CN101244388A - Nano-gold loaded on manganese oxide/cerium oxide catalyst, producing method and application thereof - Google Patents
Nano-gold loaded on manganese oxide/cerium oxide catalyst, producing method and application thereof Download PDFInfo
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- CN101244388A CN101244388A CNA2007100792369A CN200710079236A CN101244388A CN 101244388 A CN101244388 A CN 101244388A CN A2007100792369 A CNA2007100792369 A CN A2007100792369A CN 200710079236 A CN200710079236 A CN 200710079236A CN 101244388 A CN101244388 A CN 101244388A
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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
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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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a manufacturing method of a nano-gold loaded on a manganese oxide/ceria catalyst, and a technological process that a carbon monoxide catalyzed by nano-gold loaded on a manganese oxide/ceria catalyst reacts with oxygen in hydrogen-rich environment to generate carbon dioxide; wherein, the manganese oxide and the ceria are mixed according to different element proportion; the loaded gold particle is less than 5 nanometers. The invention adopts manganese oxide/ceria catalyst with the presence of carbon monoxide, oxygen and hydrogen, the molecular ratio of the oxygen and the carbon monoxide is 0.5 to 2, a continuous packed-bed is used to selectively oxidize the carbon monoxide, so as to remove the carbon monoxide to less than 100ppm and the carbon monoxide in the hydrogen of the fuel cell, thereby preventing the carbon monoxide from poisoning the electrodes of the fuel cell.
Description
Technical field
The present invention is relevant nano-gold loaded in manganese oxide/cerium oxide catalyst, manufacture method, and carbon monoxide nano-gold loaded under the catalysis of manganese oxide/cerium oxide catalyst, be rich under the hydrogen environment, with the technological process of oxygen reaction generation carbon dioxide, to remove the carbon monoxide in the hydrogen stream.This technological process can be with removing the contained carbon monoxide of hydrogen in the fuel cell to being lower than 100ppm, and to avoid poisoning the electrode of fuel cell, the present invention also can be applicable to remove the carbon monoxide in the hydrogen groove, to improve purity.
Background technology
It is the research emphasis of industry that the exploitation of new forms of energy at present and effectively utilizing stores, and fuel battery energy is the high efficiency electric energy that is converted into of chemical energy, and can easily storage power, is just meeting this demand.In the kind of numerous fuel cells, roughly can be categorized as according to operating temperature, two kinds of high-temperature fuel cell (operating temperature is higher than 250 ℃) and low form fuel cells (operating temperature is lower than 250 ℃), but be subject to safe and big or small consideration, low form more common.But because the electrode in these fuel cells is very easy to be poisoned by carbon monoxide, for example: PAFCs can only tolerate the existence of 2% carbon monoxide, can only there be the carbon monoxide of several ppm especially in PEMs, so how to obtain clean hydrogen source, just becomes the most important problem of fuel cell.
Employed hydrogen in the fuel cell, can obtain from several method, wherein the recombining reaction of methane and aqueous vapor (steam reformer) is at present most economical hydrogen source, but shortcoming is the step that needs a succession of purifying hydrogen, the cracking of adopting other hydrocarbon is also arranged in addition, or use the ammonia cracking reaction that can not produce the COx accessory substance to generate hydrogen.In recombining reaction, the reorganization of methane and aqueous vapor must generate the accessory substance carbon monoxide, and carbon monoxide is the main cause that reduces electrode usefulness, so must just hydrogen can be imported among the PEM through a succession of reaction that removes carbon monoxide; In a series of reaction, (water gas shiftreactors WGSs) operates in 350～550 ℃, often uses the mixed catalyst of iron oxide/chromium oxide, carbonomonoxide concentration can be dropped to 3% at first to utilize the aqueous vapor of high temperature and carbon monoxide oxidation reaction; Next through the WGS reaction of low temperature, use cupric oxide/zinc oxide/alumina as catalyst carbonomonoxide concentration to be dropped to 0.5% again, its temperature is 200～300 ℃; (preferential oxidation PROX) reduces to carbon monoxide several ppm to enter selective oxidation reaction at last.
