Cu2o-supported znzro composite metal oxide reverse-phase catalyst based on methanol production from carbon dioxide hydrogenation x ​

Abstract

The application relates to a Cu2O supported ZnZrO x composite metal oxide reverse-phase catalyst based on carbon dioxide hydrogenation methanol production, and belongs to the field of carbon neutralization. Carbon dioxide hydrogenation methanol production has important research value under the background of "double carbon", but due to the problems of poor stability, sintering and agglomeration of active sites, low hydrogenation performance and the like of current catalysts, the application provides a Cu2O supported ZnZrO x composite metal oxide reverse-phase catalyst with high thermal stability, strong sintering resistance and excellent hydrogenation activity. The reverse-phase catalyst has good methanol selectivity and stability.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of carbon neutralization, and particularly relates to a Cu2O loaded ZnZrO x composite metal oxide reverse phase catalyst applied to carbon dioxide hydrogenation to prepare methanol. BACKGROUND

[0002] With the continuous development of the world industry, the global greenhouse gas emission continues to increase, the greenhouse effect is increasingly serious, and climate change has brought very serious challenges to our life. According to research statistics, CO2 is the main gas causing the greenhouse effect, which accounts for more than 70% of global greenhouse gases, leading to a series of ecological and environmental problems such as sea level rise, glacier melting, ocean acidification and energy crisis. Synthesizing methanol from CO2 as raw material opens up a new way for effective utilization of carbon resources.

[0003] Cu-based catalyst is the most widely used among all types of methanol catalysts, and has the advantages of large specific surface area and high dispersion. However, research shows that Cu-based catalysts have poor stability, active site sintering and agglomeration, low hydrogenation performance and other conditions in the reaction process, and do not have the ability to effectively catalyze CO2 hydrogenation to synthesize methanol. However, the introduction of oxides such as ZnO and ZrO2 can effectively improve the dispersion degree of Cu and the stability of the catalyst, and form Cu-Zn synergistic effect.

[0004] Traditional supported oxide catalysts usually load metals on the surface of oxides, and the surface energy is large, the structure is unstable, and it is difficult to obtain single valence state as active site for research. The reverse phase catalyst disperses oxide nanoparticles on the surface of the metal, and the electronic and chemical properties of the oxide change with the size of the particles and the interaction between the metal carrier. The metal exists in the form of bulk carrier, providing metal sites. Therefore, the oxide sites, metal sites and metal-oxide interface sites in the reverse phase catalyst system can simultaneously adsorb and activate different reaction substrate molecules, and promote the further conversion of related intermediate species.

[0005] The application selects a copper-containing compound as a precursor, selects sodium citrate as a reducing agent, and adopts sodium hydroxide as a precipitant to prepare a Cu2O loaded ZnZrO xThis invention relates to a composite metal oxide reverse-phase catalyst. The innovations in the catalyst's structure and catalytic reaction pathway result in excellent catalytic performance for the CO2 hydrogenation reaction. By modifying the catalyst's surface oxides and controlling the size of the metal support, the catalytic activity, methanol selectivity, and catalyst stability are improved. Furthermore, these innovations not only enhance catalyst performance but also provide new pathways for the preparation of green energy and chemicals. Converting CO2 into high-value-added liquid methanol resources holds promise for effectively addressing both environmental and energy challenges. Summary of the Invention

[0006] This invention addresses the problems of poor catalyst stability, sintering and agglomeration of active sites, and low hydrogenation performance in current catalysts by providing a Cu2O-supported ZnZrO catalyst with high stability and resistance to reduction. x The composite metal oxide reversed-phase catalyst exhibits good methanol selectivity and stability.

[0007] In a first aspect, embodiments of the present invention provide a Cu2O-supported ZnZrO x A composite metal oxide reverse-phase catalyst, applied to the hydrogenation of CO2 to methanol, characterized in that it comprises:

[0008] Cu2O support and ZnZrO x The reverse catalyst of oxides, where x takes values ​​from 1 to 3.

[0009] Optionally, the Cu2O support has a powder size of 10–2000 nm, and ZnZrO x The powder size of the oxide is 1–100 nm.

