A supported copper-based catalyst for high-temperature synthesis of methanol and a preparation method and application thereof

Abstract

The application discloses a supported copper-based catalyst for high-temperature synthesis of methanol and a preparation method and application thereof, and belongs to the technical field of catalyst preparation and application. The catalyst takes copper as a main active component, takes oxides containing zinc and zirconium as a carrier, and adopts a high-energy plasma sputtering method to load copper nanoparticles on the carrier in one step, and can be applied to a reaction of carbon dioxide hydrogenation for preparing methanol under a relatively high reaction temperature condition. Compared with a commercially used Cu / ZnO / Al2O3 catalyst, the selectivity of methanol is increased from 10% to 85% under a reaction condition of 300 DEG C, and the space-time yield of methanol is increased by 2.6 times. The application is beneficial to opening up a new field of synthesis of methanol by using the copper-based catalyst under a relatively high reaction temperature, solves the problems of easy generation of methane or carbon monoxide byproducts by using a noble metal catalyst or an oxide catalyst, breaks through the seesaw limitation that the carbon dioxide conversion rate and the methanol selectivity cannot be compatible, and has an excellent application prospect.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation and application technology, specifically relating to a supported copper-based catalyst prepared by sputtering and its application in the carbon dioxide hydrogenation reaction at high temperature to obtain methanol products with high yield. Background Technology

[0002] The greenhouse effect caused by carbon emissions has brought about a series of environmental crises, such as ocean acidification, global warming, and sea-level rise, posing a huge threat to human survival. In the context of carbon neutrality and peak carbon emissions, methanol, as an important hydrogen storage medium, can store hydrogen obtained from renewable energy sources into the organic liquid methanol via CO2 molecules, facilitating the storage and transportation of hydrogen energy. Furthermore, methanol is an important C1 platform compound that can be further converted into important basic raw materials such as low-carbon olefins and aromatics. Connecting a CO2 hydrogenation reaction catalyst and a molecular sieve catalyst in series can convert CO2 into various fuels and high-value chemicals using methanol as an intermediate. The CO2 hydrogenation to methanol reaction is of great significance for controlling greenhouse gases and replacing fossil fuels.

[0003] Although the syngas-to-methanol process has been commercialized and industrialized after nearly a century of development, the activity of CO2 hydrogenation is generally low due to the relative stability of carbon dioxide molecules and the unfavorable activation of CO2 at low temperatures. Furthermore, the reaction temperature is limited by molecular sieve catalysts, requiring this route to be carried out at relatively high temperatures (300-400℃). However, CO2 hydrogenation is an exothermic reaction, and low temperatures favor methanol formation. While CO2 conversion increases at higher temperatures, it also produces a large amount of CO byproducts, resulting in low selectivity for the target product, methanol. Therefore, due to the dual limitations of thermodynamics and the chemical inertness of CO2, there is a "seesaw effect" between CO2 conversion and methanol selectivity on commonly used Cu catalysts, making it difficult to achieve high methanol yields. Therefore, developing CO2 hydrogenation catalysts for methanol production that can be used at higher temperatures is crucial.

