A purification co oxygen-rich base catalyst and its preparation method and application

Abstract

This invention belongs to the field of catalyst technology, providing a CO purification oxygen-rich catalyst, its preparation method, and its application. The preparation method involves dispersing γ-alumina in water, then sequentially adding copper nitrate and cerium nitrate to obtain a reaction solution. The reaction solution is mixed with an inorganic base, followed by a substitution reaction and a crystallization reaction to obtain a catalyst precursor. The catalyst precursor is calcined under a reducing atmosphere to obtain the CO purification oxygen-rich catalyst; the reducing atmosphere includes hydrogen. This preparation method generates sufficient active sites through a copper-cerium binary system, and then utilizes the basic groups provided by the inorganic base to form a low-valence metal-hydroxyl composite structure under a reducing atmosphere. Through the combined action of metal atoms, hydroxyl groups, and active oxygen sites, the research goals of high efficiency, stability, high selectivity, and economy are achieved. Furthermore, this preparation method does not use precious metals, resulting in low cost.

Description

Technical Field

[0001] This invention relates to the field of catalysis technology, and in particular to an oxygen-rich catalyst for purifying CO, its preparation method, and its application. Background Technology

[0002] With the rapid development of automobile manufacturing, automobiles consume gasoline and emit large amounts of exhaust fumes, exacerbating mobile source pollution. Therefore, the application of clean energy, such as hydrogen (H2), is essential. However, in the practical application of hydrogen energy, the presence of CO can poison Pt catalysts, severely affecting the quality of end products. Currently, methods for removing residual CO from H2 mainly include adsorption, combustion, and catalytic oxidation. Among these, catalytic oxidation has greater potential. This method can achieve efficient CO removal at lower temperatures, and the toxic CO is converted into non-toxic CO2 through interaction with the catalyst. Furthermore, the catalyst can be regenerated after use, exhibiting both environmental and economic advantages. Therefore, developing catalysts that are efficient, stable, highly selective, and economical has become a current research focus.

[0003] Chinese patent CN00122829.3 discloses a practical low-temperature CO catalytic oxidation catalyst. This method uses Au as the active component and one or more metal oxides as supports to prepare a highly efficient composite catalyst. This method can significantly improve the low-temperature catalytic activity and anti-poisoning ability of the catalyst, but the use of precious metals greatly increases the cost of the catalyst. Chinese patent CN201710812414.8 discloses a supported copper-manganese catalyst, its preparation method, and its application in low-temperature catalytic CO oxidation. This method mixes cerium dioxide and a solution containing copper and manganese salts, filters, and calcines to obtain a catalyst with copper oxide and manganese oxide as active materials. This method produces a catalyst with high activity and low cost, suitable for low-temperature CO catalytic removal in enclosed spaces. However, in catalytic processes dominated by metal oxides, the catalyst exhibits poor selectivity for CO2 in an H2 atmosphere. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide an oxygen-rich catalyst for purifying CO, its preparation method, and its application. The catalyst prepared by the method of this invention exhibits high selectivity for CO2 in an H2 atmosphere and is low in cost.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for preparing a CO-purifying oxygen-rich catalyst, comprising the following steps:

[0007] γ-alumina was dispersed in water, and then copper nitrate and cerium nitrate were added in sequence to obtain a reaction solution;

[0008] The reaction solution and an inorganic base were mixed and then subjected to a substitution reaction and a crystallization reaction in sequence to obtain a catalyst precursor.

[0009] The catalyst precursor was calcined under a reducing atmosphere to obtain the CO-purifying oxygen-rich catalyst.

[0010] The reducing atmosphere includes hydrogen.

[0011] Preferably, the mass ratio of copper to γ-alumina in the copper nitrate is 1:2 to 1:10.

[0012] Preferably, the mass ratio of cerium to γ-alumina in the cerium nitrate is 1:10 to 1:100.

[0013] Preferably, the inorganic base is one or more of KOH, KHCO3, K2CO3, and ammonia.

