CN112993285A - Catalyst for preferentially oxidizing CO in hydrogen-rich gas and preparation method and application thereof - Google Patents

Catalyst for preferentially oxidizing CO in hydrogen-rich gas and preparation method and application thereof Download PDF

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CN112993285A
CN112993285A CN202110184342.3A CN202110184342A CN112993285A CN 112993285 A CN112993285 A CN 112993285A CN 202110184342 A CN202110184342 A CN 202110184342A CN 112993285 A CN112993285 A CN 112993285A
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刘志刚
向港华
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Hunan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention belongs to the technical field of catalyst materials, and particularly relates to a catalyst capable of preferentially oxidizing CO in hydrogen-rich gas, and further discloses a preparation method and application thereof. The catalyst for preferentially oxidizing carbon monoxide in hydrogen-rich gas takes a cerium source material and a zirconium source material as precursors, and a strong-base precipitator is used for preparing a cerium-zirconium solid solution as a carrier through a coprecipitation method; taking a chloroauric acid solution as a gold precursor, and preparing a catalyst loaded with trace gold by a deposition precipitation method by using a weakly alkaline precipitator; the catalyst can be applied to preferential oxidation of carbon monoxide in hydrogen-rich gas after reduction in hydrogen, has high catalytic activity under the condition of extremely small noble metal loading capacity, realizes high conversion rate of CO, can almost completely convert CO within the working temperature range of the PEMFC, has extremely high catalytic efficiency, good stability and is not easy to inactivate.

Description

Catalyst for preferentially oxidizing CO in hydrogen-rich gas and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to a catalyst capable of preferentially oxidizing CO in hydrogen-rich gas, and further discloses a preparation method and application thereof.
Background
The fuel cell is a power generation device which can directly convert chemical energy in fuel and oxidant into electric energy, has the advantages of small environmental pollution, high power generation efficiency and the like, and is regarded as solving fossil in twenty-first centuryThe effective method of the energy crisis is widely researched by scientific research personnel. In various types of fuel cells, it is generally desirable to use pure H2Proton Exchange Membrane Fuel Cells (PEMFCs), which are fuels, are known as the fuel cells with the greatest application prospects, and are the focus of research.
H for PEMFC2Usually from catalytic reforming of hydrocarbons and partial oxidation of liquid fuels, the gas mixture generally obtained from these reactions contains mainly 40-75 vol.% H220-25 vol.% CO20.5-2 vol.% CO and small amounts of H2And O. In the operating temperature range of the PEMFC, a trace amount of CO in the mixed gas is adsorbed on the platinum-based material of the anode of the battery and is difficult to desorb, so that H is generated2Adsorption and oxidation on the electrode material are greatly suppressed, and the performance and life of the fuel cell are seriously affected. Therefore, before the hydrogen-rich raw material enters the PEMFC, the CO must be removed so that the content of the CO is reduced to be below 10-100ppm, and the normal work and the service performance of the PEMFC can be ensured.
Carbon monoxide preferential oxidation is called CO PROX for short, and specifically, CO is oxidized to the maximum extent under the action of a catalyst by introducing a small amount of oxygen or air into a hydrogen-rich atmosphere, and H is reduced at the same time2And (4) oxidizing. The method is simple to operate and direct in effect, and is the most effective and economical method for reducing the content of CO to the standard which can be endured by the electrode. At present, the key of the carbon monoxide preferential oxidation method is the design and preparation of the catalyst, and the catalyst with excellent performance is required to realize the smooth operation of CO PROX. The catalysts currently reported to have carbon monoxide preferential oxidation properties can be divided into two categories: namely, a noble metal catalyst and a non-noble metal catalyst, the noble metal catalyst is mostly represented by an Au catalyst and a Pt-based catalyst (Pd, Rh, Ir, Ru, etc.), and the non-noble metal catalyst mainly includes a Cu-based catalyst, a Co-based catalyst, a Mn-based catalyst, and the like. The Au catalyst has good low-temperature activity, and can obtain higher CO conversion rate and selectivity within the working temperature range (80-120 ℃) of the PEMFC, so that the Au catalyst is a durable research hotspot; however, it has a disadvantage that Au is easily agglomerated when the temperature is increased, resulting in enlargement of particles and reduction of active sites, which ultimately results inThe catalyst activity is decreased and the practical use of Au catalysts is limited by the high cost of noble metals.