Selectivity carbon monoxide oxidation reaction is one of the carbon monoxide method that can effectively remove at present, the catalyst that is usually used in this type of reaction in early days, usually all have the carbon monoxide oxidability of height and the oxidability of hydrogen simultaneously, be widely used most no more than being the platinum catalyst; Though but the reactivity of platinum catalyst is good, make the amount of oxidation of hydrogen also and then increase also, so along with the rising carbon monoxide conversion ratio of temperature will descend, selection rate also with reduction.In addition, use metal solvents such as Ru, Rh, Pd and be applied in this reaction, its carbon monoxide conversion ratio is as the platinum catalyst, along with temperature raises and successively decreases.The situation that the carbon monoxide conversion ratio successively decreases is respectively Ru/Al in various catalyst
2O
3＞Rh/Al
2O
3＞Pt/Al
2O
3＞Pd/Al
2O
3(same under 0.5% tenor).In addition, external correlative study shows that golden catalyst is adapted at reacting below 100 ℃, the copper catalyst then is fit to 100～200 ℃, the platinum catalyst then is at 200 ℃ 100% carbon monoxide conversion ratio to be arranged, and the existence of carbon dioxide can reduce the conversion ratio of carbon monoxide in the discovery reacting gas, and especially golden catalyst is more obvious.Compared to the platinum catalyst, the gold catalyst not only can have very high activity being lower than under 100 ℃, be that other noble metal catalyst institute can not compare, and golden raw material is also cheap and price steadiness is many than platinum, its operating temperature also is fit to the low form fuel cell, need not heat separately.
The all application in the carbon monoxide oxidation of customs gold unit catalyst patent major part had before been arranged, under hydrogen environment, do not carry out selectivity carbon monoxide oxidation reaction, and there is no use manganese oxide-cerium oxide Combination oxide as carrier, reacting below 100 ℃.In open/bulletin patent, do not have and utilize the nano-gold loaded method that is applied in the oxidation of selectivity carbon monoxide in manganese oxide and cerium oxide catalyst as disclosed in the present invention.
Aspect foreign patent, be applied in the catalyst of selectivity carbon monoxide oxidation reaction, most alloy based on platinum, ruthenium, rhodium and these several classes, and the price that the present invention and these relatively back advantages are gold is comparatively cheap, and obviously can be lower than 100 ℃ of operations down, still have high activity in temperature.Below enumerate patent in recent years, U.S. Pat 6787118 (2004/09/07) disclose a kind of in hydrogen stream the method for selective removal carbon monoxide, the catalyst of use is to load on what coprecipitation made to contain Pt, Pd and Au catalyst on the mixed oxides such as cerium and other metal such as zirconium, iron, manganese, copper.U.S. Pat 6780386 (2004/08/24) discloses a kind of carbon monoxide oxidation catalyst and makes the method for hydrogen-containing gas, is catalyst with the Ru that loads on titanium oxide and the aluminium oxide, and the CO concentration in the hydrogen-rich gas is reduced to about 10ppm by 0.6%.U.S. Pat 6673742 (2004/01/06) discloses the method for making a kind of preferential oxidation catalyst and making the hydrogen-rich fuel air-flow with US6409939 (2002/01/25), 0.5～3%Ru/Al2O3 the catalyst that makes is the carbon monoxide (0.47%) in the rich hydrogen charging of energy selective oxidation under 70～130 ℃ of temperature, and the CO concentration in the discharging gas can be reduced to 50ppm.U.S. Pat 6559094 (2003/05/06) announcements one are used for the preparation method of the catalysis material of oxidizing selectively carbon monoxide, and the catalyst that the typical case uses is 5%Pt-0.3%Fe/Al
2O
3U.S. Pat 6531106 (2003/03/11) discloses a kind of method of selective removal carbon monoxide, noble metals such as Pt, Pd, Ru, Rh or Ir is loaded on be catalyst on the crystalline silicate, handles to contain 0.6%CO, 24%CO in embodiment