[0014] The inorganic base is added in the form of an inorganic base solution, and the inorganic base solution is added dropwise at a rate of 1–20 mL / min.

[0015] The molar ratio of the inorganic base to copper nitrate is 1:1 to 1:5.

[0016] Preferably, the substitution reaction is carried out at room temperature for 5-6 hours, and the substitution reaction is carried out under stirring conditions.

[0017] Preferably, the crystallization reaction temperature is 80–240°C, the gauge pressure is 0.05–0.15 MPa, and the holding time is 12–72 h.

[0018] The atmosphere for the crystallization reaction includes oxygen and an inert gas; the volume ratio of the oxygen and the inert gas is 1:1 to 10.

[0019] Preferably, the volume concentration of hydrogen in the reducing atmosphere is 5-20%; the calcination temperature is 300-500℃, and the calcination time is 5-12h.

[0020] The present invention also provides a CO-purifying oxygen-enriched catalyst obtained by the preparation method described above, wherein monovalent copper and divalent copper coexist in the CO-purifying oxygen-enriched catalyst, and cerium is mainly trivalent; the surface of the CO-purifying oxygen-enriched catalyst is coated with a metal-hydroxyl structure.

[0021] This invention also provides the application of the CO-rich oxygen-enriched catalyst described in the above technical solution in CO purification.

[0022] Preferably, it includes the following steps:

[0023] The reactant gas undergoes a catalytic reaction under the action of a CO-purified oxygen-rich catalyst;

[0024] The reaction gas includes hydrogen, CO, oxygen, and a balance gas;

[0025] In the reaction gas, the volume concentration of hydrogen is 50%–80%, the volume concentration of CO is 1%–5%, the volume concentration of oxygen is 1.25%–10%, and the remainder is a balance gas; the balance gas is helium.

[0026] The temperature of the catalytic reaction is 30–220°C;

[0027] The rate of heating to the temperature of the catalytic reaction is 4 °C / min.

[0028] This invention provides a method for preparing a CO-purifying oxygen-rich catalyst, comprising the following steps: dispersing γ-alumina in water, then sequentially adding copper nitrate and cerium nitrate to obtain a reaction solution; mixing the reaction solution with an inorganic base, and then sequentially performing a substitution reaction and a crystallization reaction to obtain a catalyst precursor; calcining the catalyst precursor under a reducing atmosphere to obtain the CO-purifying oxygen-rich catalyst; the reducing atmosphere includes hydrogen. The preparation method provided by this invention generates sufficient active sites through a copper-cerium binary system, and then utilizes the basic groups provided by the inorganic base to form a low-valence metal-hydroxyl composite structure under a reducing atmosphere. Through the combined action of metal atoms, hydroxyl groups, and active oxygen sites, the research objectives of high efficiency, stability, high selectivity, and economy are achieved. Compared with existing catalysts, the preparation method provided by this invention is green and economical, and the catalyst is easy to reuse. It solves the CO pollution problem while responding to the national call for energy conservation and emission reduction, and has good environmental and economic benefits. Furthermore, the preparation method of this invention does not use precious metals, resulting in low cost. Attached Figure Description

[0029] Figure 1 This is a graph showing the CO conversion results of CO catalyzed by catalysts with different cerium contents in Example 4;

[0030] Figure 2 This is a graph showing the CO2 selectivity results of CO catalyzed by catalysts with different cerium contents in Example 4;

[0031] Figure 3 The graph shows the CO conversion rate results of the CO purification oxygen-rich catalyst obtained in Example 3 for reuse.

[0032] Figure 4 This is a graph showing the CO2 selectivity results of the CO purification oxygen-rich catalyst obtained in Example 3 for reuse.