In view of the above problems, the prior art (Applied Surface Science 481(2019) 1072-1079 DOI:10.1016/j. apsusc.2019.03.219) developed a CeO-based solution2Preparation of CeO by precipitation method with Au-loaded catalyst2A carrier, gold is loaded on the carrier by an adsorption impregnation method, and a gold precursor HAuCl is changed4In amounts to produce catalysts of different Au loadings (0.05%, 0.15%, 0.3%, 0.6%, 1.2%) for catalyzing the preferential oxidation of carbon monoxide in hydrogen-rich gas, with 0.3% loading of Au/CeO2The activity of (a) is optimal, and the highest conversion rate close to 100% can be obtained at 40 ℃. However, the loading amount of the noble metal Au in the catalyst needs to reach 0.3%, the dosage is large, the preparation cost is high, and the optimal activity temperature of the catalyst is not necessarily in the working temperature range of the proton exchange membrane fuel cell, so that the working efficiency and the stability are not ideal. Therefore, the development of a catalyst for preferentially oxidizing CO in hydrogen-rich gas, which has low noble metal loading and good working stability and can obtain higher CO conversion rate in the working temperature range of the PEMFC, has positive significance for the development of fuel cells.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a catalyst for preferentially oxidizing CO in hydrogen-rich gas, wherein the catalyst has low noble metal loading capacity, low production cost and good working stability, and can obtain higher CO conversion rate within the working temperature range of PEMFC;
the second technical problem to be solved by the invention is to provide a preparation method and application of the catalyst for preferentially oxidizing CO in hydrogen-rich gas.
In order to solve the technical problems, the catalyst for preferentially oxidizing CO in hydrogen-rich gas comprises a cerium-zirconium solid solution as a carrier and gold loaded on the carrier;
in the catalyst, the loading amount of the gold is 0.01-0.2 wt%.
The invention also discloses a method for preparing the catalyst for preferentially oxidizing CO in the hydrogen-rich gas, which comprises the following steps:
(1) taking a cerium source material and a zirconium source material as precursors, preparing a cerium-zirconium solid solution by a coprecipitation method by using a strong-base precipitator, and aging, drying and roasting to obtain a required carrier;
(2) and adding a chloroauric acid solution into the carrier to serve as a gold precursor, carrying out deposition and precipitation by using a weak alkaline precipitator, and carrying out aging and drying treatment on reactants to obtain the catalyst loaded with gold.
Specifically, in the step (1):
the cerium source material comprises a nitrate or chloride salt of cerium, preferably cerium nitrate hexahydrate;
the zirconium source material comprises a nitrate salt of zirconium, preferably zirconyl nitrate or zirconium nitrate;
the strongly basic precipitant is preferably sodium hydroxide.
Specifically, in the step (1):
controlling the molar ratio of Ce to Zr in the cerium source material and the zirconium source material to be 1: 1-1.5: 1;
the molar ratio of the strong-base precipitant to the Ce in the cerium source material is 8: 1-10: 1.
specifically, in the step (1):
controlling the temperature of the aging step to be 20-30 ℃;
controlling the temperature of the drying step to be 70-90 ℃;
the temperature of the roasting step is controlled to be 450-550 ℃.
Specifically, in the step (2), the weakly basic precipitant is preferably sodium carbonate or potassium carbonate.
Specifically, in the step (2):
the dosage of the chloroauric acid accounts for 0.01-0.2 wt% of the mass of the carrier by the weight of Au;
the dosage of the alkalescent precipitator is used for adjusting the pH value of a solution system to 7-8.
Specifically, in the step (2):
controlling the temperature of the aging step to be 50-70 ℃;
the temperature of the drying step is controlled to be 50-60 ℃.
The invention also discloses a catalyst for preferentially oxidizing CO in hydrogen-rich gas, which is prepared by the method.
The invention also discloses application of the catalyst in catalyzing the preferential oxidation reaction of carbon monoxide in hydrogen-rich mixed gas.
The invention also discloses a preferential oxidation reaction of carbon monoxide in the hydrogen-rich gas mixture, which comprises the step of carrying out catalytic reaction by using the catalyst.
Specifically, the preferential oxidation reaction of carbon monoxide in the hydrogen-rich gas mixture also comprises the step of placing the catalyst in 5-10% of H before the reaction2/N2In the atmosphere, carrying out in-situ pre-reduction treatment for 1-2h at the temperature of 200-250 ℃.
