Catalyst for carbon dioxide hydrogenation to methanol, its preparation method and application
By using Ga-doped Zn and Zr composite metal oxide catalysts, the lattice structure of the catalyst is changed, improving CO2 conversion and methanol selectivity. This solves the problems of easy deactivation and low conversion rate of existing catalysts, and realizes a highly efficient reaction of carbon dioxide hydrogenation to methanol.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA BLUECHEMICAL LTD
- Filing Date
- 2024-12-27
- Publication Date
- 2026-06-30
Smart Images
Figure CN122298387A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalyst preparation technology, and in particular relates to a catalyst for the hydrogenation of carbon dioxide to methanol, its preparation method and application. Background Technology
[0002] The hydrogenation of carbon dioxide to methanol not only reduces carbon dioxide emissions and mitigates ecological degradation, but also enables the resource-based conversion of carbon dioxide into methanol. Methanol, as an important chemical raw material, is mainly used in the production of hydrocarbon products such as olefins and aromatics, as well as pesticides and pharmaceuticals. Simultaneously, methanol is an important fuel with wide applications in fuel cells.
[0003] The hydrogenation of carbon dioxide to methanol primarily relies on a catalyst to facilitate the reaction of carbon dioxide with hydrogen to produce methanol. Currently, research on catalysts for carbon dioxide hydrogenation to methanol mainly focuses on two categories: copper-based catalysts and non-copper-based catalysts. Copper-based catalysts, such as Cu-ZnO / Al₂O₃ catalysts, have been widely studied in carbon dioxide hydrogenation reactions due to their low cost, high activity, and strong practicality. However, the performance of these catalysts is easily affected by the chemical state of the Cu surface, and they are prone to agglomeration and deactivation under conditions that produce large amounts of water. Furthermore, at higher temperatures, the selectivity for methanol in the product decreases. Non-copper-based catalysts, such as Pd / CeO₂ catalysts supported on noble metals, exhibit high methanol selectivity but lower carbon dioxide conversion rates.
[0004] Therefore, there is an urgent need to design a catalyst with high carbon dioxide conversion rate and methanol selectivity to realize the industrial-scale production of methanol by carbon dioxide hydrogenation. Summary of the Invention
[0005] The main objective of this invention is to provide a catalyst for the hydrogenation of carbon dioxide to methanol, its preparation method, and its application. The technical problem to be solved is to provide a composite oxide catalyst of three metals, Ga, Zn, and Zr, in which the mass percentage of Ga is 1.0-2.0%. When used in the catalytic hydrogenation of carbon dioxide to methanol, it exhibits a carbon dioxide conversion rate of 14.6-17.7% and a methanol selectivity of 80.1-83.6%, thereby facilitating the industrial-scale production of methanol from carbon dioxide hydrogenation.
[0006] The objective of this invention and the technical problem it solves are achieved by the following technical solution. A method for preparing a catalyst for the hydrogenation of carbon dioxide to methanol, according to this invention, includes the following steps:
[0007] (1) Mix an aqueous solution of zinc salt, zirconium salt and gallium nitrate with an alkaline solution; age the mixture; the mixing temperature is 65-85℃, the pH value is 8.2-11.5; the molar ratio of Zn to Zr is 0.15-1.0:1.0;
[0008] (2) The aged product is separated, dried and calcined to obtain the catalyst precursor;
[0009] (3) The catalyst precursor is reduced to obtain a catalyst for the hydrogenation of carbon dioxide to methanol; the mass percentage of Ga in the catalyst is 1.0 to 2.0%.
[0010] The objectives of this invention and the technical problems it addresses can be further achieved by the following technical measures.
[0011] Preferably, in the aforementioned preparation method, the zinc salt is selected from zinc nitrate, zinc carbonate, or basic zinc carbonate.
[0012] Preferably, in the aforementioned preparation method, the zirconium salt is selected from zirconium nitrate, zirconium oxynitrate, or zirconium acetate.
[0013] Preferably, in the aforementioned preparation method, the alkaline solution is selected from one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia water, sodium carbonate aqueous solution, potassium carbonate aqueous solution, and ammonium carbonate aqueous solution.
[0014] Preferably, in the aforementioned preparation method, the aging temperature is 65–85°C.
[0015] Preferably, in the aforementioned preparation method, the aging time is 1.5 to 3.5 hours.