[0010] Secondly, embodiments of the present invention provide a Cu2O-supported ZnZrO as described in the first aspect of the embodiments above. x The preparation method of the composite metal oxide reversed-phase catalyst is characterized by the use of a fixed-bed reactor, the introduction of a mixed gas with a molar ratio of CO2 / H2 / N2 = 1 / 1.0–5.0 / 0.5–5, the flow rate controlled at 10–150 mL / min, the reaction pressure maintained at 0.5–5 MPa, the reaction temperature set at 180–300 °C, and the online detection and calculation of CO2 conversion and methanol selectivity using gas chromatography. The specific preparation method includes the following steps:

[0011] (1) Contains Cu 2+The precursor, reducing agent, 4.8M NaOH solution and ultrapure water are mixed uniformly in a mass ratio of 1-15:10-25:10-25:500-2500, the reaction temperature is set to 50-150℃, and the reaction is stirred at a speed of 100-1000rpm for 0.5-25h. Then 0.1-15g of ascorbic acid is added, and the reaction is stirred at a speed of 100-1000rpm for 0.5-30h. After the product is cooled to room temperature, it is washed and centrifuged alternately with ultrapure water and anhydrous ethanol. The product is dried in a vacuum drying oven at 40-100℃ for 6-72h to obtain the Cu2O material.

[0012] (2) The Cu2O, Zn 2+ The precursor, Zr 4+ The precursor and ultrapure water are mixed uniformly in a mass ratio of 1.5-15:0.1-3:0.1-5:1.5-15, the reaction temperature is set to 50-250℃, and the reaction is stirred at a speed of 100-1000rpm for 0.5-30h. The product is dried in a vacuum drying oven at 40-100℃ for 6-72h. Then the dried product is calcined in a helium inert gas atmosphere for 2-10h, and the calcination temperature is set to 200-600℃ to obtain the ZnZrO x / Cu2O material.

[0013] Optionally, the Cu precursor in step (1) includes one of the following compounds:

[0014] CuSO4, CuCl2·2H2O, Cu(CH3COO)2, Cu(NO3)2·3H2O

[0015] Optionally, the reducing agent in step (1) includes one of the following compounds:

[0016] Sodium citrate, L-ascorbic acid

[0017] Optionally, the Zn 2+ precursor in step (2) includes one of the following compounds:

[0018] Zn(NO3)2·6H2O, Zn(CH3COO)2, Zn(OH)2, Zn2(OH)2CO3

[0019] Optionally, the Zr 4+ precursor in step (2) includes one of the following compounds:

[0020] Zr(NO3)4·5H2O, ZrOCl2·8H2O

[0021] Optionally, the ZnZrO xThe mass of the metal precursor is 0.02-0.4 times the mass of Cu2O, and the mass ratio of Zn to Zr is 1.0-5.0.

[0022] Optionally, in step (2), the treatment under the inert gas atmosphere of helium is carried out at a temperature of 200-600 DEG C for 1-10 hours.

[0023] Optionally, the ultrapure water in steps (1) and (2) can be replaced by deionized water.

[0024] Compared with the prior art, the scheme provided in the embodiments of the application can produce the following beneficial effects:

[0025] The application provides a preparation principle of a Cu2O-supported ZnZrO x composite metal oxide reverse-phase catalyst structure. x The active center of the reverse-phase structure of the metal oxide is relatively uniformly distributed, the contact area between the catalyst and the reactants is increased, sufficient reaction active sites are provided, and therefore the hydrogenation activity and the methanol selectivity are improved. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 SEM image of Cu2O prepared in Example 1;

[0027] Figure 2 XRD image of Cu2O prepared in Example 1;

[0028] Figure 3 XRD image of Cu2O surface-loaded ZnZrO x prepared in Example 1;

[0029] Figure 4 CO2 conversion performance graph of Cu2O surface-loaded ZnZrO x and Cu surface-loaded ZnZrO x prepared in Comparative Example 1 prepared in Example 1;

[0030] Figure 5 Methanol selectivity performance graph of Cu2O surface-loaded ZnZrO x and Cu surface-loaded ZnZrO x prepared in Comparative Example 1 prepared in Example 1. DETAILED DESCRIPTION

[0031] The embodiment of the present application provides a composite metal oxide reverse-phase catalyst with Cu2O loaded ZnZrO x , which is applied to CO2 hydrogenation to prepare methanol, and is characterized in that the reverse-phase catalyst comprises a Cu2O carrier and ZnZrO x oxide, and x is 1-3.

[0032] The powder size of the Cu2O carrier is (10-2000) nm, and the powder size of the ZnZrO x oxide is (1-100) nm.