The catalyst for preferentially oxidizing carbon monoxide in hydrogen-rich gas takes a cerium source material and a zirconium source material as precursors, and a strong-base precipitator is used for preparing a cerium-zirconium solid solution as a carrier through a coprecipitation method; taking a chloroauric acid solution as a gold precursor, and preparing a catalyst loaded with trace gold by a deposition precipitation method by using a weakly alkaline precipitator; the catalyst can be applied to preferential oxidation of carbon monoxide in hydrogen-rich gas after reduction in hydrogen, has high catalytic activity under the condition of extremely small noble metal loading capacity, realizes high conversion rate of CO, can almost completely convert CO within the working temperature range of the PEMFC, has extremely high catalytic efficiency, good stability and is not easy to inactivate. The catalyst provided by the invention has a simple preparation process, can run for a long time, is suitable for practical application, and has a good practical application prospect.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a diagram of an apparatus for CO PROX activity testing of a catalyst according to the present invention;
FIG. 2 shows the effect of different gold loadings on CO conversion;
FIG. 3 shows catalyst vs. O at different gold loadings2To CO2The effect of selectivity;
FIGS. 4 (a) - (c) are respectively TEM, HR-TEM and HAADF-STEM of the 0.02Au/CZ catalyst of the present invention, and in (c), the HAADF-STEM shows that the arrows enclosed in the circle indicate the gold monoatomic atoms embedded in the carrier lattice;
FIG. 5 shows the results of the stability test of the 0.02Au/CeZrO catalyst of the present invention;
FIG. 6 shows the comparison of the performance of the low-loading Au catalyst of the present invention and the conventional Au-Ce catalyst under the same conditions;
FIG. 7 shows the results of comparing the performances of the supports and catalysts obtained in comparative examples 1-2 and example 5.
Detailed Description
Examples 1 to 6
Dissolving 0.87g of cerium nitrate and 0.46g of zirconyl nitrate (namely, the molar ratio of Ce to Zr is 1: 1) in 50mL of deionized water for later use; dissolving 0.8g of sodium hydroxide in 50mL of deionized water, dropwise adding the sodium hydroxide solution into the nitrate solution under vigorous stirring, continuously and fully stirring for 0.5h, and then aging at room temperature for 12 h; the reaction was filtered and washed with deionized water and then ethanol until NO3 -Then, the obtained filter cake is subjected to vacuum drying at 80 ℃ for 12h, then is ground into powder, and is roasted at 500 ℃ in the air for 4h to obtain the required Ce0.5Zr0.5O2And (3) a carrier.
Respectively taking the Ce according to the amount of 0.5 g/part0.5Zr0.5O2Mixing the carrier and 50mL of deionized water to prepare a suspension, preparing 6 parts of suspensions in total, respectively adding 25 mu L, 51 mu L, 76 mu L, 127 mu L, 254 mu L and 508 mu L of chloroauric acid solution (respectively examples 1-6) into each part, stirring uniformly, respectively dropwise adding 70, 140, 210, 350, 700 and 1400 mu L of 0.1mol/L potassium carbonate solution (examples 1-6) into each part of reaction solution, aging in an oil bath at 60 ℃ for two hours, filtering and washing until no Cl exists-Then vacuum drying for 12h at 60 ℃ to respectively obtain theoretical gold loading of 0.01 wt%, 0.02 wt% and 0.03wt%, 0.05 wt%, 0.1 wt%, 0.2 wt% of the catalyst product, noted as 0.01Au/CeZrO, 0.02Au/CeZrO, 0.03Au/CeZrO, 0.05Au/CeZrO, 0.1Au/CeZrO, and 0.2Au/CeZrO, respectively.
Comparative example 1
Dissolving 0.87g of cerium nitrate and 0.46g of zirconyl nitrate (namely, the molar ratio of Ce to Zr is 1: 1) in 50mL of deionized water for later use; dissolving 0.8g of sodium hydroxide in 50mL of deionized water, dropwise adding the sodium hydroxide solution into the nitrate solution under vigorous stirring, continuously and fully stirring for 0.5h, and then aging at room temperature for 12 h; the reaction was filtered and washed with deionized water and then ethanol until NO3 -Then, the obtained filter cake is subjected to vacuum drying at 80 ℃ for 12h, then is ground into powder, and is roasted at 500 ℃ in the air for 4h to obtain the required Ce0.5Zr0.5O2A carrier, and testing the activity of the carrier.