[0033] Figure 5The images show the characterization of the catalysts obtained in Example 1 and Comparative Example 1, where the left image is a scanning electron microscope (SEM) image of the catalyst obtained in Comparative Example 1, and the right image is a scanning electron microscope (SEM) image of the catalyst obtained in Example 1. Detailed Implementation

[0034] This invention provides a method for preparing a CO-purifying oxygen-rich catalyst, comprising the following steps:

[0035] γ-alumina was dispersed in water, and then copper nitrate and cerium nitrate were added in sequence to obtain a reaction solution;

[0036] The reaction solution and an inorganic base were mixed and then subjected to a substitution reaction and a crystallization reaction in sequence to obtain a catalyst precursor.

[0037] The catalyst precursor was calcined under a reducing atmosphere to obtain the CO-purifying oxygen-rich catalyst.

[0038] The reducing atmosphere includes hydrogen.

[0039] Unless otherwise specified, all raw materials used in this invention are preferably commercially available products.

[0040] In this invention, γ-alumina is dispersed in water, and then copper nitrate and cerium nitrate are added sequentially to obtain a reaction solution.

[0041] In this invention, the particle size of the γ-alumina is preferably 10 nm, and the purity is preferably ≥99.99%. In this invention, the water is preferably distilled water.

[0042] In this invention, the mass ratio of copper to γ-alumina in the copper nitrate is preferably 1:2 to 1:10, and more preferably 1:4 to 1:8. In this invention, the mass ratio of cerium to γ-alumina in the cerium nitrate is preferably 1:10 to 1:100, and more preferably 1:30 to 1:70.

[0043] In this invention, the copper nitrate is preferably dissolved before cerium nitrate is added.

[0044] After adding the cerium nitrate, the present invention preferably involves stirring, and the stirring time is preferably 4 to 6 hours.

[0045] In this invention, the reaction solution is preferably light blue.

[0046] In this invention, after copper nitrate is added to the γ-alumina aqueous dispersion, copper ions adhere to the γ-alumina framework and pores.

[0047] After obtaining the reaction solution, the present invention mixes the reaction solution with an inorganic base and then performs a substitution reaction and a crystallization reaction in sequence to obtain a catalyst precursor.

[0048] In this invention, the inorganic base is preferably one or more of KOH, KHCO3, K2CO3, and ammonia, more preferably a mixture of KOH and Na2CO3, a mixture of KOH and NaHCO3, or a mixture of Na2CO3 and NaHCO3; the mass ratio of KOH to Na2CO3 in the KOH and Na2CO3 mixture is preferably 5:1; the mass ratio of KOH to NaHCO3 in the KOH and NaHCO3 mixture is preferably 10:1; the mass ratio of Na2CO3 to NaHCO3 in the Na2CO3 and NaHCO3 mixture is preferably 2:1. In this invention, the molar ratio of the inorganic base to copper nitrate is preferably 1:1 to 1:5, more preferably 1:2 to 1:4. In this invention, the inorganic base is preferably added in the form of an inorganic base solution, the inorganic base solution is preferably added dropwise, and the dropping rate of the inorganic base solution is preferably 1 to 20 mL / min, more preferably 5 to 15 mL / min.

[0049] In this invention, the temperature of the substitution reaction is preferably room temperature, and the time is preferably 4 to 6 hours. The timing of the substitution reaction is preferably started after the inorganic alkaline solution has been added. The substitution reaction is preferably carried out under stirring conditions.

[0050] In this invention, during the process of adding the inorganic alkali solution to the reaction solution and during the substitution reaction, the inorganic alkali undergoes a substitution reaction with the γ-alumina framework.

[0051] After the substitution reaction and before the crystallization reaction, the present invention preferably includes introducing an atmosphere for the crystallization reaction, and the introduction time of the atmosphere for the crystallization reaction is preferably 4-5 hours. The composition of the atmosphere for the crystallization reaction will preferably be described later in the present invention and will not be repeated here. In the present invention, the purpose of introducing the atmosphere for the crystallization reaction is to maintain a constant pressure in the crystallization reaction equipment and to ensure that the dissolved oxygen in the resulting liquid from the substitution reaction reaches saturation, so as to facilitate the smooth progress of the subsequent crystallization reaction.

