Methanol catalyst, preparation method and application

Abstract

The application relates to a methanol catalyst, a preparation method and application, and relates to the technical field of catalysts, and the chemical general formula of the methanol catalyst is the preparation method specifically comprises the following steps: taking and mixing an indium salt, a cerium salt and an additive in a first molar ratio to obtain a first material, dissolving the first material and citric acid in desalted water in a second molar ratio to obtain a second material, heating and stirring the second material to obtain a third material in the form of foamed gel, and performing drying, grinding, vacuum-like calcination, granulation, adding a release agent and tabletting, so that the target catalyst is obtained, the methanol catalyst can be applied to the reaction of carbon dioxide hydrogenation to prepare methanol, has a large number of indium oxide active groups In3O5, good dispersity of the indium oxide active groups In3O5 and rich In-CeO x interfaces, and exhibits good catalytic activity and methanol selectivity.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a methanol catalyst, its preparation method, and its application. Background Technology

[0002] Methanol is not only an important chemical raw material, but also a high-performance energy carrier. The production of methanol by hydrogenating carbon dioxide can effectively solve the problem of carbon dioxide emissions and generate methanol, which is conducive to achieving a sustainable carbon cycle.

[0003] Catalysts are crucial in the hydrogenation of carbon dioxide to methanol reaction. Currently, copper-based catalysts are commonly used. However, copper-based catalysts exhibit high reactivity in the reverse water-gas shift reaction, which leads to the generation of a large amount of carbon monoxide as a byproduct and a large amount of water during the carbon dioxide hydrogenation reaction. Water accelerates the sintering and deactivation of the catalyst, resulting in a lower methanol yield, thus having certain limitations. Summary of the Invention

[0004] The purpose of this invention is to provide a methanol catalyst, its preparation method, and its application, which has a large number of indium oxide active groups (In3O5) and good dispersion of the indium oxide active groups (In3O5), and also has abundant In-CeO. x The interface can effectively suppress the selectivity of the byproduct CO, which is beneficial to significantly improve the selectivity of methanol.

[0005] The present invention provides a methanol catalyst comprising indium oxide, cerium oxide and an additive, wherein the molar ratio of the indium oxide, the cerium oxide and the additive is (55-75):(20-40):(0-10), the molar mass of the additive is greater than 0, and the additive comprises at least one selected from Au, Ag, Co, Ni, Ir, Ru, Rh, Pt and Pd.

[0006] Indium oxide can serve as the active center for methanol catalysts. Since the methanol synthesis pathway is the formate pathway, it can effectively reduce the activity of the reverse water-gas shift reaction. Furthermore, the cerium oxide support in the catalyst, due to the anisotropic nature of oxygen atoms in the oxide lattice, can synergistically promote the removal of surface oxygen atoms to form In-CeO. x The interface provides more abundant oxygen vacancies, thus providing sufficient active sites for CO2 adsorption and hydrogenation conversion. It can promote the formation of the h-In2O3(104) hexagonal crystal plane and generate stronger interaction with the active group In3O5, effectively reducing the selectivity of the by-product CO, exhibiting higher catalytic activity and methanol selectivity, which is beneficial to improving the yield of methanol.

[0007] This invention provides a method for preparing a methanol catalyst, which can be selectively used to prepare the aforementioned methanol catalyst, comprising the following steps: Catalyst raw materials are prepared by weighing and mixing indium salt, cerium salt and additives in a first molar ratio to obtain a first material. The first material is dissolved in demineralized water with citric acid in a second molar ratio to obtain a second material. The second material is heated and stirred to obtain a foamy gel-like third material. Drying: The third material is dried to obtain the fourth material; Grinding: The fourth material is ground to obtain the fifth material; Calcination; the fifth material is calcined in a near-vacuum environment to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

[0008] In one embodiment, in the step of preparing the catalyst raw materials, the first molar ratio is (55-75):(20-40):(0-10), and the molar mass of the additive is greater than 0.

[0009] In one embodiment, in the step of preparing the catalyst feedstock, the second molar ratio is 1:(1 to 1.5).

[0010] In one embodiment, in the step of preparing the catalyst feedstock, the indium salt is indium nitrate trihydrate, and / or the cerium salt is cerium nitrate hexahydrate.

[0011] In one embodiment, in the step of preparing the catalyst raw materials, the auxiliary agent is at least one selected from palladium nitrate dihydrate, rhodium nitrate dihydrate, chloroauric acid tetrahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and chloroplatinic acid hexahydrate.

