CN101284239A - Nano gold loaded manganese oxide/ferric oxide catalyst and preparation method and application - Google Patents
Nano gold loaded manganese oxide/ferric oxide catalyst and preparation method and application Download PDFInfo
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- CN101284239A CN101284239A CNA2007100958928A CN200710095892A CN101284239A CN 101284239 A CN101284239 A CN 101284239A CN A2007100958928 A CNA2007100958928 A CN A2007100958928A CN 200710095892 A CN200710095892 A CN 200710095892A CN 101284239 A CN101284239 A CN 101284239A
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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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to a method for manufacturing a double-oxide gold accelerant which is a manganese oxide/ferric oxide accelerant carrying nano-gold, and a technology that a carbon monoxide reacts with oxygen to generate carbon dioxide under the catalytic action of the manganese oxide/ferric oxide accelerant carrying nano-gold in the environment rich with hydrogen, wherein, manganese oxide and ferric oxide are mixed according to different element proportions, and the carried gold particles is less than 5nm. By using a continuous-type packed bed reactor, the manufacturing method utilizes the manganese oxide/ferric oxide accelerant containing gold to selectively oxidize the carbon monoxide when the carbon monoxide, oxygen and hydrogen exist, wherein, the molecular ratio between the oxygen and the carbon monoxide ranges from 0.5 to 2, thereby reducing the concentration of the carbon monoxide in hydrogen stream until the concentration is less than 100ppm, and preventing the carbon monoxide from spoiling the electrode of a fuel cell.
Description
Technical field
The invention relates to nano-gold loaded in manganese oxide/iron oxide catalyst, and this is nano-gold loaded in manganese oxide/its manufacture method of iron oxide catalyst, and carbon monoxide nano-gold loaded under the catalysis of manganese oxide/iron oxide catalyst, be rich under the hydrogen environment, with the technology of oxygen reaction generation carbon dioxide, to remove the carbon monoxide in the hydrogen stream.
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 (phosphoric acid fuel cells) can only tolerate the existence of 2% carbon monoxide, can only there be the carbon monoxide of several ppm especially in PEMs (proton exchange membrane fuel cells), so how to obtain clean hydrogen source, just become 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 catalyst mixture 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 of temperature, the carbon monoxide conversion ratio 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/iron oxide Combination oxide as carrier, reacting below 100 ℃.In open/bulletin patent, do not utilize the nano-gold loaded method that is applied in the oxidation of selectivity carbon monoxide in manganese oxide and iron oxide catalyst just like described in the 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, the 0.5～3%Ru/Al that makes with US6409939 (2002/01/25)
2O
3Catalyst 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 known technology 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/iron oxide catalyst.
Another purpose of the present invention is providing the manufacture method of above-mentioned catalyst, and it can be applicable to remove the contained carbon monoxide of hydrogen in the fuel cell to being lower than 100ppm, to avoid poisoning the electrode of fuel cell.
Another object of the present invention is to provide a kind of carbon monoxide nano-gold loaded under the catalysis of manganese oxide/iron oxide catalyst, be rich under the hydrogen environment, technology with oxygen reaction generation carbon dioxide can be applicable to remove the carbon monoxide in the hydrogen groove, to improve the purity of hydrogen.
For achieving the above object, the catalyst of carbon monoxide oxidation provided by the invention is used for the catalyst of selectivity carbon monoxide oxidation under rich hydrogen environment, comprising: the carrier of mixed oxidization manganese and iron oxide; And load on the nanogold particle on this carrier surface.
The catalyst of described carbon monoxide oxidation, wherein, the particle diameter of this nanogold particle is less than 5 nanometers.
Provided by the invention nano-gold loaded in the manufacture method of carrier catalyst, it comprises the following steps:
(a) with manganese nitrate solution with after iron oxide 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) to wash this sediment;
(e) dry this sediment;
(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 iron oxide with the impregnation legal system, and its ferromanganese mixed proportion is 1/9 to 3/7.
Described method, wherein, calcination time is 2 to 6 hours in the step (a).
Described method, wherein, in the step (b), when precipitating this nm of gold catalyst, temperature maintenance is at 50 to 90 ℃.