[0052] In this invention, the temperature of the crystallization reaction is preferably 80–240°C, more preferably 100–200°C; the gauge pressure is preferably 0.05–0.15 MPa; and the holding time is preferably 12–72 h. In this invention, the atmosphere of the crystallization reaction preferably includes oxygen and an inert gas; the volume ratio of the oxygen to the inert gas is preferably 1:1–10, more preferably 1:2–8. In this invention, the inert gas is preferably argon. In this invention, the crystallization is preferably carried out in a reaction vessel.

[0053] Following the crystallization reaction, the present invention preferably further includes: filtration, and drying the resulting filter cake. In the present invention, the drying temperature is preferably 60–100°C, and the drying time is preferably 24–72 hours.

[0054] In this invention, the main component of the catalyst precursor is CuO-CeO2 / Al2O3.

[0055] In this invention, the crystallization reaction enables the functionalization of the catalyst surface and the expansion of pores.

[0056] After obtaining the catalyst precursor, the present invention calcines the catalyst precursor under a reducing atmosphere to obtain the CO-purifying oxygen-rich catalyst.

[0057] In this invention, the reducing atmosphere includes hydrogen; the volume concentration of hydrogen in the reducing atmosphere is preferably 5-20%, more preferably 10-15%. In this invention, the reducing atmosphere preferably also includes argon. In this invention, the calcination temperature is preferably 300-500°C, more preferably 350-450°C, and even more preferably 400°C; the calcination time is preferably 5-12 hours.

[0058] After the roasting is completed, the present invention is preferably cooled naturally to room temperature under a reducing atmosphere.

[0059] The present invention also provides a CO-purifying oxygen-enriched catalyst obtained by the preparation method described above, wherein monovalent copper and divalent copper coexist in the CO-purifying oxygen-enriched catalyst, and cerium is mainly trivalent; the surface of the CO-purifying oxygen-enriched catalyst is coated with a metal-hydroxyl structure.

[0060] This invention also provides the application of the CO-rich oxygen-enriched catalyst described in the above technical solution in CO purification.

[0061] In this invention, when the CO-purifying oxygen-rich catalyst is applied to CO purification, it includes the following steps:

[0062] The reactant gas undergoes a catalytic reaction under the action of a CO-purified oxygen-rich catalyst.

[0063] In this invention, the reaction gas includes hydrogen, CO, oxygen and a balance gas; the volume concentration of hydrogen in the reaction gas is 50% to 80%, the volume concentration of CO is 1% to 5%, the volume concentration of oxygen is 1.25% to 10%, and the remainder is the balance gas; the balance gas is helium.

[0064] In this invention, the flow rate of the reaction gas is preferably 20 mL / min.

[0065] In this invention, the temperature of the catalytic reaction is 30–220°C; the rate of heating to the temperature of the catalytic reaction is 4°C / min.

[0066] The following detailed description, in conjunction with embodiments, illustrates the CO purification oxygen-rich catalyst, its preparation method, and its application provided by the present invention. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0067] Example 1

[0068] A method for preparing a CO-purifying oxygen-rich catalyst specifically includes the following steps:

[0069] (1) Mix commercially available γ-alumina (purity 99.99%, 10nm) uniformly in distilled water, then add copper nitrate to the resulting milky white turbid liquid at a mass ratio of copper to γ-alumina of 1:2. After it dissolves, add cerium nitrate at a mass ratio of cerium to γ-alumina of 1:10. Stir continuously at room temperature for 5 hours to allow the metal salt and γ-alumina to come into full contact, and obtain a uniformly dispersed light blue mixed solution.

[0070] (2) An inorganic alkaline solution (the molar ratio of inorganic alkali to copper is 1:1, and the mass ratio of KOH to Na2CO3 in the inorganic alkali solution is 5:1) is added to the above mixed solution at a rate of 1 mL / min. The mixture is stirred at room temperature for 5 h to allow it to fully substitute with the γ-alumina framework. The mixture after substitution reaction is then transferred to a reaction vessel and aeration is carried out for 4 h under a gauge pressure of 0.05 MPa. The gas introduced into the reaction vessel is a mixture of Ar and O2 with a volume ratio of Ar to O2 of 10:1. Then, the crystallization reaction is carried out at 100 °C for 24 h to achieve surface functionalization and pore enlargement of the catalyst.