[0004] Commonly used catalysts for CO2 hydrogenation to methanol include copper-based catalysts, noble metal catalysts, and oxide catalysts. Chinese invention patent application number 202111545432.7 discloses a metal-doped Cu-Zn-Zr / SiC catalyst. Under conditions of 6 MPa, 230 °C, and 6000 mL / (h·g), the aluminum-doped catalyst exhibits the best performance, achieving a CO2 conversion rate of 26.8% and a methanol selectivity of 81.8%. However, this catalyst requires relatively harsh reaction conditions and only exhibits high methanol selectivity at low temperatures, making it unsuitable for high-temperature applications. Chinese invention patent application number 201710756830.0 discloses a ZnZrOx solid solution oxide catalyst for CO2 hydrogenation to methanol. This solid solution catalyst performs well under conditions of 5 MPa, 320 °C, and 24000 h⁻¹. -1 Under certain conditions, methanol selectivity exceeding 88% and carbon dioxide single-pass conversion rate of 10% can be achieved at high temperatures, but the reaction conditions are quite harsh. Chinese invention patent application number 202210822628.4 discloses a CuGaZrOx catalyst for the hydrogenation of carbon dioxide to methanol. Although the methanol selectivity can be stably maintained at 88-89% under conditions of 3 MPa, 280℃, and 6000 mL / (h·g), the carbon dioxide single-pass conversion rate is only 5.4-6.6%, and the methanol selectivity drops sharply above 300℃. Furthermore, although this catalyst contains Cu components, the Cu atoms are doped in the ZrO2 lattice, acting as doped promoters like Ga atoms. Essentially, it is a ZrO2-based oxide catalyst, not a Cu-based supported catalyst with Cu as the active component. Summary of the Invention

[0005] Therefore, the purpose of this invention is to provide a supported copper-based catalyst for high-temperature methanol synthesis, its preparation method, and its application. This invention solves the technical problem of the "seesaw effect" in the catalytic high-temperature CO2 hydrogenation to methanol reaction of existing copper-based catalysts, where the conversion rate and methanol selectivity are mutually exclusive, making it difficult to obtain high yields. This invention provides a copper-based catalyst that is simple to prepare, low in cost, and convenient to use. Copper nanoparticles are loaded onto an oxide support containing Zn and Zr species in a one-step process using high-energy plasma sputtering, eliminating the need for subsequent calcination treatment and simplifying equipment and processes. During the reduction process, the prepared supported copper-based catalyst can generate new interfacial active sites between the metal and Zn species, which not only facilitates the further hydrogenation conversion of formate intermediates but also promotes the desorption of methanol products. It maintains high methanol selectivity even at high temperatures, while simultaneously improving CO2 conversion rate, significantly increasing methanol yield and laying the foundation for further conversion into high-value chemicals.

[0006] The objective of this invention is achieved through the following means:

[0007] This invention provides a method for preparing a supported copper-based catalyst, using copper as the main active component and an oxide containing zinc and zirconium components as a support. Copper nanoparticles are loaded onto the oxide support using a high-energy plasma sputtering method, followed by reduction treatment to form strong interactions between zinc species in the copper metal and the support, thereby obtaining a supported copper-based catalyst with a tunable copper-zinc active interface.

[0008] Based on the above technical solution, further, the mass fraction of copper component in the supported copper-based catalyst is 1-30%, preferably 5-20%; the molar content of zinc in the support is 1-90%, preferably 10-50%, and the remainder is zirconium component.

[0009] Based on the above technical solution, the oxide support containing zinc and zirconium components can be further prepared by any one of the following methods: co-precipitation, deposition precipitation, sol-gel method, and flame jetting method.

[0010] Based on the above technical solution, the preparation method further includes the following steps:

[0011] (1) A drum-type sputtering device is used to prepare the catalyst. The drum is a cylinder with a cylindrical cavity inside. The diameter of the cylindrical cavity is 20-80cm, preferably 30-50cm. The drum is placed in the sputtering instrument with its axis parallel to the horizontal plane. The carrier powder is placed at the bottom inside the drum. The sputtering target is placed directly above the carrier powder inside the drum. A copper target is installed with its surface facing down and directly facing the carrier powder. The drum is sealed inside the sputtering instrument cavity.

[0012] (2) Evacuate the sputtering chamber to a pressure of 8.0*10. -4 Below Pa, Ar gas or a mixture containing Ar gas is introduced into the drum, wherein the volume percentage concentration of Ar gas is 50-100%, the flow rate is 5-50 ml / min, and the pressure inside the drum is maintained at 0.1-1.0 Pa.

[0013] (3) Adjust the sputtering power of the plasma generator to 100-450W, increase the cylinder speed to 1-20rpm, and bombard the copper target with Ar ions. The resulting nano-metallic copper particles are uniformly deposited on the surface of the carrier. The sputtering time is 10-360min.

