solubleness high molecular compound and aluminum nitrate solution mix, regulator solution pH value, form gel, add an amount of alkali metal or alkaline-earth metal and thulium, obtain imbedding type ruthenium system transformation reaction catalyst after drying, the roasting.This catalyst for water-gas shift reaction has not only been abandoned the crome metal element that human body and environment is had damaging effect, and, because active component is embedded in the inside of catalyst carrier in the catalyst, active component communicates with the external world by the trickle duct that macromolecule decomposition process forms on carrier, thereby can play the conversion catalytic action, but be in the catalytic active component of inside, duct, but can not blown away, thereby have very high catalytic activity and service life by reaction gas flow.
The present invention has following characteristics:
1, adopts the RuO of above-mentioned sol method preparation
2Grain diameter and can obtain the RuO of different-grain diameter by changing preparation condition about 5nm
2Particle.
2, the interpolation of other auxiliary agent of catalyst (referring to other effective active composition except that ruthenic oxide) has changed traditional siccative mixed method, adopts liquid phase to disperse new technology, and it is more even that auxiliary agent is distributed.
3, add water-soluble high-molecular compound, can in roasting process, form the passage that the catalyst activity component contacts with external environment condition, make the active component that is embedded in carrier inside also can play catalytic action.
4, adopt the carrier of sol-gel process preparation to have very high specific area.
Because above characteristics, the prepared transformation catalyst of the present invention has very high catalytic activity, particularly compares with traditional iron-chromium catalyst for water-gas shift reaction, and light-off temperature can be reduced to 150 ℃.
The present invention compared with prior art has following advantage:
1, the present invention's employing is a carrier to the stable magnesium aluminate spinel of steam at high temperature, and traditional transformation catalyst does not have carrier, and the active component consumption descends greatly by contrast, has particularly reduced the consumption of high price active component.
2, the present invention is a kind of chromium-free environment-friendly type transformation catalyst, therefore, for the protection environment important social meaning is arranged.
3, adopt the RuO of sol method preparation
2RuO in the colloidal sol
2Nano particle diameter only has several nanometers, has very high catalytic activity for transformationreation.Embedding bury type transformation catalyst light-off temperature is about 150 ℃, and the serviceability temperature interval is about 150-550 ℃, and traditional transformation catalyst serviceability temperature interval is 300-500 ℃.
4, the embedding bury type transformation catalyst is embedded in carrier inside with various effective active compositions, and active component communicates with the external world by the carrier inside pore, has reduced active component by the possibility that reaction gas flow purges, and has improved the service life of catalyst.
Description of drawings
Accompanying drawing 1 is the RuO of the present invention's preparation
2Transmission electron microscope picture, as can be seen from the figure RuO
2Particle diameter about about 5nm.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one:
Pipette the RuCl that 3.2mL concentration is 0.0922mol/L
3The aqueous solution (2.97 * 10
-4Mol), (V: V=1: 1) dilution obtains brown solution ([RuCl with the 40mL ethanol/water
3]=7.43 * 10
-3Mol/L), water-bath is heated to 60 ℃.According to mol ratio PVP: Ru=15: 1 (PVP is by monomer) adds protective agent PVP 0.495g.The NH that dropwise adds 1mol/L under the magnetic agitation
4HCO
3The aqueous solution, regulator solution pH8 continues to stir 2h, obtains stablizing the black ruthenic oxide colloidal sol of depositing.Ruthenic oxide colloidal sol is repeatedly dialysed until no Cl by bag filter with deionized water
-Till ion detected, Cl was removed
-The ruthenic oxide colloidal sol of ion.The ruthenic oxide nano particle diameter is 5nm.The ratio that changes Ru and PVP can be regulated nanometer titanium dioxide ruthenium grain diameter size.
The mixed aqueous solution of magnesium nitrate, aluminum nitrate and PVA (contains 5.42g Mg (NO
3)
26H
2O, 15.85gAl (NO
3)
39H
2O and 0.3g PVA) regulate pH=5～6 with ammoniacal liquor (10～25%).Ruthenic oxide colloidal sol and metal oxide, potassium oxide and calcium oxide compounding agent solution are added mixed solution by formula rate under strong agitation,, continue to stir 3h with ammoniacal liquor (25%) regulator solution pH to 10.Reduction vaporization on Rotary Evaporators removes and desolvates, and obtains the gelatinous mass of grey black.120 ℃ of oven dry place muffle furnace at 600 ℃ of following roasting 4h, and compressing tablet is pulverized, and gets 15-20 order particle, gets embedding bury type RuO
2/ MgAl
2O
4Catalyst.