2, 20%H
2O, 0.6%O
2, 54.8%H
2Gas, majority can be reduced to CO concentration below the 50ppm under the different temperatures.Japan Patent JP2003-104703 (2003/04/09) discloses method and the fuel cell system that reduces carbon monoxide, prepares Ru-Pt/Al among the embodiment
2O
3Catalyst can be reduced to 4ppm by 6000ppm with the CO concentration in the hydrogeneous reorganization gas.U.S. Pat 6287529 (2001/09/11) discloses the apparatus and method of selective catalytic oxidation carbon monoxide, and this device is for multistage segmentation CO oxidation reactor, to load on Al
2O
3Or the Pt on the zeolite or Ru be catalyst, the CO in the hydrogen rich stream can be reduced to below the 40ppm.Japan Patent JP2000-169107 (2000/06/20) discloses and reduces the method that carbon monoxide is made hydrogen-containing gas, preparation loads on the alkali metal containing on titanium oxide and the alumina carrier or the Ru catalyst of alkaline-earth metal among the embodiment, the CO concentration in the hydrogen-containing gas can be reduced to below the 50ppm by 0.6% in 60～160 ℃ of scopes.Japan Patent JP05201702 (1993/08/10) discloses the method and the device of selective removal carbon monoxide, with Ru/Al
2O
3And Rh/Al
2O
3Be catalyst, in the CO concentration in the hydrogen-containing gas being reduced to below 0.01% below 120 ℃.The application patent of the at present relevant selectivity carbon monoxide oxidation of the U.S. as previously mentioned.The application of prior art does not have catalyst and the method for making of using the present invention to disclose.
Summary of the invention
The object of the present invention is to provide a kind of nano-gold loaded in manganese oxide/cerium oxide catalyst.
Another purpose of the present invention is to provide the manufacture method of above-mentioned catalyst.
For achieving the above object, provided by the invention nano-gold loaded in manganese oxide/cerium oxide catalyst, the catalyst that it is used for selectivity carbon monoxide oxidation under rich hydrogen environment comprises:
The carrier of one mixed oxidization manganese and cerium oxide; And
Load on the nanogold particle on this carrier surface.
Described catalyst, wherein the particle diameter of this nanogold particle is less than 5 nanometers.
Manufacturing provided by the invention is above-mentioned nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, and it comprises the following steps:
(a) with manganese nitrate solution with after ceria mixes, calcining between 300 ℃ to 500 ℃ is to form monoxide as carrier;
(b) gold-containing solution and this oxide are placed in the water to form a sediment of a nm of gold catalyst;
(c) control the pH-value of this gold-containing solution and continue stirring with an alkaline solution;
(d) with this sediment of distillation washing;
(e) dry this sediment; And
(f) this sediment after 120 ℃ to 200 ℃ calcining oven dry.
Described method, wherein, this carrier is equipped with the mixed oxide of manganese oxide and cerium oxide with the impregnation legal system, and its manganese cerium mixed proportion is 1/99 to 50/50.
Described method, wherein calcination time is 2 to 6 hours among this step a.
Described method, wherein among this step b, when precipitating this nm of gold catalyst, temperature maintenance is at 50 to 90 ℃.
Described method, wherein among this step c, when precipitating this nm of gold catalyst, this alkaline solution of control pH-value is an ammoniacal liquor.
Described method, wherein among this step c, when precipitating this nm of gold catalyst, pH-value is 5 to 9.
Described method, wherein among this step c, when precipitating this nm of gold catalyst, its lasting mixing time is 1 to 10 hour.
Described method, wherein in this steps d, the temperature of this distilled water is 60 ℃ to 70 ℃.
Described method, wherein among this step e, this bake out temperature is 80 ℃ to 90 ℃.
Described method, wherein among this step e, this drying time is 10 to 12 hours.