[0014] (4) After sputtering, a mixture of O2 and Ar gas is introduced into the cylinder until the pressure reaches atmospheric pressure. The volume percentage concentration of O2 in the mixture is 0.5-5%. The sputtering instrument is turned on and the catalyst powder is collected.

[0015] (5) Place the catalyst powder collected in step (4) in a hydrogen atmosphere and reduce it for 0.5-5 hours at a temperature of 200-600℃ and a pressure of 0.1-2MPa to obtain the catalyst powder.

[0016] Based on the above technical solution, further, the particle size of the carrier powder in step (1) is 0.01-1000μm, preferably 0.5-200μm; the filling amount of carrier powder inside the drum is 0.01-20% of the internal volume of the drum, preferably 0.1-5%.

[0017] Based on the above technical solution, further, in step (2), the vacuum is drawn until the pressure reaches 9.9*10. -6 -9.0*10 - 4 The volume percentage concentration of Ar gas is 80-100%, and the remaining gas is He. The flow rate is 10-30 ml / min, and the pressure inside the cylinder is maintained at 0.2-0.7 Pa.

[0018] Based on the above technical solution, further, the copper target material mentioned in step (3) has a purity of 98% or higher, preferably 99.9% or higher; the cylinder rotation speed is increased to 5-10 rpm, and the sputtering time is 15-240 min.

[0019] Based on the above technical solution, further, the volume percentage concentration of O2 in the mixed gas in step (4) is 1-3%.

[0020] Based on the above technical solution, further, in step (5), the reduction temperature is 300-500℃ and the pressure is 0.1-0.5MPa.

[0021] The present invention also provides a supported copper-based catalyst prepared by the above preparation method.

[0022] The present invention also provides the application of the above-mentioned supported copper-based catalyst in the reaction of CO2 hydrogenation to prepare methanol.

[0023] Based on the above technical solution, the further conditions for the CO2 hydrogenation reaction are as follows: the molar ratio of H2 to CO2 is 1-10, preferably 2-5; the reaction temperature is 260-360℃, preferably 280-320℃; and the reaction pressure is 0.1-10.0MPa, preferably 0.1-5MPa.

[0024] The advantages of this invention over the prior art are as follows:

[0025] The supported copper-based catalyst of this invention can be prepared in one step by high-energy plasma sputtering. During the reduction process, the prepared supported copper-based catalyst utilizes the strong metal-support interaction, with the metal and the Zn component in the support forming an active interface. This facilitates hydrogen activation, thereby promoting further hydrogenation of formate intermediates, and also promotes the desorption of methanol products. While improving CO2 conversion, it maintains high methanol selectivity. Compared with commercially used Cu / ZnO / Al2O3 catalysts, at a reaction temperature of 300℃, the methanol selectivity increases from 9% to 85%, and the space-time yield of methanol increases by 2.6 times. This invention opens up new avenues for the synthesis of methanol using copper-based catalysts at higher reaction temperatures. It solves the problem of methane or carbon monoxide byproducts easily generated on noble metal catalysts or oxide catalysts, and overcomes the trade-off between CO2 conversion and methanol selectivity, demonstrating excellent application prospects. Attached Figure Description

[0026] To more clearly illustrate the embodiments of the present invention, the accompanying drawings involved in the embodiments will be briefly described below.

[0027] Figure 1 The performance of SP-Cu / ZnZr catalysts with different Cu contents in the catalytic reaction of CO2 hydrogenation to methanol was investigated.

[0028] Figure 2 The performance of SP-Cu / ZnZr catalysts with different Zn and Zr ratios in catalyzing the hydrogenation of CO2 to methanol was investigated.

[0029] Figure 3 The performance of SP-Cu / ZnZr catalysts treated at different reduction temperatures in the catalytic reaction of CO2 hydrogenation to methanol was investigated.