[0012] In one embodiment, in the step of preparing the catalyst feedstock, the auxiliary agent is at least one selected from Au salt, Ag salt, Co salt, Ni salt, Ir salt, Ru salt, Rh salt, Pt salt, and Pd salt.

[0013] In one embodiment, in the step of preparing the catalyst raw materials, the heating and stirring temperature is 90°C to 150°C, or the heating and stirring temperature is 100°C, 120°C, 130°C or 150°C.

[0014] In one embodiment, during the calcination step, the vacuum-like environment is 0.5 Torr to 10.0 Torr, or the vacuum-like environment is 0.5 Torr, 0.8 Torr, 1.0 Torr, 2.0 Torr, 3.0 Torr, 4.0 Torr, 5.0 Torr, 6.0 Torr, 7.0 Torr, 8.0 Torr, 9.0 Torr, or 10.0 Torr, and / or the calcination temperature is 400°C to 600°C, or the calcination temperature is 400°C, 425°C, 450°C, 475°C, 500°C, 525°C, 550°C, 575°C, or 600°C.

[0015] The present invention also proposes an application of the aforementioned methanol catalyst, or the application of the methanol catalyst prepared according to the aforementioned methanol catalyst preparation method, specifically for the reaction of producing methanol by hydrogenation of carbon dioxide.

[0016] By calcining in a near-vacuum environment, more oxygen vacancies can be generated in indium cerium oxide at high temperatures, thereby increasing the number and dispersion of the active groups In3O5 in indium oxide, which is beneficial to improving the methanol reactivity and selectivity of the catalyst. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a schematic diagram of a methanol catalyst preparation method according to an embodiment of the present invention. Detailed Implementation

[0019] The specific embodiments of the present invention will now be described in detail with reference to the accompanying drawings. Obviously, the described embodiments are merely some, not all, of the embodiments of the present invention. Based on the description of the present invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of the present invention.

[0020] Unless otherwise explicitly specified and limited, the terms "setup," "installation," and "connection" should be interpreted broadly. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to mechanical connections or electrical connections; they can refer to direct connections or indirect connections through an intermediate medium. Those skilled in the art can understand the specific meaning of these terms based on the specific circumstances.

[0021] The terms “upper,” “lower,” “left,” “right,” “front,” “back,” “top,” “bottom,” “inner,” and “outer,” etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of the invention is in use. They are only for the convenience of description and simplification, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the present invention.

[0022] The terms “first,” “second,” “third,” etc., are used merely to distinguish elements with similar properties, not to indicate or imply relative importance or a specific order.

[0023] The terms “include,” “comprising,” or any other variation thereof are intended to cover non-exclusive inclusion, which includes not only the elements listed but also other elements not expressly listed.

[0024] The methanol catalyst proposed in this invention comprises indium oxide, cerium oxide and an additive, wherein the molar ratio of indium oxide, cerium oxide and additive is (55-75):(20-40):(0-10), wherein the molar mass of the additive is greater than 0, and the additive includes at least one of Au, Ag, Co, Ni, Ir, Ru, Rh, Pt and Pd.

[0025] like Figure 1 As shown, the methanol catalyst preparation method proposed in this invention includes the following steps: Catalyst raw materials are prepared by weighing and mixing indium salt, cerium salt and additives in a first molar ratio to obtain the first material. The first material is dissolved in demineralized water with citric acid in a second molar ratio to obtain the second material. The second material is heated and stirred to obtain the third material, which is a foamy gel. Drying: The third material is dried to obtain the fourth material; Grinding: Grind the fourth material to obtain the fifth material; Calcination; Under a near-vacuum environment, the fifth material is calcined to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

[0026] For example, in the aforementioned step of preparing catalyst raw materials, the first molar ratio is (55-75):(20-40):(0-10), and the molar mass of the additive is greater than 0.

[0027] For example, in the aforementioned step of preparing the catalyst feedstock, the second molar ratio is 1:(1 to 1.5).

[0028] Furthermore, the molar ratio of citric acid to the first material can be 1, 1.1, 1.2, 1.3, 1.4 or 1.5.

[0029] For example, in the aforementioned steps of preparing catalyst feedstock, the indium salt is indium nitrate trihydrate.

[0030] For example, in the aforementioned step of preparing the catalyst feedstock, the cerium salt is cerium nitrate hexahydrate.

[0031] For example, in the aforementioned step of preparing catalyst feedstock, the auxiliary agent may be at least one of Au salt, Ag salt, Co salt, Ni salt, Ir salt, Ru salt, Rh salt, Pt salt, and Pd salt.