Described method, wherein among this step f, this sediment time after this calcining oven dry is 2 to 10 hours.
Provided by the inventionly nano-gold loadedly be used for removing the method that gas contains carbon monoxide in manganese oxide/cerium oxide catalyst, it comprises following steps:
Nano-gold loadedly containing under the reacting gas that hydrogen exists to contain in manganese oxide and cerium oxide catalyst, reaction between 20 ℃ to 200 ℃, wherein this reacting gas comprises oxygen, carbon monoxide, hydrogen and helium, and wherein oxygen/carbon monoxide mol ratio is 0.5 to 3.
Described method wherein contains nano-gold loadedly in the catalyst of manganese oxide and cerium oxide, and wherein golden percentage by weight is between 1% to 3%.
Described method, wherein the ratio of carbon monoxide and oxygen is 1 to 2 in this reacting gas.
Described method, wherein operating temperature is between 25 ℃ to 100 ℃.
In other words, the present invention can be applicable to remove the carbon monoxide in fuel of fuel cell to being lower than 100ppm, to avoid poisoning electrode; And can be used for removing the contained carbon monoxide of hydrogen in the fuel cell to being lower than 100ppm, to avoid poisoning the electrode of fuel cell.
Carbon monoxide provided by the invention, is being rich under the hydrogen environment under the catalysis of manganese oxide/cerium oxide catalyst nano-gold loaded, and the technological process with oxygen reaction generation carbon dioxide can be applicable to remove the carbon monoxide in the hydrogen groove, to improve the purity of hydrogen.
Manganese oxide of the present invention and cerium oxide can mix according to different element ratios, the gold grain unbounded size system of its carrying, and preferable particle diameter is for approximately less than 5 nanometers.
The present invention with nano-gold loaded in manganese oxide/cerium oxide catalyst in the presence of carbon monoxide, oxygen, hydrogen and helium, use the continous way packed bed reactor, in order to oxidizing selectively carbon monoxide.
Provided by the invention nano-gold loaded in manganese oxide/cerium oxide catalyst, it is used for the catalyst of selectivity carbon monoxide oxidation under rich hydrogen environment, and it comprises that the carrier of mixed oxidization manganese and cerium oxide loads on the nanogold particle on carrier surface.Nanogold particle particle size of the present invention is unrestricted, and preferable particle diameter is for approximately less than 5 nanometers.
Disclosed by the invention nano-gold loaded in the manufacture method of manganese oxide/cerium oxide catalyst, it mainly comprises the following step: (a) with manganese nitrate solution with after ceria mixes, calcining is to form monoxide as carrier between 300 ℃ to 500 ℃; (b) solution and this oxide that contains gold is placed in the water to form a sediment of a nm of gold catalyst; (c) control the pH-value of this gold-containing solution with an alkaline solution; (d) with this sediment of distillation washing; (e) dry this sediment; And (f) in 120 ℃ to 200 ℃ these sediments of calcining after drying.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, and wherein this carrier is the mixed oxide that is equipped with manganese oxide and cerium oxide with the impregnation legal system, and its manganese cerium mixed proportion is unrestricted, and preferable manganese cerium mixed proportion is 1/99 to 50/50.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, and wherein manganese nitrate solution is mixed the back calcination time with ceria unrestricted, and preferable calcination time is 2 to 6 hours.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, and wherein the temperature when precipitating this nm of gold catalyst is unrestricted, and preferable temperature maintenance is at 50 to 90 ℃.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, and wherein when precipitating this nm of gold catalyst, the alkaline solution of control pH-value is unrestricted, is preferably ammoniacal liquor.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, wherein when precipitating this nm of gold catalyst, controls its pH-value approximately less than 10, and preferable pH-value is 5 to 9.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, wherein must continue when precipitating this nm of gold catalyst to stir, and its mixing time is unrestricted, and preferable lasting mixing time is 1 to 10 hour.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, wherein is the distilled water flushing sediment to be lower than 80 ℃, and the temperature of preferable distilled water is 60 ℃ to 70 ℃.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, wherein dries its sediment and be being lower than under 95 ℃ the temperature to dry, and the bake out temperature that is preferably is 80 ℃ to 90 ℃.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, and it is unrestricted wherein to dry the sedimentary time, and preferable drying time is 10 to 12 hours.