[0033] The embodiment of the present application provides a preparation method of a composite metal oxide reverse-phase catalyst with Cu2O loaded ZnZrO x , which is characterized in that a fixed bed reactor is used, a mixed gas with a molar ratio of CO2 / H2 / N2=1 / 1.0-5.0 / 0.5-5 is introduced, the flow rate is controlled at 10-150 mL / min, the reaction pressure is maintained at 0.5-5 MPa, the reaction temperature is set at 180-300 DEG C, and a gas chromatograph is used for online detection and calculation to obtain the conversion rate of CO2 and the selectivity of methanol.

[0034] (1) a Cu 2+ precursor, a reducing agent, a 4.8M NaOH solution and ultrapure water are mixed uniformly according to a mass ratio of 1-15:10-25:10-25:500-2500, the reaction temperature is set at 50-150 DEG C, and stirring is performed at a rotation speed of 100-1000 rpm for 0.5-25 h. Then, 0.1-15 g of ascorbic acid is added, and stirring is performed at a rotation speed of 100-1000 rpm for 0.5-30 h. After the product is cooled to room temperature, it is washed and centrifuged alternately by using ultrapure water and anhydrous ethanol. The product is dried in a vacuum drying box at 40-100 DEG C for 6-72 h, and the Cu2O material is obtained.

[0035] (2) the Cu2O obtained in the step (1), a Zn 2+ precursor, a Zr 4+ precursor and ultrapure water are mixed uniformly according to a mass ratio of 1.5-15:0.1-3:0.1-5:1.5-15, the reaction temperature is set at 50-250 DEG C, and stirring is performed at a rotation speed of 100-1000 rpm for 0.5-30 h. The product is dried in a vacuum drying box at 40-100 DEG C for 6-72 h. Then, the dried product is calcined under a helium inert gas atmosphere for 2-10 h, and the calcination temperature is set at 200-600 DEG C, and the ZnZrO x / Cu2O material is obtained.

[0036] Optionally, the Cu precursor in the step (1) comprises one of the following compounds:

[0037] CuSO4, CuCl2·2H2O, Cu(CH3COO)2, Cu(NO3)2·3H2O

[0038] Optionally, the reducing agent in step (1) includes one of the following compounds:

[0039] Sodium citrate, L-ascorbic acid

[0040] Optionally, the Zn in step (2) 2+ The precursors include one of the following compounds:

[0041] Zn(NO3)2·6H2O, Zn(CH3COO)2, Zn(OH)2, Zn2(OH)2CO3

[0042] Optionally, the Zr in step (2) 4+ The precursors include one of the following compounds:

[0043] Zr(NO3)4·5H2O, ZrOCl2·8H2O

[0044] Optionally, the ZnZrO added in step (2) x The mass of the metal precursor is 0.02 to 0.4 times the mass of Cu2O, wherein the molar ratio of Zn to Zr is 1.0 to 5.0.

[0045] Optionally, in step (2), the gas is treated with helium inert gas at a temperature of 200–600°C for 1–10 hours.

[0046] Optionally, the ultrapure water described in steps (1) and (2) can be replaced with deionized water.

[0047] The following detailed examples illustrate Cu2O-loaded ZnZrO. x The structure and preparation process of the composite metal oxide reversed-phase catalyst.

[0048] Example 1: Preparation of Cu2O-supported ZnZrO x Reverse catalyst structure

[0049] 0.80 g of sodium citrate, 100 mL of ultrapure water were added into a round bottom flask and mixed well, heated in a 90 °C water bath for 20 min. Then 1 ml of 1.2 M CuSO4 solution was injected with a pipette. After 30 min, 1 mL of 4.8 M NaOH solution was injected into the solution. Then 1.2 M ascorbic acid (AA) 1 mL was injected, and kept in the water bath for 30 min. Filtered and washed three times with deionized water and alcohol. Dried in a vacuum drying oven at 60 °C for 2 h to obtain Cu2O material with a size of 800 nm.

[0050] The above obtained Cu2O and ultrapure water were mixed well in a mass ratio of 1:2, 0.2 g of Zn(NO3)2·6H2O and 0.1314 g of Zr(NO3)4·5H2O were added and soaked for 12 h. Dried in a vacuum drying oven at 200 °C for 24 h. Then the dried product was calcined in a helium inert gas atmosphere for 5 h to obtain ZnZrO x / Cu2O material, wherein ZnZrO x The material size is 50 nm.