[0071] (3) The mixture after reaction was filtered and dried at 100°C for 24 hours to obtain a completely dry catalyst precursor.

[0072] (4) Finally, the catalyst precursor is calcined at 400℃ for 12h in a reducing atmosphere (Ar to H2 volume ratio of 9:1) to obtain the desired catalyst. After the calcination process, a protective atmosphere should be continued to be introduced until the temperature naturally cools to room temperature to ensure that monovalent and divalent copper coexist in the catalyst, cerium is mainly trivalent, and metal-hydroxyl structures are attached to the catalyst surface.

[0073] The obtained catalyst was used to purify CO under the following reaction conditions:

[0074] The reaction gases consist of 50% H2, 1% CO, and 1.25% O2 by volume; the balance is helium. The flow rate of the reaction gases is 20 mL / min, the reaction temperature window is 30–220 °C, and the heating rate is 4 °C / min.

[0075] Experimental results show that the CO conversion rate can reach 95% in the low temperature range (80-120℃), the CO2 selectivity can reach 70%, and the catalyst reuse efficiency is 91.5%.

[0076] Example 2

[0077] A method for preparing a CO-purifying oxygen-rich catalyst specifically includes the following steps:

[0078] (1) Mix commercially available γ-alumina (purity 99.99%, 10nm) uniformly in distilled water, then add copper nitrate to the resulting milky white turbid liquid at a mass ratio of copper to γ-alumina of 1:5. After it dissolves, add cerium nitrate at a mass ratio of cerium to γ-alumina of 1:50. Stir continuously at room temperature for 6 hours to allow the metal salt and γ-alumina to come into full contact, and obtain a uniformly dispersed light blue mixed solution.

[0079] (2) An inorganic alkaline solution (the molar ratio of inorganic alkali to copper is 1:2, and the mass ratio of KOH to NaHCO3 in the inorganic alkali solution is 10:1) was added to the above mixed solution at a rate of 5 mL / min. The mixture was stirred at room temperature for 6 h to allow it to fully react with the γ-alumina framework. The resulting mixture was then transferred to a reaction vessel and vented for 5 h under a gauge pressure of 0.1 MPa. The gas introduced into the reaction vessel was a mixture of Ar and O2 with a volume ratio of Ar to O2 of 5:1. The reaction was then carried out at 200 °C for 48 h to achieve surface functionalization and pore enlargement of the catalyst.

[0080] (3) The reaction mixture was filtered and dried at 80°C for 48 hours to obtain a completely dry catalyst precursor.

[0081] (4) Finally, the catalyst precursor is calcined at 500°C for 5 hours in a reducing atmosphere (Ar to H2 volume ratio of 4:1) to obtain the desired catalyst. After the calcination process, a protective atmosphere should be continued to be introduced until the temperature naturally cools to room temperature to ensure that monovalent and divalent copper coexist in the catalyst, cerium is mainly trivalent, and metal-hydroxyl structures are attached to the catalyst surface.

[0082] The obtained catalyst was used to purify CO under the following reaction conditions:

[0083] The reaction gases consist of 50% H2, 1% CO, and 1.25% O2 by volume, with the balance being helium. The flow rate of the reaction gases is 20 mL / min, the reaction temperature window is 30–220 °C, and the heating rate is 4 °C / min.

[0084] Experimental results show that the CO conversion rate can reach 92% in the low temperature range (80-120℃), the CO2 selectivity can reach 63%, and the catalyst reuse efficiency is 90.8%.