The present invention makes nano-gold loaded in the method for manganese oxide/cerium oxide catalyst, and wherein calcining this, to dry the sedimentary time unrestricted, and preferable calcination time is 2 to 10 hours.
The present invention also discloses a kind of method that contains carbon monoxide in the gas of removing, its step comprises: nano-gold loadedly containing under the reacting gas that hydrogen exists in manganese oxide and cerium oxide catalyst to contain, reaction between 20 ℃ to 200 ℃, make carbon monoxide be oxidized to carbon dioxide, wherein reacting gas has oxygen, carbon monoxide, hydrogen and helium, and wherein oxygen/carbon monoxide mol ratio is 0.5 to 3.
The present invention is nano-gold loadedly containing under the reacting gas that hydrogen exists in manganese oxide and cerium oxide catalyst to contain, and removes in the gas and contains in the method for carbon monoxide, and wherein Jin percentage by weight is preferably percentage by weight in 1% to 3% without limits.
The present invention is nano-gold loadedly containing under the reacting gas that hydrogen exists in manganese oxide and cerium oxide catalyst to contain, remove in the gas and contain in the method for carbon monoxide, wherein the ratio of carbon monoxide in the reactor body and oxygen is 0.5 to 3, and preferable ratio is 1 to 2.
The present invention is nano-gold loadedly containing under the reacting gas that hydrogen exists in manganese oxide and cerium oxide catalyst to contain, and removes in the gas and contains in the method for carbon monoxide, and its operating temperature is 20 ℃ to 200 ℃, and preferable operating temperature is 25 ℃ to 100 ℃.
The specific embodiment
Embodiment 1
Be equipped with manganese cerium mixed oxide 8 grams with the impregnation legal system, as the carrier of load gold, its method for making following steps 1 to 2, again gold is utilized the method for deposition sedimentation, load on the carrier oxide that above-mentioned preparation finishes, its detailed step following steps 3 to 8 can be finished w%Au/MnO
2/ CeO
2(Mn/Ti=x/10-x), wherein w is 1, and x is 1 catalyst;
1, weighs manganese nitrate (Mn (NO
3)
2.4H
2O) 1.12 grams (molecular weight 251 is available from Aldrich company) dissolve it with 3 ml distilled waters, to prepare manganese/cerium than the oxide carrier that is 1/9;
2, weigh 6.88 gram cerias (molecular weight 172 is available from Degussa company), the aqueous solution of step 1 is slowly splashed into wherein and stirs, 400 ℃ of calcinings are 4 hours in air, promptly generate grey manganese dioxide-cerium oxide powder, and take out and grind;
3, powder 2.475 gram that weighs step 2 is put into 150 ml distilled waters, stirs with magnetite, and is heated to 65 ℃, and keep;
4, weigh tetra chlorauric acid 0.048 gram (available from Strem Chemicals company), it is dissolved in 50 ml distilled waters, wherein gold accounts for 0.025 gram;
5, with 0.1M ammoniacal liquor the pH value of solution of step 3 is controlled at 8 ± 0.2, again the speed of tetra chlorauric acid solution with 10 milliliters of per minutes is splashed in this solution, and control base number simultaneously, 65 ℃ of temperature maintenance 8 ± 0.2;
6, mixed two hours with magnetite after titration is finished, keep pH-value 8.5 ± 0.2,65 ℃ of temperature react completely it;
7, the sediment that obtains is filtered, and wash repeatedly, up to removing chlorion fully, again in 80 ℃ of oven dry 12 hours with 70 ℃ distilled water;
8, the catalyst after will drying burnt 4 hours in air at 180 ℃, promptly generated darkviolet 1%Au/MnO
2-CeO
2Powder, manganese/cerium mole ratio is 1/9;
Embodiment 2
With embodiment 1, only manganese/cerium atom the ratio with step 1 changes 5/5 into, weighs manganese nitrate (Mn (NO
3)
2.4H
2O) 4.75 grams (molecular weight 251 is available from Aldrich company), the ceria of step 2 takes by weighing 3.25 grams (molecular weight 80 is available from Degussa company).