[0016] Preferably, in the aforementioned preparation method, the drying temperature is 70–100°C.
[0017] Preferably, in the aforementioned preparation method, the drying time is 5 to 8 hours.
[0018] Preferably, in the aforementioned preparation method, the calcination temperature is 550–650°C.
[0019] Preferably, in the aforementioned preparation method, the calcination time is 2.5 to 4.5 hours.
[0020] Preferably, in the aforementioned preparation method, the calcination heating rate is 90–150 °C / h.
[0021] Preferably, in the aforementioned preparation method, the reduction space velocity is 3500–4500 ml / g / h.
[0022] Preferably, in the aforementioned preparation method, the reduction pressure is 0.1 to 1.0 MPa.
[0023] Preferably, in the aforementioned preparation method, the reduction time is 5 to 10 hours.
[0024] Preferably, in the aforementioned preparation method, the reduction temperature is 420–550°C.
[0025] The objective of this invention and the technical problem it solves are also achieved by the following technical solution. A catalyst for the hydrogenation of carbon dioxide to methanol, according to this invention, comprises: Ga, Zn, and Zr; the molar ratio of Zn to Zr is 0.15–1.0:1.0; and the mass percentage of Ga in the catalyst is 1.0–2.0%.
[0026] Preferably, in the aforementioned catalyst, the molar ratio of Zn to Zr is 0.15 to 0.5:1.0.
[0027] The objective of this invention and the technical problem it solves are also achieved by the following technical solution: The application of the catalyst described above in the hydrogenation of carbon dioxide to methanol, according to this invention.
[0028] By employing the above technical solution, the catalyst for the hydrogenation of carbon dioxide to methanol, its preparation method, and its application, as described in this invention, have at least the following advantages:
[0029] The Ga-doped Zn and Zr composite metal oxide catalyst provided by this invention for the hydrogenation of carbon dioxide to methanol effectively alters the crystal structure of the Zn and Zr composite metal oxide catalyst by doping with 1.0–2.0% Ga by mass, resulting in more defect sites in the crystal structure. When used in the hydrogenation of carbon dioxide to methanol reaction, this catalyst effectively improves the adsorption and conversion capacity of CO2, effectively promotes the dissociation and activation of H2, facilitates the formation of CH bonds and the coupling of equimolar proton transfer to produce methanol, and improves the selectivity of methanol.
[0030] This invention provides a Ga-doped Zn and Zr composite metal oxide catalyst for the hydrogenation of carbon dioxide to methanol, wherein the mass percentage of Ga in the catalyst is 1.0–2.0%. When this catalyst is used in the hydrogenation of carbon dioxide to methanol reaction, it exhibits a carbon dioxide conversion rate of 14.6–17.7% and a methanol selectivity of 80.1–83.6%, confirming that a Ga doping mass percentage of 1.0–2.0% is beneficial for simultaneously improving carbon dioxide conversion and methanol selectivity. Furthermore, the Ga mass percentage of only 1.0–2.0% helps reduce costs and enables the industrial-scale production of methanol from carbon dioxide hydrogenation. The catalyst preparation method described in this invention for the hydrogenation of carbon dioxide to methanol is simple, easy to operate, and industrially feasible.
[0031] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings. Attached Figure Description
[0032] Figure 1 This is a SEM image of the catalyst for the hydrogenation of carbon dioxide to methanol prepared in Example 1 of this invention, which has a Ga mass percentage of 1%. Detailed Implementation
[0033] To further illustrate the technical means and effects adopted by the present invention to achieve its intended purpose, the following, in conjunction with the accompanying drawings and preferred embodiments, details the catalyst for the hydrogenation of carbon dioxide to methanol proposed according to the present invention, its preparation method, and its specific implementation methods, structures, features, and effects. In the following description, different "embodiments" or "embodiments" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable form.
[0034] The first aspect of this invention provides a method for preparing a catalyst for the hydrogenation of carbon dioxide to methanol, comprising the following steps:
[0035] (1) Mix an aqueous solution of zinc salt, zirconium salt and gallium nitrate with an alkaline solution; age the mixture; the mixing temperature is 65-85℃, the pH value is 8.2-11.5; the molar ratio of Zn to Zr is 0.15-1.0:1.0;
[0036] (2) The aged product is separated, dried and calcined to obtain the catalyst precursor;
[0037] (3) The catalyst precursor is reduced to obtain a catalyst for the hydrogenation of carbon dioxide to methanol; the mass percentage of Ga in the catalyst is 1.0 to 2.0%.