Described method, wherein, in the step (c), when precipitating this nm of gold catalyst, this alkaline solution of control pH-value is an ammoniacal liquor.
Described method, wherein, in the step (c), when precipitating this nm of gold catalyst, pH-value is 8 to 9.
Described method, wherein, in the step (c), when precipitating this nm of gold catalyst, its lasting mixing time is 1 to 10 hour.
Described method, wherein, in the step (d), the temperature of this water is 60 ℃ to 70 ℃.
Described method, wherein, in the step (e), this bake out temperature is 100 ℃ to 110 ℃.
Described method, wherein, in the step (e), this drying time is 10 to 12 hours.
Described method, wherein, in the step (f), this sediment time after this calcining oven dry is 2 to 10 hours.
Contain the method for carbon monoxide in the removal gas provided by the invention, it comprises following steps:
Nano-gold loadedly containing under the reacting gas that hydrogen exists to contain in manganese oxide and iron 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 4.
Described method wherein, contains nano-gold loadedly in the catalyst of manganese oxide and iron oxide, and wherein golden percentage by weight is between 1% to 3%.
Described method, wherein, the ratio of carbon monoxide and oxygen is 2 to 3 in this reacting gas.
Described method, wherein, operating temperature is between 25 ℃ to 100 ℃.
In other words, manganese oxide of the present invention and iron 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 be with contain gold loaded in manganese oxide/iron 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.
The present invention is a kind of catalyst of carbon monoxide oxidation, and 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 iron 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.
The present invention mainly discloses a kind of nano-gold loaded in the manufacture method of carrier catalyst, and it mainly comprises the following step: (a) with manganese nitrate solution with after iron oxide 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) to wash this sediment; (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 carrier catalyst, and wherein this carrier is the mixed oxide that is equipped with manganese oxide and iron oxide with the impregnation legal system, and its ferromanganese mixed proportion is unrestricted, and preferable ferromanganese mixed proportion is 1/9 to 3/7.
The present invention makes nano-gold loaded in the method for carrier catalyst, and wherein manganese nitrate solution is mixed the back calcination time with iron oxide unrestricted, and preferable calcination time is 2 to 6 hours.
The present invention makes nano-gold loaded in the method for carrier 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 carrier 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 carrier catalyst, wherein when precipitating this nm of gold catalyst, controls its pH-value approximately less than 10, and preferable pH-value is 8 to 9.
The present invention makes nano-gold loaded in the method for carrier 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 carrier catalyst, wherein is the water flushing sediment to be lower than 80 ℃, and the temperature of preferable water is 60 ℃ to 70 ℃.
The present invention makes nano-gold loaded in the method for carrier catalyst, and wherein drying its sediment is to dry under 110 ℃ temperature, and the bake out temperature that is preferably is 100 ℃ to 110 ℃.
The present invention makes nano-gold loaded in the method for carrier 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 carrier 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 iron 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 4.
The present invention is nano-gold loadedly containing under the reacting gas that hydrogen exists in manganese oxide and iron 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 iron oxide catalyst to contain, remove in the gas and contain in the method for carbon monoxide, wherein the ratio of carbon monoxide in the reacting gas and oxygen is 0.5 to 4, and preferable ratio is 2 to 3.
The present invention is nano-gold loadedly containing under the reacting gas that hydrogen exists in manganese oxide and iron 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 ferromanganese mixed oxide 10 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/ Fe
2O
3(Mn/Fe=10-x/x), wherein w is 1, and x is 9 catalyst;
1, preparation manganese/iron weighs manganese nitrate (Mn (NO than the oxide carrier that is 1/9
3)
24H
2O) 2.58 grams (molecular weight 251 is available from Aldrich company) dissolve it with 2 ml distilled waters;
2, weigh 7.42 gram iron oxide (molecular weight 160), the aqueous solution of step 1 is slowly splashed into wherein and stirs, 180 ℃ of calcinings are 4 hours in air, promptly generate dark brown manganese dioxide/croci, and take out and grind;
3, powder 4.95 gram that weighs step 2 is put into 150 ml distilled waters, and stir with magnetite, and be heated to 60 ℃, and keep;
4, weigh tetra chlorauric acid 0.096 gram (available from Strem Chemicals company), it is dissolved in 50 ml distilled waters, wherein gold accounts for 0.05 gram;
5, with pure ammoniacal liquor the pH value of solution of step 3 is controlled at 9 ± 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, 60 ℃ of temperature maintenance 9 ± 0.2;
6, mixed two hours with magnetite after titration is finished, keep pH-value 9 ± 0.2,60 ℃ of temperature react completely it;
7, the sediment that obtains is filtered, and wash repeatedly, up to removing chlorion fully, again in 110 ℃ of oven dry 12 hours with 70 ℃ distilled water;
8, the catalyst after will drying burnt 4 hours in air at 180 ℃, promptly generated dark brown 1%Au/MnO
2-Fe
2O
3Powder, manganese/iron mole ratio is 1/9.