The desired catalyst was prepared as the catalyst prepared as in example 5, by adding 254. mu.L of chloroauric acid solution + 700. mu.L of potassium carbonate solution to the support.
The catalyst was not reduced in situ with hydrogen prior to the CO PROX test to test its activity as 0.1Au/CeZrO-no reduction.
Comparative example 2
Dissolving 0.87g of cerium nitrate and 0.46g of zirconyl nitrate (namely, the molar ratio of Ce to Zr is 1: 1) in 50mL of deionized water for later use; dissolving 0.8g of sodium hydroxide in 50mL of deionized water, dropwise adding the sodium hydroxide solution into the nitrate solution under vigorous stirring, continuously and fully stirring for 0.5h, and then aging at room temperature for 12 h; the reaction was filtered and washed with deionized water and then ethanol until NO3 -Then, the obtained filter cake is subjected to vacuum drying at 80 ℃ for 12h, then is ground into powder, and is roasted at 500 ℃ in the air for 4h to obtain the required Ce0.5Zr0.5O2And (3) a carrier.
0.5g of the above Ce was taken0.5Zr0.5O2Mixing the carrier and 50mL of deionized water to prepare a suspension, adding 254 mu L of 0.01mol/L chloroauric acid solution, stirring uniformly, and placing in an oil bath at 60 ℃ for aging for two hoursThen, the mixture is filtered and washed until no Cl is formed-Then dried in vacuum at 60 ℃ for 12h, and the activity of the obtained catalyst product (i.e. without adding potassium carbonate precipitant) is tested as shown in the figure (pre-reduction activation treatment before test), and is recorded as 0.1Au/CeZrO-no-K2CO3。
Examples of the experiments
In the following experimental examples of the present invention, the apparatus for testing the activity of the catalyst is shown in FIG. 1, and the reaction gases are respectively represented by H2、CO、O2、N2Four paths of gas are mixed and introduced, and each gas path is provided with a pressure dividing valve, a stop valve, a mass flow meter and a flow display instrument. The catalyst activity test is carried out in a quartz tube type fixed bed reactor, the inner diameter of the quartz tube is 6mm, the length of the quartz tube is 310mm, a selected amount of catalyst is placed in a constant temperature area in the reaction tube, two sides of the catalyst are fixed by quartz wool, an electric furnace is adopted for heating, and a thermocouple is inserted into the furnace wall for temperature test and control.
The raw material gas composition is as follows: 1 vol% CO, 1 vol% O2、50vol％H2、N2The total flow rate of the gas as the balance gas is 30mL/min, wherein H2Flow rate of 15mL/min, CO flow rate of 0.3mL/min, O2The flow rate is 0.3mL/min, N2The flow rate was 14.4mL/min, and the mass flowmeters were all calibrated with soap film flowmeters. The tail gas analysis adopts Pannao A60 gas chromatograph autoinjection, online analysis, and the gas chromatograph sets up to circulation autosampling, and online analysis tail gas constitutes. In the experimental process, the gas composition at each temperature point needs to be stabilized for 30min before detection.
1. Catalyst to CO conversion and O2To CO2Influence of Selectivity
100mg of the catalysts prepared in examples 1 to 6 and having different Au loadings were placed in constant temperature zones in quartz tubes of fixed bed reactors, both sides were fixed with quartz wool, and the electric furnace was heated. Hydrogen pre-reduction treatment is carried out before reaction, and 5% H is introduced2/N2The flow rate of the mixed gas is 30mL/min, the mixed gas is heated to 250 ℃ and kept for 2h, and after the temperature is reduced to room temperature, the reaction gas is introduced according to the method, and the specific composition is as follows: 1 vol% CO, 1 vol% O2、50vol％H2、48vol％N2The total flow rate of gas is 30mL/min, the reaction temperature interval is controlled to be 40-150 ℃, samples are taken at intervals of 10 ℃, and each temperature point needs to be stabilized for 30min before testing. The tail gas analysis adopts A60 gas chromatograph to automatically sample and analyze on line.