[0032] For example, in the aforementioned step of preparing catalyst raw materials, the auxiliary agent may be at least one of palladium nitrate dihydrate, rhodium nitrate dihydrate, chloroauric acid tetrahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and chloroplatinic acid hexahydrate.

[0033] For example, in the aforementioned step of preparing catalyst raw materials, the heating and stirring temperature is 90°C to 150°C, or the heating and stirring temperature is 90°C, 100°C, 120°C, 130°C or 150°C.

[0034] For example, in the aforementioned drying step, the drying temperature is 100°C to 180°C, or the drying temperature is 100°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C.

[0035] For example, in the aforementioned drying step, the drying time is 3h to 8h, or the drying time is 3h, 4h, 5h, 6h, 7h or 8h.

[0036] For example, in the aforementioned calcination step, the vacuum-like environment is specifically 0.5 Torr to 10.0 Torr, or the vacuum-like environment is specifically 0.5 Torr, 0.8 Torr, 1.0 Torr, 2.0 Torr, 3.0 Torr, 4.0 Torr, 5.0 Torr, 6.0 Torr, 7.0 Torr, 8.0 Torr, 9.0 Torr, or 10.0 Torr.

[0037] For example, the aforementioned roasting step further includes roasting the fifth material in a tube furnace.

[0038] For example, in the aforementioned roasting step, the roasting temperature is 400℃~600℃, or the roasting temperature is 400℃, 425℃, 450℃, 475℃, 500℃, 525℃, 550℃, 575℃ or 600℃.

[0039] For example, in the aforementioned roasting step, the roasting time is 2h to 8h, or the roasting time is 2h, 3h, 4h, 5h, 6h, 7h or 8h.

[0040] For example, in the aforementioned molding step, the release agent is graphite.

[0041] The present invention also proposes an application of a methanol catalyst, which is the aforementioned methanol catalyst or is prepared by the aforementioned methanol catalyst preparation method, specifically applied to the reaction of carbon dioxide hydrogenation to methanol.

[0042] In the reaction of carbon dioxide hydrogenation to methanol, the selectivity of methanol mainly depends on the hydrogenation rate of CO2 and the decomposition rate of intermediate products. By promoting the CO2 hydrogenation activity of the catalyst and the rate of conversion of intermediate products to methanol, the selectivity of by-product CO can be suppressed, thereby increasing the yield of methanol.

[0043] The methanol catalyst proposed in this invention allows cerium oxide and indium oxide to synergistically form In-CeO. x The interface provides a richer supply of oxygen vacancies, which can effectively promote Ce 3+ The formation of the hexagonal indium oxide broadens the stable range of the hexagonal phase, inhibits the transformation of the hexagonal phase to the inert cubic phase at high temperature, and promotes the preferential exposure of the highly active h-In2O3(104) crystal plane. The loosely arranged h-In2O3(104) crystal plane, combined with the lattice oxygen imbalance caused by the In-Ce valence cycle, can further provide a greater number of oxygen vacancies and promote the further deep hydrogenation of key intermediate products to produce methanol.

[0044] The preparation method of the methanol catalyst and the methanol catalyst of the present invention will now be described with reference to the following examples and comparative examples.

[0045] Example 1 The molar ratio of indium salt, cerium salt, and auxiliary palladium is 60:35:5. Indium nitrate trihydrate is used as the indium salt, cerium nitrate hexahydrate is used as the cerium salt, and palladium nitrate dihydrate is used as the auxiliary agent. The specific preparation method is as follows: Catalyst raw materials were prepared by dissolving 0.6 mol indium nitrate trihydrate, 0.35 mol cerium nitrate hexahydrate, 0.05 mol palladium nitrate dihydrate and 1 mol citric acid in demineralized water and heating and stirring at 130°C to obtain the third material, a foamy gel. Drying: The third material was dried at 130°C for 4 hours to obtain the fourth material; Grinding: Grind the fourth material to obtain the fifth material; Calcination; Under a near-vacuum environment of 1 Torr, the fifth material was calcined at 400°C for 5 hours to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