Embodiment 2:
With embodiment 1, only manganese/iron atom the ratio with step 1 changes 3/7 into, weighs manganese nitrate (Mn (NO
3)
24H
2O) 5.735 grams (molecular weight 251 is available from Aldrich company), the iron oxide of step 2 takes by weighing 4.265 grams (molecular weight 160).
Embodiment 3:
Weigh iron oxide 4.95 grams, all the other are with step 3～step 8 of embodiment 1.
The catalyst of the various embodiments described above is got the 1wt.%Au/MnO of about 0.10 gram
2/ Fe
2O
3Place 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 1.33/2.66/64/32 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 35,50,65,100 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 among the every embodiment of table 1
Reaction result among the every embodiment of table 1 (continuing)
The foregoing description only is to give an example for convenience of description, and the interest field that the present invention advocated should be as the criterion so that the claim scope is described certainly, but not only limits to the foregoing description.
Claims (17)
1, a kind of catalyst of carbon monoxide oxidation is used for the catalyst of selectivity carbon monoxide oxidation under rich hydrogen environment, comprising: the carrier of mixed oxidization manganese and iron oxide; And load on the nanogold particle on this carrier surface.
2, the catalyst of carbon monoxide oxidation as claimed in claim 1, wherein, the particle diameter of this nanogold particle is less than 5 nanometers.
3, a kind of nano-gold loaded in the manufacture method of carrier catalyst, it comprises the following steps:
(a) with manganese nitrate solution with after iron oxide 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) to wash this sediment;
(e) dry this sediment;
(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 iron oxide with the impregnation legal system, and its ferromanganese mixed proportion is 1/9 to 3/7.
5, method as claimed in claim 3, wherein, calcination time is 2 to 6 hours in the step (a).
6, method as claimed in claim 3, wherein, in the step (b), when precipitating this nm of gold catalyst, temperature maintenance is at 50 to 90 ℃.
7, method as claimed in claim 3, wherein, in the 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, in the step (c), when precipitating this nm of gold catalyst, pH-value is 8 to 9.
9, method as claimed in claim 3, wherein, in the 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 the step (d), the temperature of this water is 60 ℃ to 70 ℃.
11, method as claimed in claim 3, wherein, in the step (e), this bake out temperature is 100 ℃ to 110 ℃.
12, method as claimed in claim 3, wherein, in the step (e), this drying time is 10 to 12 hours.
13, method as claimed in claim 3, wherein, in the step (f), this sediment time after this calcining oven dry is 2 to 10 hours.
14, a kind of method that contains carbon monoxide in the gas of removing, it comprises following steps:
Nano-gold loadedly containing under the reacting gas that hydrogen exists to contain in manganese oxide and iron 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 4.
15, method as claimed in claim 14 wherein, contains nano-gold loadedly in the catalyst of manganese oxide and iron oxide, and 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 2 to 3 in this reacting gas.
17, method as claimed in claim 14, wherein, operating temperature is between 25 ℃ to 100 ℃.
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113156554A (en) * | 2020-01-03 | 2021-07-23 | 杭州柔谷科技有限公司 | Optical functional film, preparation method thereof and flexible optoelectronic device |
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|---|---|---|---|---|
| CN113156554A (en) * | 2020-01-03 | 2021-07-23 | 杭州柔谷科技有限公司 | Optical functional film, preparation method thereof and flexible optoelectronic device |
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