The test results are respectively shown in the attached figures 2-3, and different Au loading amounts are investigated for CO conversion rate and O2To CO2The influence of the selectivity. When the Au loading is more than or equal to 0.03 wt%, the catalyst has good low-temperature activity, the CO conversion rate of more than 90% can be obtained at 80 ℃, and the conversion rates of more than 50% can be obtained at 40 ℃ by 0.1Au/CeZrO and 0.2 Au/CeZrO; when the Au loading was 0.02 wt%, the catalyst could convert CO almost completely at 100 ℃; when the Au loading is 0.01 wt%, the catalyst can obtain CO conversion rate higher than 99% at 140 ℃, and the highest conversion rate corresponds to O at the temperature point2To CO2The selectivity remained around 50%, indicating that CO was maximally oxidized, while H2Is suppressed.
2. Catalyst structural characterization
The best 0.02Au/CeZrO was characterized, the TEM image, HR-TEM image and HAADF-STEM are shown in (a) - (c) of FIG. 4, and the uniform particle size distribution of the catalyst between 8-15nm was observed from the TEM image shown in (a); from the HR-TEM image shown in the image (b), clear lattice stripes can be observed without the existence of gold nanoparticles and gold nanoclusters, and the lattice spacings of 0.19nm, 0.27nm and 0.31nm respectively correspond to the (111), (200) and (220) crystal faces of the cerium-zirconium solid solution; the point of the HAADF-STEM shown in the graph (c) where the brightness is the highest is the gold monoatomic atom (i.e., the circled arrow in the graph). The gold monatomic catalyst can obtain the highest atom utilization rate and reduce the dosage of noble metal on the one hand, and can inhibit H on the other hand2Dissociative adsorption on gold species to increase CO to O ratio of catalyst2Selectivity of (2).
3. Catalyst stability
100mg of the above 0.02Au/CeZrO catalyst was placed in a constant temperature zone in a quartz tube of a fixed bed reactor shown in FIG. 1, both sides were fixed with quartz wool, and heated by an electric furnace. Hydrogen pre-reduction treatment is carried out before reaction, and 5% H is introduced2/N2The flow rate of the mixed gas is 30mL/min, heating to 250 ℃ for 2h, and introducing reaction gas after the temperature is reduced to room temperature, wherein the reaction gas specifically comprises the following components: 1 vol% CO, 1 vol% O2、50vol％H2、48vol％N2The total flow rate of gas is 30mL/min, the reaction temperature is 80 ℃, the reaction time is 72h, and sampling is carried out at intervals, so as to determine the stability of the catalyst.
The test results are shown in FIG. 5, which examines the stability of the catalysts of the invention for CO PROX. The result shows that when the reaction temperature is 80 ℃, the 0.02Au/CeZrO catalyst can keep high activity for a long time in the reaction atmosphere, the activity is not attenuated after 72 hours, the CO conversion rate can still be kept above 95%, the selectivity can be kept about 50%, and the catalyst has better practical application prospect.
4. Performance difference from conventional catalyst
100mg of 0.01Au/CeZrO (example 1), 0.02Au/CeZrO (example 2), and 0.01Au/CeO prepared in a conventional manner were taken2、0.02Au/CeO2Catalyst, CO PROX test was performed under the same conditions.
The raw material gas composition is as follows: 1 vol% CO, 1 vol% O2、50vol％H2、48vol％N2The total gas flow rate is 30mL/min, the temperature interval is 40-150 ℃, samples are taken once every 10 ℃, and the gas composition at each temperature point is stabilized for 30min before detection.
The structure is shown in figure 6, and it can be seen that under the condition of extremely low gold loading, the catalyst prepared by the invention has obviously better performance compared with the traditional gold-cerium catalyst, and can almost completely convert CO at a proper temperature.
5. Comparative example catalyst Performance
For the carrier Ce prepared in comparative examples 1 and 2 above, respectively0.5Zr0.5O2Carrier, 0.1Au/CeZrO-no reduction, 0.1Au/CeZrO-no-K2CO3And the activity of 0.1Au/CeZrO of the catalyst prepared in example 5, and the test results are shown in FIG. 7.
As can be seen from the above results, pure Ce is not loaded with gold0.5Zr0.5O2The carrier has little activity for the CO-PROX reaction; negative poleIn the gold-loading process, if a proper amount of alkalescent precipitator is not added, the activity of the gold-loading catalyst is greatly reduced, and the highest CO conversion rate can only reach about 80 percent; if the catalyst obtained by adding the alkalescent precipitator in the gold loading process is not subjected to hydrogen pre-reduction treatment before activity test, the activity is obviously reduced, which is shown as extremely poor low-temperature activity, the highest CO conversion rate is less than 80%, and the requirement of reducing the CO concentration to be below 100ppm is obviously not met.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. A catalyst for preferentially oxidizing CO in hydrogen-rich gas, which is characterized in that the catalyst comprises a cerium-zirconium solid solution as a carrier, and gold loaded on the carrier;
in the catalyst, the loading amount of the gold is 0.01-0.2 wt%.