[0046] Example 2 The molar ratio of indium salt, cerium salt, and auxiliary agent palladium is 70:28:2. Indium nitrate trihydrate is used as the indium salt, cerium nitrate hexahydrate is used as the cerium salt, and palladium nitrate dihydrate is used as the auxiliary agent. The specific preparation method is as follows: Catalyst raw materials were prepared by dissolving 0.7 mol indium nitrate trihydrate, 0.28 mol cerium nitrate hexahydrate, 0.02 mol palladium nitrate dihydrate and 1 mol citric acid in demineralized water and heating and stirring at 100°C to obtain the third material, a foamy gel. Drying: The third material is dried at 100℃ for 4 hours to obtain the fourth material; Grinding: Grind the fourth material to obtain the fifth material; Calcination; Under a near-vacuum environment of 1 Torr, the fifth material was calcined at 500°C for 4 hours to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

[0047] Example 3 The molar ratio of indium salt, cerium salt, and rhodium additive is 65:33:2. Indium nitrate trihydrate is used as the indium salt, cerium nitrate hexahydrate as the cerium salt, and rhodium nitrate dihydrate as the additive. The specific preparation method is as follows: Catalyst raw materials were prepared by dissolving 0.65 mol indium nitrate trihydrate, 0.33 mol cerium nitrate hexahydrate, 0.02 mol rhodium nitrate dihydrate and 1.5 mol citric acid in demineralized water and heating and stirring at 120°C to obtain the third material, a foamy gel. Drying: The third material was dried at 120°C for 4 hours to obtain the fourth material; Grinding: Grind the fourth material to obtain the fifth material; Calcination; Under a near-vacuum environment of 0.5 Torr, the fifth material was calcined at 500°C for 3 hours to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

[0048] Example 4 The molar ratio of indium salt, cerium salt, and gold additive is 60:35:5. Indium nitrate trihydrate is used as the indium salt, cerium nitrate hexahydrate is used as the cerium salt, and chloroauric acid tetrahydrate is used as the additive. The specific preparation method is as follows: Catalyst raw materials were prepared by dissolving 0.60 mol indium nitrate trihydrate, 0.35 mol cerium nitrate hexahydrate, 0.05 mol chloroauric acid tetrahydrate and 1.5 mol citric acid in demineralized water and heating and stirring at 100°C to obtain the third material, a foamy gel. Drying: The third material was dried at 150°C for 4 hours to obtain the fourth material; Grinding: Grind the fourth material to obtain the fifth material; Calcination; Under a near-vacuum environment of 0.8 Torr, the fifth material was calcined at 600°C for 2 hours to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

[0049] Example 5 The molar ratio of indium salt, cerium salt, and nickel additive is 75:20:5. Indium nitrate trihydrate is used as the indium salt, cerium nitrate hexahydrate as the cerium salt, and nickel nitrate hexahydrate as the additive. The specific preparation method is as follows: Catalyst raw materials were prepared by dissolving 0.75 mol indium nitrate trihydrate, 0.20 mol cerium nitrate hexahydrate, 0.05 mol nickel nitrate hexahydrate and 1.5 mol citric acid in demineralized water and heating and stirring at 130°C to obtain the third material, a foamy gel. Drying: The third material was dried at 130°C for 5 hours to obtain the fourth material; Grinding: Grind the fourth material to obtain the fifth material; Calcination; Under a near-vacuum environment of 0.8 Torr, the fifth material was calcined at 500°C for 3 hours to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

[0050] Example 6 The molar ratio of indium salt, cerium salt, and cobalt additive is 55:35:10. Indium nitrate trihydrate is used as the indium salt, cerium nitrate hexahydrate as the cerium salt, and cobalt nitrate hexahydrate as the additive. The specific preparation method is as follows: Catalyst raw materials were prepared by dissolving 0.55 mol indium nitrate trihydrate, 0.35 mol cerium nitrate hexahydrate, 0.10 mol cobalt nitrate hexahydrate and 1.5 mol citric acid in demineralized water and heating and stirring at 150°C to obtain the third material, a foamy gel. Drying: The third material is dried at 150°C for 3 hours to obtain the fourth material; Grinding: Grind the fourth material to obtain the fifth material; Calcination; Under a near-vacuum environment of 1.0 Torr, the fifth material was calcined at 400°C for 5 hours to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

[0051] Example 7 The molar ratio of indium salt, cerium salt, and platinum additive is 70:28:2. Indium nitrate trihydrate is used as the indium salt, cerium nitrate hexahydrate as the cerium salt, and chloroplatinic acid hexahydrate as the additive. The specific preparation method is as follows: Catalyst raw materials were prepared by dissolving 0.70 mol indium nitrate trihydrate, 0.28 mol cerium nitrate hexahydrate, 0.02 mol chloroplatinic acid hexahydrate and 1.0 mol citric acid in demineralized water and heating and stirring at 100°C to obtain the third material, a foamy gel. Drying: The third material was dried at 120°C for 4 hours to obtain the fourth material; Grinding: Grind the fourth material to obtain the fifth material; Calcination; Under a near-vacuum environment of 5.0 Torr, the fifth material was calcined at 500°C for 3 hours to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