[0030] Figure 4 The images show the electron microscope (A) image of the reduced Cu catalyst and the Zn elemental energy loss spectrum (B) from Example 8.

[0031] Figure 5 A comparison of the performance of different preparation methods and catalysts with different compositions in the catalytic hydrogenation of CO2 to methanol. Detailed Implementation

[0032] The technical details of this invention are described in detail in the following embodiments. It should be noted that the embodiments are only intended to further illustrate the technical features of this invention, and are not intended to limit the invention.

[0033] In this invention, CO2 conversion rate refers to the molar percentage of CO2 consumed at the reactor outlet to the amount of CO2 at the reactor inlet, wherein the CO2 consumed at the reactor outlet is the difference between the amount of CO2 at the reactor inlet and the amount of CO2 at the reactor outlet.

[0034] In this invention, methanol selectivity refers to the molar percentage of methanol in the product relative to all carbon-containing products (including methanol and carbon monoxide).

[0035] Example 1

[0036] The catalyst was prepared using a drum-type sputtering apparatus. The drum was a cylindrical shell with an internal cylindrical cavity, 35 cm in diameter. The drum was placed inside the sputtering apparatus with its axis parallel to the horizontal plane. The sputtering target was positioned directly above (at the top) inside the drum, and the drum was sealed within the sputtering apparatus cavity. 3 g of ZnZrO2 composite oxide carrier powder prepared by flame jetting (molar ratio Zn:Zr = 1:1) (see Comparative Example 1 for details) was mixed with 15 g of quartz sand particles (20-40 mesh). The mixture was then placed in a tray directly below the drum, and a copper target (99.9% purity) was installed with its surface facing down and directly opposite the carrier powder. The drum was evacuated to a pressure of 9.9 × 10⁻⁶. -4 High-purity Ar gas was introduced into the sputtering drum at a flow rate of 20 ml / min to maintain an internal pressure of 0.5 Pa. The Ar ion generator power was adjusted to 300 W, and the drum rotation speed was increased to 5.0 rpm, allowing the nano-sized copper particles generated by Ar ion bombardment of the copper target to be uniformly deposited on the carrier surface. The sputtering time was 10 minutes. After sputtering, a 1% O2 / Ar mixed gas was introduced into the drum to passivate the catalyst. After 30 minutes, the passivation gas was turned off, and Ar gas was introduced until the pressure reached atmospheric pressure. The sputtering instrument cavity was opened, and the catalyst powder was collected. Analysis showed that the Cu mass loading was 4.9%, and the average Cu particle size was 3.1 nm, denoted as SP-Cu / ZnZr-1.

[0037] Catalyst evaluation experiments were conducted in a fixed-bed microreactor. The reactor was a stainless steel reactor lined with quartz tubes. The catalyst was first reduced with pure hydrogen at atmospheric pressure and 400°C for 1 hour, then switched to a mixture of CO2 and H2 (volume ratio CO2:H2 = 1:3) at 3.0 MPa and 4800 ml / (g) cat. Under the condition of a mass hourly space velocity (h), the reaction was carried out at reaction temperatures of 260, 280, 300, 320, and 340 °C, respectively. The products after 1 hour of reaction were monitored by online gas chromatography. The reaction results are shown in [Figure number missing]. Figure 1 .

[0038] Example 2

[0039] The catalyst preparation and evaluation processes were the same as in Example 1, except that the sputtering time was increased to 15 minutes. The mass loading of Cu was found to be 9.5%, and the average particle size of Cu particles was 2.5 nm, denoted as SP-Cu / ZnZr-2. The reaction results are shown in [Figure Number]. Figure 1 .

[0040] Example 3

[0041] The catalyst preparation and evaluation processes were the same as in Example 1, except that the sputtering time was increased to 30 minutes. The mass loading of Cu was found to be 22.0%, and the average particle size of Cu particles was 2.5 nm, denoted as SP-Cu / ZnZr-3. The reaction results are shown below. Figure 1 .