[0051] Comparative Example 1: Preparation of ZnZrO x structure

[0052] A sufficient amount of Cu2O synthesized in the example was weighed into a magnetic boat and calcined in a tube furnace at 400 °C in a 10% H2 / Ar mixed gas atmosphere for 4 h, with a heating rate controlled at 5 °C / min. After cooling to room temperature, a Cu carrier material with a size of 800 nm was obtained.

[0053] 1 g of Cu carrier was ultrasonically dispersed in 2 mL of ultrapure water, 0.0916 g of Zn(NO3)2·6H2O and 0.1314 g of Zr(NO3)4·5H2O were added and soaked and stirred for 10 h until the ultrapure water was completely evaporated, and then dried in an oven for 6 h. Then the sample was calcined in a helium inert gas atmosphere at 400 °C for 4 h, with a heating rate controlled at 5 °C / min, to obtain a Cu carrier loaded ZnZrO x material (ZnZrO x / Cu), wherein ZnZrO x The material size is 50 nm.

[0054] ZnZrO x was loaded on the surface of Cu2O obtained in Example 1, and ZnZrO xThe sample was subjected to CO2 hydrogenation catalytic reaction. A fixed bed reactor was used, and a mixed gas with a molar ratio of CO2 / H2 / N2=1.0 / 1.0 / 5.0 was introduced at a flow rate of 100 mL / min. The reaction pressure was maintained at 3 MPa, and the reaction temperature was set to 250°C. The CO2 conversion rate and methanol selectivity were obtained by online detection and calculation using a gas chromatograph. The prepared Cu2O surface loaded ZnZrO x The sample was subjected to CO2 hydrogenation catalytic reaction. A fixed bed reactor was used, and a mixed gas with a molar ratio of CO2 / H2 / N2=1.0 / 1.0 / 5.0 was introduced at a flow rate of 100 mL / min. The reaction pressure was maintained at 3 MPa, and the reaction temperature was set to 250°C. The CO2 conversion rate and methanol selectivity were obtained by online detection and calculation using a gas chromatograph. The prepared Cu2O surface loaded ZnZrO x The CO2 hydrogenation catalytic performance of the sample was significantly improved. The CO2 conversion rate at 300°C was as high as 28.88%, which was higher than that of the metal Cu surface loaded ZnZrO x (15.24%). At the same time, the prepared Cu2O surface loaded ZnZrO x The methanol selectivity of the sample was as high as 45.13%, which was higher than that of the metal Cu particle surface loaded ZnZrO x The sample was 15% higher. It showed that the Cu2O surface loaded ZnZrO x The sample had good CO2 conversion rate and methanol selectivity.

[0055] Example 2

[0056] Cu2O loaded ZnZrO x The preparation method of the composite metal oxide reverse phase catalyst comprises the following steps:

[0057] 0.40 g of sodium citrate and 400 mL of ultrapure water were added to a round-bottom flask and mixed uniformly. The mixture was heated in a 20°C water bath for 20 min. Then 1 ml of 1.2M CuSO4 solution was injected using a pipette. After 5 min, 1 mL of 4.8M NaOH solution was injected into the solution. Then 1.2M ascorbic acid (AA) 1 mL was injected, and the mixture was kept in the water bath for 30 min. The mixture was filtered and washed three times with deionized water and alcohol. The mixture was dried in a vacuum drying oven at 60°C for 2 h to obtain Cu2O material with a size of 500 nm.

[0058] The obtained Cu2O and ultrapure water were mixed uniformly at a mass ratio of 1:2, and 0.0916 g of Zn(NO3)2·6H2O and 0.1314 g of Zr(NO3)4·5H2O were added and soaked for 12 h. The mixture was dried in a vacuum drying oven at 200°C for 24 h. Then the dried product was calcined in a helium inert gas atmosphere for 5 h to obtain ZnZrO x / Cu2O material, wherein the ZnZrO x The size of the material was 50 nm.

[0059] CO2 hydrogenation reaction was carried out on the ZnZrO xThe Cu2O material was placed in a fixed bed reactor, and a mixed gas with a molar ratio of CO2 / H2 / N2=1.0 / 1.0 / 5.0 was introduced at a flow rate of 100 mL / min, the reaction pressure was maintained at 3 MPa, the reaction temperature was set to 250°C, and the CO2 conversion rate and methanol selectivity were obtained by online detection and calculation using a gas chromatograph. At 300°C, the CO2 conversion rate reached 23.67%, and the methanol selectivity reached 42.67%.