Work as K
2O content 3.2%, La
2O
3When content 3.7% and CaO content 1.3%, air speed 2000h
-1, liquid to steam ratio is reaction condition following 350 ℃ and 400 ℃ of temperature of 1.0, the conversion ratio of CO reaches 88% and 95% respectively.
Embodiment two:
Pipette the RuCl that 3.2mL concentration is 0.0922mol/L
3The aqueous solution (2.97 * 10
-4Mol), (V: V=1: 1) dilution obtains brown solution ([RuCl with the 40mL ethanol/water
3]=7.43 * 10
-3Mol/L), water-bath is heated to 60 ℃.Change the PVP among the embodiment one into PVA, according to mol ratio PVA: Ru=30: 1 (PVP is by monomer) adds protective agent PVA 0.392g.The NH that dropwise adds 1mol/L under the magnetic agitation
4HCO
3The aqueous solution, regulator solution pH8 continues to stir 2h, obtains stablizing the black ruthenic oxide colloidal sol of depositing.Ruthenic oxide colloidal sol is repeatedly dialysed until no Cl by bag filter with deionized water
-Till ion detected, Cl was removed
-The ruthenic oxide colloidal sol of ion.The ruthenic oxide nano particle diameter is 5nm.
The mixed aqueous solution of magnesium nitrate, aluminum nitrate and PVA (contains 5.42g Mg (NO
3)
26H
2O, 15.85gAl (NO
3)
39H
2O and 0.3g PVA) regulate pH=5～6 with ammoniacal liquor (10～25%).Ruthenic oxide colloidal sol and metal oxide, potassium oxide and calcium oxide compounding agent solution are added mixed solution by formula rate under strong agitation,, continue to stir 3h with ammoniacal liquor (25%) regulator solution pH to 10.Reduction vaporization on Rotary Evaporators removes and desolvates, and obtains the gelatinous mass of grey black.120 ℃ of oven dry place muffle furnace at 600 ℃ of following roasting 4h, and compressing tablet is pulverized, and gets 15-20 order particle, gets embedding bury type RuO
2/ MgAl
2O
4Catalyst.
Work as K
2O content 5.0%, La
2O
3Content 3.0%, Sm
2O
3When content 0.5% and CaO content 1.0%, air speed 2000h
-1, liquid to steam ratio is reaction condition following 350 ℃ and 400 ℃ of temperature of 1.0, the conversion ratio of CO is respectively 85% and 92%.
Embodiment three:
Pipette the RuCl that 3.2mL concentration is 0.0922mol/L
3The aqueous solution (2.97 * 10
-4Mol), (V: V=1: 1) dilution obtains brown solution ([RuCl with the 40mL ethanol/water
3]=7.43 * 10
-3Mol/L), water-bath is heated to 60 ℃.With the PVP among the embodiment one change into 3.5 generation daiamid type branch molecule, press metal: branch molecule=40 (mole than) mixed ruthenic oxide colloidal sol.The ruthenic oxide nano particle diameter is about 5nm.Ruthenic oxide colloidal sol is repeatedly dialysed until no Cl by bag filter with deionized water
-Till ion detected, Cl was removed
-The ruthenic oxide colloidal sol of ion.
The mixed aqueous solution of magnesium nitrate, aluminum nitrate and PVA (contains 5.42g Mg (NO
3)
26H
2O, 15.85gAl (NO
3)
39H
2O and 0.3g PVA) regulate pH=5～6 with ammoniacal liquor (10～25%).Ruthenic oxide colloidal sol and metal oxide, potassium oxide and calcium oxide compounding agent solution are added mixed solution by formula rate under strong agitation, transfer pH value of solution to 10, continue to stir 3h with concentrated ammonia liquor (25%).Reduction vaporization on Rotary Evaporators removes and desolvates, and obtains the gelatinous mass of grey black.120 ℃ of oven dry place muffle furnace at 600 ℃ of following roasting 4h, and compressing tablet is pulverized, and gets 15-20 order particle, gets embedding bury type RuO
2/ MgAl
2O
4Catalyst.