[0085] Example 3

[0086] A method for preparing a CO-purifying oxygen-rich catalyst specifically includes the following steps:

[0087] (1) Mix commercially available γ-alumina (purity 99.99%, 10nm) uniformly in distilled water, then add copper nitrate to the resulting milky white turbid liquid at a mass ratio of copper to γ-alumina of 1:10. After it dissolves, add cerium nitrate at a mass ratio of cerium to γ-alumina of 1:10. Stir continuously at room temperature for 4 hours to allow the metal salt and γ-alumina to come into full contact, and obtain a uniformly dispersed light blue mixed solution.

[0088] (2) An inorganic alkali solution (the molar ratio of inorganic alkali to copper is 1:5, and the mass ratio of Na2CO3 to NaHCO3 in the inorganic alkali solution is 2:1) was added to the above mixed solution at a rate of 20 mL / min. The mixture was stirred at room temperature for 4 h to allow it to fully react with the γ-alumina framework. The resulting mixture was then transferred to a reaction vessel and aerated at a gauge pressure of 0.15 MPa for 4 h. The gas introduced into the reaction vessel was a mixture of Ar and O2 with a volume ratio of Ar to O2 of 2:1. The reaction was then carried out at 240 °C for 72 h to achieve surface functionalization and pore enlargement of the catalyst.

[0089] (3) The reaction mixture was filtered and dried at 60°C for 72 hours to obtain a completely dry catalyst precursor.

[0090] (4) Finally, the catalyst precursor is calcined at 300℃ for 8 hours under a reducing atmosphere (Ar to H2 volume ratio of 19:1) to obtain the desired catalyst. After the calcination process, a protective atmosphere should be continued to be introduced until the temperature naturally cools to room temperature to ensure that monovalent and divalent copper coexist in the catalyst, cerium is mainly trivalent, and metal-hydroxyl structures are attached to the catalyst surface.

[0091] The obtained catalyst was used to purify CO under the following reaction conditions:

[0092] The reaction gases consist of 50% H2, 1% CO, and 1.25% O2 by volume, with the balance being helium. The reaction gas flow rate is 20 mL / min, the reaction temperature window is 30–220 °C, and the heating rate is 4 °C / min.

[0093] Experimental results show that the CO conversion rate can reach 98% in the low temperature range (80-120℃), the CO2 selectivity can reach 75%, and the catalyst reuse efficiency is 95.2%.

[0094] Example 4

[0095] The difference from Example 3 is that the mass ratio of cerium to γ-alumina was changed to 1:100, 3:100, 5:100, and 8:100, and cerium nitrate was added. Otherwise, it was the same as Example 3.

[0096] Comparative Example 1

[0097] The difference from Example 1 is that cerium nitrate is not added, while other parameters and steps are the same.

[0098] Figure 1 This is a graph showing the CO conversion results of CO catalyzed by catalysts with different cerium contents in Example 4; from Figure 1 It can be seen that under low temperature conditions (80-120℃), the catalyst containing 10% copper and loaded with 10% cerium and 8% cerium has a catalytic effect of nearly 70% on CO, which is significantly improved compared to the single copper loading (measured at about 40%).

[0099] Figure 2 This is a graph showing the CO2 selectivity results of CO catalyzed by catalysts with different cerium contents in Example 4. Figure 2 It can be seen that under low-temperature conditions, the higher cerium-supported catalyst exhibits better selectivity for CO2 generation, reaching 85-90%, which is a significant improvement compared to previously reported catalysts (50-60%). Considering factors such as effectiveness and economy, 10% copper and 8% cerium are selected as the optimal raw material ratio at present.

[0100] Figure 3 This is a graph showing the CO conversion rate results of the CO purification oxygen-rich catalyst obtained in Example 3 that can be reused. Figure 4 This is a graph showing the CO2 selectivity results for the reuse of the CO-purifying oxygen-rich catalyst obtained in Example 3. Figure 3 and Figure 4It can be seen that the copper-cerium-alkali combination catalyst has good repeatability and stability. After repeated exposures, the obtained CO purification oxygen-rich catalyst still maintains a high level (>90%) in both CO conversion capacity and CO2 selectivity. This meets the characteristics of high efficiency and durability of catalysts in actual production. Combined with the advantages of low catalyst synthesis cost, the catalyst synthesized in this invention has great application potential in industrial production and environmental remediation.