Embodiment 3
With embodiment 1, only the calcination temperature of step 8 is changed into 120 ℃ and in air, burnt 4 hours.
Embodiment 4
With embodiment 2, only the calcination temperature of step 8 is changed into 120 ℃ and in air, burnt 4 hours.
Embodiment 5
With embodiment 4, only change feed gas carbon monoxide/oxygen/hydrogen/helium volume ratio into 1/1.5/49/48.5.
The catalyst of the various embodiments described above is got the 1wt.%Au/MnO of about 0.10 gram
2/ TiO
2Place in the vertical type packed bed reactor, carry out the reaction of oxidizing selectively carbon monoxide under rich hydrogen environment, experimentize with fixed bed reactors, pipe has melting quartz sand in the middle of the inner and outer diameter, supporting the catalyst of reaction, but can breathe freely, bottom sealed glass tube in reaction tube in addition is to place the thermocouple thermometer of measuring the catalyst surface temperature;
It is that the mist of 1.33/2.66/64.01/32 is 50 milliliters of per minutes with mass flowrate controller control total flow that feed gas is contained carbon monoxide/oxygen/hydrogen/helium volume ratio, at room temperature feed in the reactor, the reacting gas product is analyzed with gas chromatograph (Chinese chromatography model 9800), uses 3.5 meters Molecular sieve 5A stainless-steel tubing pillars;
Temperature of reactor is by cylindric galvanic couple Heating Furnace Control, its inside heating furnace is covered with the heat-preserving equipment of 4 centimeters glass fibres, temperature of reactor is raise by room temperature with per minute 2 degree, and respectively 25,50,80 degree Celsius temperature balances 10 minutes, and in balance sample analysis such as following table 1 in the time of 5 minutes.
The reaction result of above-mentioned all embodiment of test shows below table 1; Wherein carbon monoxide conversion ratio and selection rate are defined as follows:
Carbon monoxide conversion ratio=(import carbonomonoxide concentration-outlet carbonomonoxide concentration) ÷ import carbonomonoxide concentration;
Carbon monoxide selection rate=carbon monoxide oxidation consumption amount of oxygen ÷ (carbon monoxide oxygen consumed tolerance+oxidation of hydrogen oxygen consumed tolerance).
All embodiment confirm that the carbon monoxide conversion ratio reaches 100%, and the carbon monoxide of outlet all is lower than 50ppm.Confirm that by these results catalyst of the present invention can effectively remove the carbon monoxide in the gas, further can be applicable to remove the carbon monoxide in fuel of fuel cell, to avoid poisoning electrode; And can be used for removing the contained carbon monoxide of hydrogen in the fuel cell to being lower than 100ppm, to avoid poisoning the electrode of fuel cell, also can be applicable to remove the carbon monoxide in the hydrogen groove, to improve purity.
Reaction result in the every implementation method of table 1
The foregoing description is only given an example for convenience of description, and the interest field that the present invention advocated should be as the criterion so that claim is described certainly, but not only limits to the foregoing description.
Claims (17)
- One kind nano-gold loaded in manganese oxide/cerium oxide catalyst, the catalyst that it is used for selectivity carbon monoxide oxidation under rich hydrogen environment comprises:The carrier of one mixed oxidization manganese and cerium oxide; AndLoad on the nanogold particle on this carrier surface.
- 2. catalyst as claimed in claim 1, wherein, the particle diameter of this nanogold particle is less than 5 nanometers.