Work as K
2O content 3.0%, La
2O
3During content 5.0%, air speed 2000h
-1, liquid to steam ratio 1.0 reaction condition following 350 ℃ and 400 ℃ of temperature, the conversion ratio of CO reaches 90% and 98% respectively.
Embodiment four:
Pipette the RuCl that 3.2mL concentration is 0.0922mol/L
3The aqueous solution (2.97 * 10
-4Mol), (V: V=1: 1) dilution obtains brown solution ([RuCl with the 40mL ethanol/water
3]=7.43 * 10
-3Mol/L), water-bath is heated to 60 ℃.With among the embodiment three 3.5 generation daiamid type branch molecule change into 5.5 generation daiamid type branch molecule, press metal: branch molecule=60 (mole than) mixed ruthenic oxide colloidal sol.Ruthenic oxide colloidal sol is repeatedly dialysed until no Cl by bag filter with deionized water
-Till ion detected, Cl was removed
-The ruthenic oxide colloidal sol of ion.
The mixed aqueous solution of magnesium nitrate, aluminum nitrate and PVA (contains 5.42g Mg (NO
3)
26H
2O, 15.85gAl (NO
3)
39H
2O and 0.3g PVA) regulate pH=5～6 with ammoniacal liquor (10～25%).Ruthenic oxide colloidal sol and metal oxide, potassium oxide and calcium oxide compounding agent solution are added mixed solution by formula rate under strong agitation, transfer pH value of solution to 10, continue to stir 3h with concentrated ammonia liquor (25%).Reduction vaporization on Rotary Evaporators removes and desolvates, and obtains the gelatinous mass of grey black.120 ℃ of oven dry place muffle furnace at 600 ℃ of following roasting 4h, and compressing tablet is pulverized, and gets 15-20 order particle, gets embedding bury type RuO
2/ MgAl
2O
4Catalyst.
Work as K
2O content 3.0%, La
2O
3Content 3.0%, Sm
2O
3Content 0.75%, CeO
2During content 0.25%, air speed 2000h
-1, liquid to steam ratio 1.0 reaction condition following 350 ℃ and 400 ℃ of temperature, the conversion ratio of CO reaches 82% and 94% respectively.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit essence is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (8)
1, a kind of imbedding type ruthenium system transformation reaction catalyst is characterized in that: mainly be made up of effective active composition and carrier, the component and the weight percentage of its effective active composition and carrier are respectively:
(1), effective active composition
Ruthenic oxide, molecular formula are RuO
20.5～5.0%;
Metal oxide, general formula are MO 1.0～5.0%;
Potassium oxide, molecular formula are K
2O 0.25～10.0%;
Wherein, metal oxide select one of following three kinds of compositions or lanthana and other both one of or three's mixture:
Lanthanum sesquioxide, molecular formula are La
2O
3
Samarium sesquioxide, molecular formula are Sm
2O
3
Ceria, molecular formula are CeO
2
(2), carrier
Magnesium aluminate spinel, molecular formula are MgAI
2O
4Surplus.
2, catalyst according to claim 1 is characterized in that: the content of described each effective active components is respectively:
Ruthenic oxide 1.7～2.0%;
Metal oxide 1.5～2.0%;
Potassium oxide 2.0～4.5%.
3, catalyst according to claim 1 and 2 is characterized in that: described effective active components also comprises:
Calcium oxide, molecular formula are CaO 0.5～2.0%.
4, catalyst according to claim 1 and 2 is characterized in that: three's weight mixing ratio is La in the described metal oxide
2O
3: Sm
2O
3: CeO
2=10～5: 1～0.1 :～1: 0.5.