2. A method of making a catalyst for the preferential oxidation of CO in hydrogen-rich gas according to claim 1, comprising the steps of:
(1) taking a cerium source material and a zirconium source material as precursors, preparing a cerium-zirconium solid solution by a coprecipitation method by using a strong-base precipitator, and aging, drying and roasting to obtain a required carrier;
(2) and adding a chloroauric acid solution into the carrier to serve as a gold precursor, carrying out deposition and precipitation by using a weak alkaline precipitator, and carrying out aging and drying treatment on reactants to obtain the catalyst loaded with gold.
3. The method of claim 2, wherein in step (1):
controlling the molar ratio of Ce to Zr in the cerium source material and the zirconium source material to be 1: 1-1.5: 1;
the molar ratio of the using amount of the strong alkaline precipitator to Ce in the cerium source material is 8: 1-10: 1.
4. the method for producing a catalyst for preferential oxidation of CO in hydrogen-rich gas according to claim 2 or 3, wherein in the step (1):
controlling the temperature of the aging step to be 20-30 ℃;
controlling the temperature of the drying step to be 70-90 ℃;
the temperature of the roasting step is controlled to be 450-550 ℃.
5. The method for preparing a catalyst for the preferential oxidation of CO in hydrogen-rich gas according to any one of claims 2 to 4, wherein in the step (2):
the dosage of the chloroauric acid accounts for 0.01-0.2 wt% of the mass of the carrier by the weight of Au;
the dosage of the alkalescent precipitator is used for adjusting the pH value of a solution system to 7-8.
6. The method for preparing a catalyst for the preferential oxidation of CO in hydrogen-rich gas according to any one of claims 2 to 5, wherein in the step (2):
controlling the temperature of the aging step to be 50-70 ℃;
the temperature of the drying step is controlled to be 50-60 ℃.
7. A catalyst for the preferential oxidation of CO in hydrogen-rich gas produced by the process of any one of claims 2 to 6.
8. Use of a catalyst according to claim 1 or 7 for catalysing the preferential oxidation of carbon monoxide in a hydrogen-rich gas mixture.
9. A process for preferentially oxidizing carbon monoxide in a hydrogen-rich gas mixture, which comprises the step of catalyzing the reaction with the catalyst of claim 1 or 7.
10. The process of claim 9, further comprising exposing the catalyst to 5-10% H prior to the reaction2/N2In the atmosphere, carrying out in-situ pre-reduction treatment for 1-2h at the temperature of 200-250 ℃.
CN202110184342.3A 2021-02-08 2021-02-08 Catalyst for preferentially oxidizing CO in hydrogen-rich gas and preparation method and application thereof Pending CN112993285A (en)

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CN114042457A (en) * 2021-11-09 2022-02-15 上海化工研究院有限公司 Catalyst for purifying CO in hydrogen-rich gas and preparation method and application thereof
CN114289033A (en) * 2021-12-13 2022-04-08 湖南大学 Platinum catalyst loaded on flower-like cerium-iron oxide and application of platinum catalyst in catalyzing preferential oxidation of carbon monoxide in hydrogen-rich gas
CN115069242A (en) * 2022-05-05 2022-09-20 有研工程技术研究院有限公司 Catalyst for hydrogen production by oxidation and reforming of ethanol and preparation and activation methods thereof

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CN114042457A (en) * 2021-11-09 2022-02-15 上海化工研究院有限公司 Catalyst for purifying CO in hydrogen-rich gas and preparation method and application thereof
CN114289033A (en) * 2021-12-13 2022-04-08 湖南大学 Platinum catalyst loaded on flower-like cerium-iron oxide and application of platinum catalyst in catalyzing preferential oxidation of carbon monoxide in hydrogen-rich gas
CN115069242A (en) * 2022-05-05 2022-09-20 有研工程技术研究院有限公司 Catalyst for hydrogen production by oxidation and reforming of ethanol and preparation and activation methods thereof

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