[0038] This invention provides a Ga-doped Zn and Zr composite metal oxide catalyst for the hydrogenation of carbon dioxide to methanol. By doping with 1.0–2.0% Ga by mass, the lattice structure of the Zn and Zr composite metal oxide catalyst is effectively altered, resulting in more defect sites. When this catalyst is used in the carbon dioxide hydrogenation to methanol reaction, it effectively improves the adsorption and conversion capacity of CO2, effectively promotes the dissociation and activation of H2, facilitates the formation of CH bonds and the coupling of equimolar proton transfer to produce methanol, and improves methanol selectivity, exhibiting a carbon dioxide conversion rate of 14.6–17.7% and a methanol selectivity of 80.1–83.6%.
[0039] According to the present invention, the zinc salt is selected from zinc nitrate, zinc carbonate, or basic zinc carbonate; the zirconium salt is selected from zirconium nitrate, zirconium oxynitrate, or zirconium acetate; and the alkaline solution is selected from one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia water, sodium carbonate aqueous solution, potassium carbonate aqueous solution, and ammonium carbonate aqueous solution.
[0040] In this invention, the aqueous solutions of zinc salt, zirconium salt, and gallium nitrate are mixed with the alkaline solution at a temperature of 65–85°C. Controlling the mixing temperature within this range is mainly to control the particle size distribution and crystal phase structure of the solid precipitates of zinc hydroxide, zirconium hydroxide, and gallium hydroxide generated by the reaction. At the same time, the pH value of the mixture is controlled within 8.2–11.5. Under alkaline conditions, it is more conducive to the reaction to generate the desired solid precipitates.
[0041] In this invention, aqueous solutions of zinc salt, zirconium salt, and gallium nitrate are mixed with an alkaline solution and then aged. The aging temperature is 65–85°C and the time is 1.5–3.5 h. The aging temperature and time are controlled within the above range mainly to ensure that zinc ions, zirconium ions, and gallium ions react fully with hydroxide ions, thereby improving the conversion rate of zinc ions, zirconium ions, and gallium ions.
[0042] In this invention, the method for separating the solid precipitates of zinc hydroxide, zirconium hydroxide, and gallium hydroxide generated by the reaction can be selected by those skilled in the art according to actual needs, as long as the aged solid precipitates can be separated. This invention does not limit the method; for example, it can be filtration separation, centrifugal separation, etc.
[0043] According to the present invention, the separated solid precipitate is dried. The drying method is a conventional choice in the art and is not limited by the present invention. For example, it can be vacuum drying, infrared drying, etc.
[0044] In this invention, the temperature for drying the separated solid precipitate is 70-100°C and the time is 5-8 hours. The drying temperature and time are controlled within this range mainly to thoroughly remove residual moisture from the zinc hydroxide, zirconium hydroxide and gallium hydroxide solid precipitates.
[0045] According to the present invention, the dried solid precipitate is calcined. By controlling the calcination temperature to be 550-650°C, the time to be 2.5-4.5 h, and the heating rate to be 90-150°C / h, zinc hydroxide, zirconium hydroxide, and gallium hydroxide can be calcined into Ga, Zn, and Zr composite metal oxides. Furthermore, the crystal structure of the Ga, Zn, and Zr composite metal oxides can be effectively changed, and Ga, Zn, and Zr composite metal oxides with more crystal defects can be obtained.
[0046] According to the present invention, a Ga, Zn, and Zr composite metal oxide whose crystal structure is altered after calcination is reduced. The reduction is carried out at a space velocity of 3500–4500 ml / g / h, a pressure of 0.1–1.0 MPa, a reduction time of 5–10 h, a temperature of 420–550 °C, and hydrogen as the reducing gas. This enables the reduction preparation of Ga-doped Zn and Zr composite metal oxide catalysts for the hydrogenation of carbon dioxide to methanol.
[0047] A second aspect of this invention provides a catalyst for the hydrogenation of carbon dioxide to methanol, comprising Ga, Zn, and Zr; wherein the molar ratio of Zn to Zr is 0.15–1.0:1.0; and the mass percentage of Ga in the catalyst is 1.0–2.0%. Thus, when this catalyst is used in the hydrogenation of carbon dioxide to methanol reaction, it exhibits a carbon dioxide conversion rate of 14.6–17.7% and a methanol selectivity of 80.1–83.6%.