[0042] Depend on Figure 1 It can be seen that different Cu contents (5-20%) have little effect on CO2 conversion rate, and no corresponding relationship between CO2 conversion rate and Cu content was found. In addition, when the Cu content is below 10%, it has little effect on methanol selectivity, but when the Cu content is high (around 20%), methanol selectivity is significantly reduced.

[0043] Example 4

[0044] The catalyst preparation process was the same as in Example 2, except that the molar ratio of Zn to Zr in the flame-jet-prepared ZnZrO2 composite oxide support was Zn:Zr = 1:3, denoted as SP-Cu / ZnZr-4. The reaction results are shown in Table 1. 0.25 g of the SP-Cu / ZnZr-4 catalyst prepared in Example 4 was loaded into the reactor and reduced at 400°C for 1 hour in a pure hydrogen atmosphere at a pressure of 0.1 MPa. A mixture of reactants CO2 and H2 (volume ratio CO2:H2 = 1:3) was introduced at a pressure of 3.0 MPa and a mass hourly space velocity (WHSV) of 4800 ml / (g). cat Under the conditions of ·h), the reaction was carried out at reaction temperatures of 260, 280, 300, 320, 340℃, and 360℃ for 1 hour, respectively. The results are shown in the figure. Figure 2 .

[0045] Example 5

[0046] The catalyst preparation and evaluation processes are the same as in Example 4, except that the molar ratio of Zn to Zr in the flame-jet-prepared ZnZrO2 composite oxide support is Zn:Zr = 1:2, denoted as SP-Cu / ZnZr-5. The reaction results are shown in [Figure 4]. Figure 2 .

[0047] Depend on Figure 2 It can be seen that adjusting the molar ratio of Zn to Zr in the support can significantly change the catalytic performance. When the ratio of Zn to Zr is 1:3 and 1:2, the methanol yield reaches its maximum at a reaction temperature of 280 degrees Celsius; when the ratio of Zn to Zr is 1:1, the methanol yield reaches its maximum at a reaction temperature of 300 degrees Celsius.

[0048] Example 6

[0049] The reactor was loaded with 0.25 g of the SP-Cu / ZnZr-2 catalyst prepared in Example 2, and reduced at 200 °C for 1 hour in a pure hydrogen atmosphere at a pressure of 0.1 MPa. A mixture of reactants CO2 and H2 (volume ratio CO2:H2 = 1:3) was introduced, and the reaction was carried out at a pressure of 3.0 MPa and a mass hourly space velocity of 4800 ml / (g). cat Under the conditions of (·h), the reaction was carried out at 260, 280, 300, 320, and 340 °C for 1 hour, respectively. The results are shown in […]. Figure 3 .

[0050] Example 7

[0051] The catalyst evaluation process was the same as in Example 6, with the reduction treatment temperature at 300℃. The results are shown below. Figure 3 .

[0052] Example 8

[0053] The catalyst evaluation process was the same as in Example 6, with the reduction treatment temperature at 400℃. The results are shown below. Figure 3 Electron micrographs and elemental analyses of the reduced catalyst are shown below. Figure 4 .

[0054] Depend on Figure 4 Electron microscopy images show that Cu particles are loaded on the support, and there is an amorphous coating layer on the surface of the Cu particles. Elemental analysis by energy loss spectroscopy shows that, compared with the sample-free region (region II), the coating layer (region I) contains a Zn signal, indicating that the region is a Zn species. This confirms that the method of the present invention can induce the formation of a Cu-Zn interface on the surface of a supported Cu catalyst by utilizing strong metal-support interactions.

[0055] Example 9

[0056] The catalyst evaluation process was the same as in Example 6, with the reduction treatment temperature at 500℃. The results are shown below. Figure 3 .

[0057] Depend on Figure 3 It can be seen that the methanol yield first increases and then decreases with the reaction temperature, reaching a maximum at 300 degrees Celsius. Furthermore, the reduction temperature significantly affects the catalyst performance, with the methanol yield reaching a maximum at a reduction temperature of 400 degrees Celsius.