[0060] Example 3

[0061] Preparation method of Cu2O supported ZnZrO x The preparation method of the composite metal oxide reverse phase catalyst comprises the following steps:

[0062] 0.20 g of sodium citrate and 400 mL of ultrapure water were added to a round-bottom flask and mixed uniformly, and heated in a 20°C water bath for 20 min. Then 1 ml of 1.2M CuSO4 solution was injected using a pipette. After 5 min, 1 mL of 4.8M NaOH solution was injected into the solution. Then 1.2M ascorbic acid (AA) 1 mL was injected, and it was kept in the water bath for 30 min. Filtration and washing were performed three times with deionized water and alcohol. Drying was performed in a vacuum drying box at 60°C for 2 h, and the Cu2O material with a size of 100 nm was obtained.

[0063] The Cu2O obtained above and ultrapure water were mixed uniformly at a mass ratio of 1:2, 0.0916 g of Zn(NO3)2·6H2O and 0.1314 g of Zr(NO3)4·5H2O were added, and impregnation was performed for 12 h. The product was placed in a vacuum drying box, the reaction temperature was set to 200°C, and drying was performed for 24 h. Then the dried product was calcined under a helium inert gas atmosphere for 5 h, and the ZnZrO x / Cu2O material was obtained, wherein the ZnZrO x material had a size of 50 nm.

[0064] CO2 hydrogenation reaction was performed on the ZnZrO x / Cu2O material in Example 3, which was placed in a fixed bed reactor, and a mixed gas with a molar ratio of CO2 / H2 / N2=1.0 / 1.0 / 5.0 was introduced at a flow rate of 100 mL / min, the reaction pressure was maintained at 3 MPa, the reaction temperature was set to 250°C, and the CO2 conversion rate and methanol selectivity were obtained by online detection and calculation using a gas chromatograph. At 300°C, the CO2 conversion rate reached 19.12%, and the methanol selectivity reached 40.67%.

[0065] Example 4

[0066] Preparation method of Cu2O supported ZnZrO xA method for preparing a composite metal oxide reverse phase catalyst, comprising the following steps:

[0067] 0.05 g of sodium citrate and 400 mL of ultrapure water were added to a round-bottom flask and mixed well, and heated in a 20°C water bath for 20 min. Then 1 mL of 1.2M CuSO4 solution was injected with a pipette. After 5 min, 1 mL of 4.8M NaOH solution was injected into the solution. Then 1 mL of 1.2M ascorbic acid (AA) was injected, and it was kept in the water bath for 30 min. It was filtered and washed three times with deionized water and alcohol. It was dried in a vacuum drying oven at 60°C for 2 h, and Cu2O material with a size of 50 nm was obtained.

[0068] The Cu2O obtained above and ultrapure water were mixed well in a mass ratio of 1:2, 0.0916 g of Zn(NO3)2·6H2O and 0.1314 g of Zr(NO3)4·5H2O were added, and impregnated for 12 h. It was dried in a vacuum drying oven at 200°C for 24 h. Then the dried product was calcined in a helium inert gas atmosphere for 5 h, and ZnZrO x / Cu2O material was obtained, wherein the size of the ZnZrO x material was 50 nm.

[0069] The ZnZrO x / Cu2O material in Example 4 was placed in a fixed bed reactor, and a mixed gas with a molar ratio of CO2 / H2 / N2=1.0 / 1.0 / 5.0 was introduced, with a flow rate controlled at 100 mL / min, the reaction pressure was maintained at 3 MPa, and the reaction temperature was set at 250°C. Gas chromatography was used for online detection and calculation to obtain the CO2 conversion rate and methanol selectivity. At 300°C, the CO2 conversion rate reached 17.54%, and the methanol selectivity reached 38.12%.