- One kind nano-gold loaded in the manufacture method of manganese oxide/cerium oxide catalyst, it comprises the following steps:(a) with manganese nitrate solution with after ceria mixes, calcining between 300 ℃ to 500 ℃ is to form monoxide as carrier;(b) gold-containing solution and this oxide are placed in the water to form a sediment of a nm of gold catalyst;(c) control the pH-value of this gold-containing solution and continue stirring with an alkaline solution;(d) with this sediment of distillation washing;(e) dry this sediment; And(f) this sediment after 120 ℃ to 200 ℃ calcining oven dry.
- 4. method as claimed in claim 3, wherein, this carrier is equipped with the mixed oxide of manganese oxide and cerium oxide with the impregnation legal system, and its manganese cerium mixed proportion is 1/99 to 50/50.
- 5. method as claimed in claim 3, wherein, calcination time is 2 to 6 hours among this step a.
- 6. method as claimed in claim 3, wherein, among this step b, when precipitating this nm of gold catalyst, temperature maintenance is at 50 to 90 ℃.
- 7. method as claimed in claim 3, wherein, among this step c, when precipitating this nm of gold catalyst, this alkaline solution of control pH-value is an ammoniacal liquor.
- 8. method as claimed in claim 3, wherein, among this step c, when precipitating this nm of gold catalyst, pH-value is 5 to 9.
- 9. method as claimed in claim 3, wherein, among this step c, when precipitating this nm of gold catalyst, its lasting mixing time is 1 to 10 hour.
- 10. method as claimed in claim 3, wherein, in this steps d, the temperature of this distilled water is 60 ℃ to 70 ℃.
- 11. method as claimed in claim 3, wherein, among this step e, this bake out temperature is 80 ℃ to 90 ℃.
- 12. method as claimed in claim 3, wherein, among this step e, this drying time is 10 to 12 hours.
- 13. method as claimed in claim 3, wherein, among this step f, this sediment time after this calcining oven dry is 2 to 10 hours.
- 14. remove the method that contains carbon monoxide in the gas for one kind, it comprises following steps:Nano-gold loadedly containing under the reacting gas that hydrogen exists to contain in manganese oxide and cerium oxide catalyst, reaction between 20 ℃ to 200 ℃, wherein this reacting gas comprises oxygen, carbon monoxide, hydrogen and helium, and wherein oxygen/carbon monoxide mol ratio is 0.5 to 3.
- 15. method as claimed in claim 14 wherein, contains nano-gold loadedly in the catalyst of manganese oxide and cerium oxide, wherein golden percentage by weight is between 1% to 3%.
- 16. method as claimed in claim 14, wherein, the ratio of carbon monoxide and oxygen is 1 to 2 in this reacting gas.
- 17. method as claimed in claim 14, wherein, operating temperature is between 25 ℃ to 100 ℃.
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|---|---|---|---|
| CNA2007100792369A CN101244388A (en) | 2007-02-13 | 2007-02-13 | Nano-gold loaded on manganese oxide/cerium oxide catalyst, producing method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211025A (en) * | 2011-04-07 | 2011-10-12 | 大连圣迈新材料有限公司 | Salt mist-resistant moisture-resistant catalyst for removing carbon monoxide at low temperature |
| CN106563464A (en) * | 2016-12-23 | 2017-04-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Cerium-based catalyst for benzene low-temperature catalytic removal, and preparation and application thereof |
-
2007
- 2007-02-13 CN CNA2007100792369A patent/CN101244388A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211025A (en) * | 2011-04-07 | 2011-10-12 | 大连圣迈新材料有限公司 | Salt mist-resistant moisture-resistant catalyst for removing carbon monoxide at low temperature |
| CN102211025B (en) * | 2011-04-07 | 2013-04-10 | 大连圣迈新材料有限公司 | Salt mist-resistant moisture-resistant catalyst for removing carbon monoxide at low temperature |
| CN106563464A (en) * | 2016-12-23 | 2017-04-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Cerium-based catalyst for benzene low-temperature catalytic removal, and preparation and application thereof |
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