[0058] Comparative Example 1

[0059] Preparation of Zn:Zr = 1:1 (molar ratio) zinc zirconium oxide catalyst by flame jet method: 21.31 g of zinc 2-ethylhexanoate was weighed and dissolved in 135 ml of xylene. 29.18 g of zirconium acetylacetonate was weighed and dissolved in 100 ml of 2-ethylhexanoic acid solvent. The solutions were mixed and ultrasonicated for 1 hour. The prepared solution was then pumped into a flame jet apparatus at a flow rate of 5 ml / min. After the experiment, the catalyst powder was collected on filter paper and labeled as ZnZrO2. 0.25 g of the ZnZrO2 catalyst prepared in Comparative Example 1 was loaded into a reactor and reduced at 400 °C for 1 hour in a pure hydrogen atmosphere at a pressure of 0.1 MPa. A mixture of reactants CO2 and H2 (volume ratio CO2:H2 = 1:3) was introduced at a pressure of 3.0 MPa and a mass hourly space velocity (WHSV) of 4800 ml / (g·kg⁻¹). cat The reaction was carried out at 300℃ for 1 hour under the conditions of ·h), and the results are shown in […]. Figure 5 .

[0060] Comparative Example 2

[0061] A one-step preparation of Cu / ZnZr catalyst using a flame jet method: 2.42 g of copper acetate monohydrate powder was weighed and dissolved in a mixture of 50 ml methanol and 50 ml xylene. 25.89 g of zirconium n-butoxide was weighed and dissolved in 40 ml xylene. 19.62 g of zinc 2-ethylhexanoate was weighed and dissolved in 100 ml xylene. The three solutions were mixed and sonicated for 1 hour. The prepared solution was then pumped into the flame jet apparatus at a flow rate of 5 ml / min. After the experiment, the catalyst powder was collected on filter paper and denoted as CuZnZr. The catalyst evaluation process was the same as in Comparative Example 1, and the results are shown in [Figure 1]. Figure 5 .

[0062] Comparative Example 3

[0063] The reactor was loaded with 0.25 g of commercial CuZnAl catalyst (manufactured by Asia Union Company), and reduced at 400 °C for 1 hour in a pure hydrogen atmosphere at a pressure of 0.1 MPa. A mixture of reactants CO2 and H2 (volume ratio CO2:H2 = 1:3) was introduced, and the reaction was carried out at a pressure of 3.0 MPa and a mass hourly space velocity of 4800 ml / (g). cat The reaction was carried out at 300℃ for 1 hour under the conditions of ·h), and the results are shown in […]. Figure 5 .

[0064] Depend on Figure 5It can be seen that, compared with the ZnZr oxide catalyst without Cu in Comparative Example 1, the SP-Cu / ZnZr catalyst has comparable methanol selectivity but higher conversion rate, resulting in a 2.6-fold increase in methanol yield. Compared with the one-step flame-jet Cu / ZnZr catalyst in Comparative Example 2, the SP-Cu / ZnZr catalyst shows a 10-fold increase in methanol selectivity. Although the CO2 conversion rate is higher on the catalyst in Comparative Example 2, the methanol yield is limited by selectivity and cannot be improved. Compared with the commercial CuZnAl catalyst in Comparative Example 3, the methanol yield in Comparative Example 3 is also limited by selectivity and cannot be improved. In summary, the SP-Cu / ZnZr catalyst of this invention has high methanol selectivity and conversion rate, while achieving a high methanol yield.