Claims

1. A Cu2O supported ZnZrO2 composite metal oxide reverse phase catalyst for the hydrocarbonation of carbon dioxide to methanol. x A composite metal oxide reverse phase catalyst characterized by, Comprising: Cu2o-containing support and znzro x inverse catalyst of oxides, x having a value of 1-3; the method for its preparation comprises the following steps: (1) Cu-containing 2+ The precursor, the reducing agent, the 4.8 M NaOH solution and the ultrapure water are mixed uniformly in a mass ratio of 1-15:10-25:10-25:500-2500, the reaction temperature is set to 50-150℃, and the reaction is stirred at a rotation speed of 100-1000 rpm for 0.5-25 h; then 0.1-15 g of ascorbic acid is added, and the reaction is stirred at a rotation speed of 100-1000 rpm for 0.5-30 h; after the product is cooled to room temperature, it is washed and centrifuged alternately by ultrapure water and anhydrous ethanol; and the product is dried in a vacuum drying box at 40-100℃ for 6-72 h, to obtain the Cu2O material; the Cu-containing 2+ The precursor is one of the following compounds: CuSO4, CuCl2·2H2O, Cu(CH3COO)2, Cu(NO3)2·3H2O; and the reducing agent is sodium citrate. (2) mixing the Cu2O, Zn 2+ precursor, Zr 4+ The precursor and ultrapure water are mixed uniformly at a mass ratio of 1.5-15:0.1-3:0.1-5:1.5-15, the reaction temperature is set to 50-250℃, the reaction is stirred at a rotation speed of 100-1000rpm for 0.5-30h, dried in a vacuum drying oven at 200℃ for 24h, and then the dried product is calcined in a helium inert gas atmosphere for 2-10h, with the calcination temperature set to 200-600℃, to obtain a ZnZrO x / Cu2O material.

2. The Cu2O supported ZnZrO according to claim 1 x The composite metal oxide reverse phase catalyst is characterized by comprising: The powdered size of the Cu2O support is 10-2000 nm, the ZnZrO x The powdered size of the oxide is 1-100 nm.

3. Process for the preparation of the reversed phase catalyst according to claim 1 or 2, characterized in that, The preparation method specifically comprises the following steps: (1) Cu-containing 2+ The precursor, reducing agent, 4.8 M NaOH solution and ultrapure water are mixed uniformly at a mass ratio of 1-15:10-25:10-25:500-2500, the reaction temperature is set to 50-150°C, and the reaction is stirred at a speed of 100-1000 rpm for 0.5-25 h; then 0.1-15 g of ascorbic acid is added, and the reaction is stirred at a speed of 100-1000 rpm for 0.5-30 h; after the product is cooled to room temperature, it is washed and centrifuged alternately with ultrapure water and anhydrous ethanol; and the product is dried in a vacuum drying box at 40-100°C for 6-72 h to obtain a Cu2O material. (2) mixing the Cu2O, Zn 2+ precursor, Zr 4+ The precursor and ultrapure water are mixed uniformly at a mass ratio of 1.5-15:0.1-3:0.1-5:1.5-15, the reaction temperature is set to 50-250℃, the reaction is stirred at a rotation speed of 100-1000rpm for 0.5-30h, dried in a vacuum drying oven at 200℃ for 24h, and then the dried product is calcined in a helium inert gas atmosphere for 2-10h, with the calcination temperature set to 200-600℃, to obtain a ZnZrO x / Cu2O material; The Cu-containing precursor of step (1) 2+ The precursor is one of the following compounds: CuSO4, CuCl2·2H2O, Cu(CH3COO)2, Cu(NO3)2·3H2O; The reducing agent in step (1) is sodium citrate.

4. The method of claim 3, wherein, The precursor of Zn 2+ comprises one of the following compounds: Zn(NO3)2·6H2O, Zn(CH3COO)2, Zn(OH)2, Zn2(OH)2CO3.

5. The method of claim 3, wherein, The precursor of Zr 4+ comprises one of the following compounds: Zr(NO3)4·5H2O, ZrOCl2·8H2O.

6. The preparation method according to claim 3, characterized in that, Zn added in step (2) 2+ precursor and Zr 4+ the sum of the masses of the precursors is 0.02 to 0.4 times the mass of Cu2O, and the molar ratio of Zn to Zr is 1.0 to 5.

0.

7. The method of claim 3, wherein, The ultrapure water in steps (1) and (2) is replaced by deionized water.

8. Use of the reverse phase catalyst according to claim 1 or 2, characterized in that: A fixed bed reactor is applied, mixed gas with a molar ratio of CO2 / H2 / N2=1 / 1.0~5.0 / 0.5~5 is introduced, the flow rate is controlled at 10~150mL / min, the reaction pressure is maintained at 0.5~5MPa, and the reaction temperature is set at 180~300℃.

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