[0048] According to the present invention, the molar ratio of Zn to Zr is 0.15 to 0.5:1.0. This further facilitates the simultaneous improvement of carbon dioxide conversion rate and methanol selectivity.
[0049] A third aspect of this invention proposes the application of the catalyst described above in the hydrogenation of carbon dioxide to methanol. In this invention, the reaction conditions for applying the catalyst in the hydrogenation of carbon dioxide to methanol can be selected by those skilled in the art according to actual needs, and this invention does not limit them. For example, the conditions can be as follows: 0.1–0.3 g of catalyst is packed into a fixed-bed reactor, the reaction temperature is 350–450 °C, the reaction time is 4–7 h, the reaction space velocity is 7000–20000 ml / g / h, the CO2 / H2 ratio is 1:4–1:7, and the reaction pressure is 4–7 MPa.
[0050] The present invention will be further described below with reference to specific embodiments, but this should not be construed as a limitation on the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.
[0051] Unless otherwise specified, all materials and reagents mentioned below are commercially available products well known to those skilled in the art; unless otherwise specified, all methods described are methods known in the art. Unless otherwise defined, the technical or scientific terms used should have the ordinary meaning understood by those skilled in the art to which this invention pertains.
[0052] Example
[0053] The catalysts prepared in the following examples and comparative examples were applied to the production of methanol by carbon dioxide hydrogenation, and catalyst activity was tested. The catalyst activity was expressed as the CO2 conversion rate in the production of methanol by CO2 hydrogenation, and the CO2 conversion rate (%) was calculated as (CO2 inlet - CO2 outlet) / CO2 inlet × 100%. The specific test procedure was as follows: 0.1 g of catalyst was packed into a fixed-bed reactor, the reaction temperature was 400 °C, the reaction time was 5 h, the reaction space velocity was 7000 ml / g / h, the CO2 / H2 ratio was 1:4, and the reaction pressure was 4 MPa.
[0054] Example 1
[0055] 1.23 g of zinc nitrate, 14.75 g of zirconium nitrate, and 0.04 g of gallium nitrate were weighed and transferred to 100 mL of deionized water to prepare solution A1 (zinc / zirconium = 0.15:1). 5.2 g of sodium hydroxide was weighed and transferred to 50 mL of deionized water to prepare solution B1. Solutions A1 and B1 were mixed at 70 °C under nitrogen protection, with the pH controlled at 8.2. After mixing, the reaction was continued at 70 °C for 3 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to obtain a solid precipitate, dried at 60 °C for 12 h, and then calcined at 500 °C for 3 h at a heating rate of 150 °C / h. The calcined solid oxide was reduced with hydrogen at 0.1 MPa, with a reduction space velocity of 3000 ml / g / h, a reduction temperature of 400 °C, and a reduction time of 12 h, yielding a composite metal oxide catalyst C1 with a Ga content of 1 wt%. Figure 1 As shown.
[0056] Catalyst activity tests showed that after 5 hours of reaction, the CO2 conversion rate was 14.6% and the methanol selectivity was 80.1%.
[0057] Example 2
[0058] 0.95 g of zinc nitrate, 1.70 g of zirconium nitrate, and 0.08 g of gallium nitrate were weighed and transferred to 50 mL of deionized water to prepare solution A2 (zinc / zirconium = 1:1). 8.6 g of sodium carbonate was then weighed and transferred to 50 mL of deionized water to prepare solution B2. Solutions A2 and B2 were mixed at 70 °C under nitrogen protection, with the pH controlled at 8.5. After mixing, the reaction was continued at 60 °C for 3 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to obtain a solid precipitate, dried at 60 °C for 12 h, and then calcined at 500 °C for 3 h at a heating rate of 150 °C / h. The calcined solid oxide was then reduced with hydrogen at 0.1 MPa, with a reduction space velocity of 3000 ml / g / h, a reduction temperature of 400 °C, and a reduction time of 12 h, yielding a composite metal oxide catalyst C2 with a Ga content of 2 wt%.
[0059] Catalyst activity tests showed that after 5 hours of reaction, the CO2 conversion rate was 17.7% and the methanol selectivity was 83.6%.