[0065] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. Use of a supported copper-based catalyst, characterized in that, It is applied to the reaction of CO2 hydrogenation to prepare methanol; the supported copper-based catalyst takes copper as the main active component, takes the oxide containing zinc and zirconium components as the carrier, loads copper nanoparticles on the oxide carrier by using high-energy plasma sputtering method, and reduces treatment to form a strong interaction between copper metal and zinc species in the carrier, so that a supported copper-based catalyst with a controllable copper-zinc active interface is obtained; The mass fraction of the copper component in the supported copper-based catalyst is 1-30%; the molar content of zinc in the carrier is 1-90%, and the rest is the zirconium component; The oxide carrier containing zinc and zirconium components is prepared by any one of a coprecipitation method, a deposition precipitation method, a sol-gel method, and a flame spraying method; The preparation method of the supported copper-based catalyst comprises the following steps: (1) a drum-type sputtering device is used to prepare the catalyst, the drum is a cylinder with a cylindrical cavity inside, the diameter of the cylindrical cavity is 20-80 cm, the drum is placed in the sputtering instrument with the axis parallel to the horizontal plane, the carrier powder is placed at the bottom of the inside of the drum, the sputtering target head is placed directly above the carrier powder in the inside of the drum, the copper target material is installed with the surface downward facing the carrier powder, and the drum is sealed in the sputtering instrument cavity; (2) The sputtering instrument cavity is vacuumed to a pressure of 8.0*10 -4 The volume percentage concentration of Ar gas in the mixed gas is 50-100%, the flow rate of Ar gas is 5-50 mL / min, and the pressure in the cylinder is maintained at 0.1-1.0 Pa. (3) the sputtering power of the plasma generator is adjusted to 100-450 W, the drum rotation speed is increased to 1-20 rpm, the copper target material is bombarded by Ar ions, and the generated nano copper particles are uniformly deposited on the surface of the carrier; the sputtering time is 10-360 min; (4) after the sputtering is completed, the mixed gas of O2 and Ar is introduced into the drum to reach the pressure of normal pressure, the volume percentage concentration of O2 in the mixed gas is 0.5-5%, the sputtering instrument is opened, and the catalyst powder is collected; (5) The catalyst powder collected in step (4) is reduced in a hydrogen atmosphere at a temperature of 200-600 o C and a pressure of 0.1-2 MPa for 0.5-5 h.

2. Use according to claim 1, characterized in that, The diameter of the cylindrical cavity is 30-50 cm.

3. Use according to claim 1, characterized in that, The mass fraction of the copper component in the supported copper-based catalyst is 5-20%; the molar content of zinc in the carrier is 10-50%, and the rest is the zirconium component.

4. Use according to claim 1, characterized in that, The particle size of the carrier powder in step (1) is 0.01-1000 µm; the loading amount of the carrier powder inside the drum is 0.01-20% of the internal volume of the drum; in step (2), the vacuum is drawn to a pressure of 9.9*10 -6 - 9.0*10 -4 Pa, the volume percentage concentration of Ar gas is 80-100%, the rest is He, the flow rate is 10-30 mL / min, and the internal pressure of the drum is maintained at 0.2-0.7 Pa.

5. Use according to claim 4, characterized in that, The particle size of the carrier powder in step (1) is 0.5-200 µm; the filling amount of the carrier powder in the inside of the drum is 0.1-5% of the internal volume of the drum.

6. The use according to claim 1, characterized in that, The mass purity of the copper target material in step (3) is more than 98%; the drum rotation speed is increased to 5-10 rpm, the sputtering time is 15-240 min; and the volume percentage concentration of O2 in the mixed gas in step (4) is 1-3%.

7. Use according to claim 6, characterized in that, The mass purity of the copper target material in step (3) is more than 99.9%.

8. The use according to claim 1, characterized in that, The reduction temperature in step (5) is 300-500 o C and the pressure is 0.1-0.5 MPa.

9. The use according to claim 1, characterized in that, The CO2 hydrogenation reaction conditions are: the molar ratio of H2 and CO2 is 1-10, the reaction temperature is 260-360 o C, and the reaction pressure is 0.1-10.0 MPa.

10. Use according to claim 9, characterized in that, The CO2 hydrogenation reaction conditions are: the molar ratio of H2 and CO2 is 2-5, the reaction temperature is 280-320 o C, and the reaction pressure is 0.1-5 MPa.

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