5, a kind of preparation method of imbedding type ruthenium system transformation reaction catalyst is characterized in that:
(1), RuO
2The preparation of colloidal sol
With ruthenium trichloride, molecular formula RuCI
3Be raw material, water and ethanol are solvent, in the presence of water-soluble high-molecular compound, with alkaline aqueous solution regulator solution pH value to 7～10, are heated to 40～60 ℃ and stir 2～5 hours, obtain nanometer RuO
2Colloidal sol; Repeatedly dialyse through deionized water with dialysis again until RuO
2There is not Cl in the colloidal sol
-Till ion detects;
Wherein:
Water-soluble high-molecular compound is selected a kind of in three kinds of the daiamid type branch molecules of polyvinylpyrrolidone, polyvinyl alcohol, 3-8, and the mol ratio of ruthenium trichloride and water-soluble high-molecular compound is controlled at 1: between the 50-1;
Alkaline aqueous solution adopts NH
4HCO
3Or ammoniacal liquor;
(2), Preparation of catalysts
Magnesium nitrate, aluminum nitrate are mixed with the aqueous solution by 1: 2 mol ratio, add described water-soluble high-molecular compound, the mol ratio of magnesium nitrate and aluminum nitrate and water-soluble high-molecular compound is controlled at 10: between the 100-1, after between 10～25% ammoniacal liquor regulator solution pH value to 6～7, add nanometer RuO by the proportioning in the claim 1
2Colloidal sol and metal oxide and potassium oxide effective active composition solution stir, and add 20～25% concentrated ammonia liquors again system pH is transferred to 10～11, obtain containing the catalytic active component gel, and reduction vaporization removes and desolvates then; Then will be except that the oven dry of the gel after desolvating, 400～600 ℃ of following roastings 4～8 hours, after post processing gets goods.
6, preparation method according to claim 5 is characterized in that: described RuO
2In the preparation of colloidal sol, the volume ratio of aqueous solvent and etoh solvent=0.5～1.5.
7, preparation method according to claim 5 is characterized in that: described RuO
2In the preparation of colloidal sol, the mol ratio that changes ruthenium trichloride and water-soluble high-molecular compound can be regulated nanometer RuO
2The particle size of particle, the ratio of ruthenium trichloride and water-soluble high-molecular compound is high more, and the particle diameter of nano particle is big more, otherwise more little.
8, preparation method according to claim 5 is characterized in that: in the described Preparation of catalysts, remove gel after desolvating 110～120 ℃ of oven dry.
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|---|---|---|---|
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|---|---|---|---|
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ID=37442447
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100415A (en) * | 2012-12-03 | 2013-05-15 | 北京化工大学 | Catalyst with active component nano particles embedded in molecular sieve to crystallize, method and application |
| CN111477880A (en) * | 2020-03-05 | 2020-07-31 | 浙江工业大学 | CeOx/RuO2(iii) MC and CeOx/RuO2Preparation and application of composite nanosheet material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8600445D0 (en) * | 1986-01-09 | 1986-02-12 | British Petroleum Co Plc | Syngas conversion catalyst |
| JPH0576776A (en) * | 1991-09-19 | 1993-03-30 | Toyota Motor Corp | Catalyst for purification of exhaust gas |
| US20040043900A1 (en) * | 2002-08-12 | 2004-03-04 | Combs Glenn A. | Heterogeneous gaseous chemical reactor catalyst |
| CN1233555C (en) * | 2003-05-13 | 2005-12-28 | 中国科学院生态环境研究中心 | Catalyst for selective oxidation of CO under hydrogen-enriched condition |
-
2006
- 2006-06-08 CN CNB200610085942XA patent/CN100431694C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100415A (en) * | 2012-12-03 | 2013-05-15 | 北京化工大学 | Catalyst with active component nano particles embedded in molecular sieve to crystallize, method and application |
| CN103100415B (en) * | 2012-12-03 | 2015-06-10 | 北京化工大学 | Catalyst with active component nano particles embedded in molecular sieve to crystallize, method and application |
| CN111477880A (en) * | 2020-03-05 | 2020-07-31 | 浙江工业大学 | CeOx/RuO2(iii) MC and CeOx/RuO2Preparation and application of composite nanosheet material |
| CN111477880B (en) * | 2020-03-05 | 2021-07-27 | 浙江工业大学 | CeOx/RuO2(iii) MC and CeOx/RuO2Preparation and application of composite nanosheet material |
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