[0060] Example 3
[0061] Weigh out 6.44 g of zinc nitrate, 22.39 g of zirconium nitrate, and 0.04 g of gallium nitrate, and then transfer them to 100 mL of deionized water to prepare solution A3 (zinc / zirconium = 0.5:1). Weigh out 15.8 g of ammonia and 4.5 g of sodium carbonate, and transfer them to 50 mL of deionized water to prepare solution B3. Mix solutions A3 and B3 at 70 °C under nitrogen protection, controlling the pH value at 8.2. After mixing, continue the reaction at 70 °C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered to obtain a solid precipitate. The solid precipitate was dried at 60°C for 12 h, and then heated to 500°C at a rate of 150°C / h. The precipitate was then calcined at 500°C for 3 h. The calcined solid oxide was reduced with hydrogen at 0.1 MPa, with a reduction space velocity of 3000 ml / g / h, a reduction temperature of 300°C, and a reduction time of 12 h, to obtain a composite metal oxide catalyst C3 with a Ga content of 1 wt%.
[0062] Catalyst activity tests showed that after 5 hours of reaction, the CO2 conversion rate was 15.1% and the methanol selectivity was 81.3%.
[0063] Example 4
[0064] 1.23 g of zinc nitrate, 14.75 g of zirconium nitrate, and 0.04 g of gallium nitrate were weighed and transferred to 150 mL of deionized water to prepare solution A4. 5.2 g of sodium hydroxide was weighed and transferred to 100 mL of deionized water to prepare solution B4. Solutions A4 and B4 were mixed at 70 °C under nitrogen protection, with the pH controlled at 8.2. After mixing, the reaction was continued at 70 °C for 3 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to obtain a solid precipitate, dried at 60 °C for 12 h, and then calcined at 500 °C for 3 h at a heating rate of 150 °C / h. The calcined solid oxide was then reduced with hydrogen at 0.1 MPa, with a reduction space velocity of 3000 ml / g / h, a reduction temperature of 400 °C, and a reduction time of 12 h, yielding a composite metal oxide catalyst C4 with a Ga content of 1 wt%.
[0065] Catalyst activity tests showed that after 5 hours of reaction, the CO2 conversion rate was 16.6% and the methanol selectivity was 82.5%.
[0066] Example 5
[0067] 1.23 g of zinc nitrate, 14.75 g of zirconium nitrate, and 0.04 g of gallium nitrate were weighed and transferred to 150 mL of deionized water to prepare solution A5. 15.8 g of ammonia and 4.5 g of sodium carbonate were weighed and transferred to 100 mL of deionized water to prepare solution B5. Solutions A5 and B5 were mixed at 70 °C under nitrogen protection, with the pH controlled at 8.2. After mixing, the reaction was continued at 70 °C for 3 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to obtain a solid precipitate, dried at 60 °C for 12 h, and then calcined at 500 °C for 3 h at a heating rate of 150 °C / h. The calcined solid oxide was then reduced with hydrogen at 0.1 MPa, with a reduction space velocity of 3000 ml / g / h, a reduction temperature of 320 °C, and a reduction time of 12 h, yielding a composite metal oxide catalyst C5 with a Ga content of 1 wt%.
[0068] Catalyst activity tests showed that after 5 hours of reaction, the CO2 conversion rate was 17.2% and the methanol selectivity was 82.6%.
[0069] Comparative Example 1
[0070] 1.23 g of zinc nitrate, 14.75 g of zirconium nitrate, and 0.4 g of gallium nitrate were weighed and transferred to 150 mL of deionized water to prepare solution M1. 6.8 g of sodium hydroxide was weighed and transferred to 100 mL of deionized water to prepare solution N1. Solutions M1 and N1 were mixed at 70 °C under nitrogen protection, with the pH controlled at 9.2. After mixing, the reaction was continued at 80 °C for 3 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to obtain a solid precipitate, dried at 60 °C for 12 h, and then calcined at 500 °C for 3 h at a heating rate of 150 °C / h. The calcined solid oxide was then reduced with hydrogen at 0.1 MPa, with a reduction space velocity of 3000 ml / g / h, a reduction temperature of 400 °C, and a reduction time of 12 h, yielding a composite metal oxide catalyst D1 with a Ga content of 10 wt%.
[0071] Catalyst activity tests showed that after 5 hours of reaction, the CO2 conversion rate was 21.7% and the methanol selectivity was 45.6%.