[0101] Figure 5 The images show characterization diagrams of the catalysts obtained in Example 1 and Comparative Example 1, where the left image is a scanning electron microscope (SEM) image of the catalyst obtained in Comparative Example 1, and the right image is a scanning electron microscope (SEM) image of the catalyst obtained in Example 1. Figure 5 The left figure shows that after calcination in a reducing atmosphere, the catalyst supported on a single copper layer exhibits a partial transformation of its surface structure into a layered or quasi-layered structure, while retaining the integrity of its pores. This provides more adhesion sites for the metal. However, copper compounds may aggregate during calcination, leading to uneven dispersion on the catalyst surface and directly affecting catalytic performance. Figure 5 As can be seen from the right figure, more and more uniform particulate metal compounds appear on the catalyst surface, which indicates that the addition of cerium can effectively promote the dispersion of active components and improve the catalytic activity and selectivity of the catalyst.

[0102] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a CO purification oxygen-rich base catalyst, characterized by, The method comprises the following steps: dispersing γ-alumina in water, then adding copper nitrate and cerium nitrate in sequence to obtain a reaction solution; mixing the reaction solution with an inorganic base, then sequentially performing a substitution reaction and a crystallization reaction to obtain a catalyst precursor; calcining the catalyst precursor under a reducing atmosphere to obtain the CO purification oxygen-based catalyst; the reducing atmosphere comprises hydrogen; the mass ratio of copper in the copper nitrate to γ-alumina is 1:2-1:10; the mass ratio of cerium in the cerium nitrate to γ-alumina is 1:10-1:100; the temperature of the substitution reaction is room temperature, and the time is 5-6 hours; the temperature of the crystallization reaction is 80-240 ℃, the table pressure is 0.05-0.15 MPa, and the time for maintaining the temperature and pressure is 12-72 hours; the volume concentration of hydrogen in the reducing atmosphere is 5-20 %; the temperature of the calcination is 300-500 ℃, and the time for the calcination is 5-12 hours; in the CO purification oxygen-based catalyst, monovalent copper and divalent copper coexist, and cerium is mainly in the trivalent state; and the surface of the CO purification oxygen-based catalyst is attached with a metal-hydroxyl structure.

2. The production method according to claim 1, characterized by, the inorganic base is one or more of KOH, KHCO3, K2CO3 and ammonia water; the inorganic base is added in the form of an inorganic base solution, the inorganic base solution is added in the form of drops, and the drop adding speed of the inorganic base solution is 1-20 mL / min; the molar ratio of the inorganic base to copper nitrate is 1:1-1:

5.

3. The preparation method according to claim 1, characterized in that, the substitution reaction is performed under stirring.

4. The production method according to claim 1, characterized by, the atmosphere of the crystallization reaction comprises oxygen and inert gas; and the volume ratio of the oxygen to the inert gas is 1:1-10.

5. The purified CO oxygenate base catalyst produced by the process of any one of claims 1 to 4, characterized in that, in the CO purification oxygen-based catalyst, monovalent copper and divalent copper coexist, and cerium is mainly in the trivalent state; and the surface of the CO purification oxygen-based catalyst is attached with a metal-hydroxyl structure.

6. The CO purification oxygen-based catalyst in claim 5 is applied to purify CO.

7. Use according to claim 6, characterized in that, The method comprises the following steps: catalytically reacting a reaction gas under the action of the CO purification oxygen-based catalyst; the reaction gas comprises hydrogen, CO, oxygen and balance gas; in the reaction gas, the volume concentration of hydrogen is 50 %-80 %, the volume concentration of CO is 1 %-5 %, the volume concentration of oxygen is 1.25 %-10 %, and the balance is the balance gas; and the balance gas is helium; the temperature of the catalytic reaction is 30-220 ℃; the rate of temperature rise to the temperature of the catalytic reaction is 4 ℃ / min.

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