[0072] Comparative Example 2
[0073] 1.23 g of zinc nitrate, 14.75 g of zirconium nitrate, and 0.04 g of gallium nitrate were weighed and transferred to 150 mL of deionized water to prepare solution M2. 15.8 g of ammonia and 4.5 g of sodium carbonate were weighed and transferred to 100 mL of deionized water to prepare solution N2. Solutions M2 and N2 were mixed at 70 °C under nitrogen protection, with the pH controlled at 8.2. After mixing, the reaction was continued at 70 °C for 3 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to obtain a solid precipitate, dried at 60 °C for 12 h, and then calcined at 500 °C for 3 h at a heating rate of 150 °C / h. The calcined solid oxide was then reduced with hydrogen at 0.1 MPa, with a reduction space velocity of 3000 ml / g / h, a reduction temperature of 400 °C, and a reduction time of 12 h, yielding a composite metal oxide catalyst D2 with a Ga content of 0.1 wt%.
[0074] Catalyst activity tests showed that after 5 hours of reaction, the CO2 conversion rate was 8.4% and the methanol selectivity was 85.8%.
[0075] As can be seen from the data in the above embodiments and comparative examples, the Ga-doped Zn and Zr composite metal oxide catalyst for the hydrogenation of carbon dioxide to methanol described in this invention, by controlling the mass percentage of Ga doping within the range of 1.0 to 2.0%, can effectively change the crystal structure of the Zn and Zr composite metal oxide catalyst, causing the crystal structure to generate more defect sites, effectively improving the adsorption and conversion capacity of CO2, effectively promoting the dissociation and activation of H2, and more easily forming CH bonds and coupling an equimolar amount of proton transfer to produce methanol. As a result, the reaction of hydrogenating carbon dioxide to methanol has a carbon dioxide conversion rate of 14.6 to 17.7% and a methanol selectivity of 80.1 to 83.6%.
[0076] The technical features in the claims and / or specification of this invention can be combined, and the combination is not limited to the combinations obtained through reference in the claims. Technical solutions obtained by combining the technical features in the claims and / or specification are also within the scope of protection of this invention.
[0077] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.
Claims
1. A method for preparing a catalyst for the hydrocarbon monoxide of carbon dioxide, characterized by, It includes the following steps: (1) Mix an aqueous solution of zinc salt, zirconium salt and gallium nitrate with an alkaline solution; age the mixture; the mixing temperature is 65-85℃, the pH value is 8.2-11.5; the molar ratio of Zn to Zr is 0.15-1.0:1.0; (2) The aged product is separated, dried and calcined to obtain the catalyst precursor; (3) The catalyst precursor is reduced to obtain a catalyst for the hydrogenation of carbon dioxide to methanol; the mass percentage of Ga in the catalyst is 1.0 to 2.0%.
2. The method of claim 1, wherein, In step (1), The zinc salt is selected from zinc nitrate, zinc carbonate, or basic zinc carbonate; The zirconium salt is selected from zirconium nitrate, zirconium oxynitrate, or zirconium acetate. The alkaline solution is selected from one of the following: sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia water, sodium carbonate aqueous solution, potassium carbonate aqueous solution, and ammonium carbonate aqueous solution.
3. The method of claim 1, wherein, In step (1), the aging temperature is 65-85°C and the time is 1.5-3.5h.
4. The method of claim 1, wherein, In step (2), the drying temperature is 70-100℃ and the time is 5-8h.
5. The method of claim 1, wherein, In step (2), the calcination temperature is 550-650℃; the heating rate is 90-150℃ / h; and the time is 2.5-4.5h.
6. The method of claim 1, wherein, In step (3), the reduction space velocity is 3500-4500 ml / g / h; the pressure is 0.1-1.0 MPa.
7. The method of claim 1, wherein, In step (3), the reduction time is 5 to 10 hours and the temperature is 420 to 550°C.
8. A catalyst for the hydrocarbon of carbon dioxide to methanol, characterized by, It includes: Ga, Zn and Zr; The molar ratio of Zn to Zr is 0.15–1.0:1.0; the mass percentage of Ga in the catalyst is 1.0–2.0%.
9. The catalyst of claim 8, wherein The molar ratio of Zn to Zr is 0.15 to 0.5:1.
0.
10. The application of the catalyst according to claim 8 in the hydrogenation of carbon dioxide to methanol.