[0052] Comparative Example 1 Without adding any additives, the molar ratio of indium salt to cerium salt is 60:40. Indium nitrate trihydrate is used as the indium salt, and cerium nitrate hexahydrate is used as the cerium salt. The specific preparation method is as follows: 0.60 mol indium nitrate trihydrate, 0.40 mol cerium nitrate hexahydrate, and 1.0 mol citric acid were dissolved in demineralized water and heated and stirred at 130 °C to obtain a foamy gel. The gel was dried at 130 °C for 6 h to complete the gel drying. The dried gel was then ground and calcined at 400 °C for 4 h under a near-vacuum environment of 1.0 Torr. Granulation was performed, and a release agent was mixed in for tableting to obtain a comparative catalyst.

[0053] Comparative Example 2 Without using cerium salts, the molar ratio of indium nitrate trihydrate to palladium nitrate dihydrate is 95:5. The preparation method is as follows: 0.95 mol indium nitrate trihydrate, 0.05 mol palladium nitrate dihydrate, and 1.0 mol citric acid were dissolved in demineralized water and heated and stirred at 130 °C to obtain a foamy gel. The gel was dried at 130 °C for 4 h to complete the gel drying. The dried gel was then ground and calcined at 400 °C for 5 h under a near-vacuum environment of 1.0 Torr. Granulation was performed, and a release agent was mixed in for tableting to obtain a comparative catalyst.

[0054] Comparative Example 3 Without using cerium salts, the molar ratio of indium nitrate trihydrate to rhodium nitrate dihydrate is 98:2. The preparation method is as follows: 0.98 mol indium nitrate trihydrate, 0.02 mol rhodium nitrate dihydrate, and 1.0 mol citric acid were dissolved in demineralized water and heated and stirred at 100°C to obtain a foamy gel. The gel was dried at 120°C for 4 hours to complete the gel drying. The dried gel was then ground and calcined at 500°C for 3 hours under a near-vacuum environment of 5.0 Torr. Granulation was performed, and a release agent was mixed in for tableting to obtain a comparative catalyst.

[0055] Comparative Example 4 The molar ratio of indium salt, cerium salt, and rhodium additive is 85:13:2. Indium nitrate trihydrate is used as the indium salt, cerium nitrate hexahydrate is used as the cerium salt, and rhodium nitrate dihydrate is used as the additive. The specific preparation method is as follows: Catalyst raw materials were prepared by dissolving 0.85 mol indium nitrate trihydrate, 0.13 mol cerium nitrate hexahydrate, 0.02 mol rhodium nitrate dihydrate and 1.0 mol citric acid in demineralized water and heating and stirring at 130°C to obtain the third material, a foamy gel. Drying: The third material was dried at 130°C for 5 hours to obtain the fourth material; Grinding: Grind the fourth material to obtain the fifth material; Calcination; Under a near-vacuum environment of 1.5 Torr, the fifth material was calcined at 500°C for 3 hours to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain a comparative catalyst.

[0056] The catalysts used in Examples 1 to 7 and Comparative Examples 1 to 4 were subjected to a carbon dioxide hydrogenation reaction to produce methanol under the following conditions: at 250°C, GHSV (Gas Hourly Space Velocity) = 10000 ml gcat. -1 h -1 , 5MPa, H2:CO2:N2=23.5:70.5:6.

[0057] Table 1: Methanol production performance of the catalysts in Examples 1 to 7 and Comparative Examples 1 to 4

[0058] Referring to the data in Table 1, the methanol space-time yields of the catalysts in Examples 1 to 7 are significantly higher than those of the catalysts prepared in Comparative Examples 1 to 4, exhibiting higher methanol space-time yields.

[0059] The methanol catalyst proposed in this invention has a large number of In3O5 indium oxide active groups and good dispersion of In3O5 indium oxide active groups, and also has abundant In-CeO. x At the interface, the indium oxide active group In3O5 can follow the energy-optimal formate reaction mechanism in the reaction of carbon dioxide hydrogenation to methanol, thus efficiently activating CO2, cracking H2 in a heterolytic manner, and finally generating methanol through the continuous addition reaction of hydride ions and protons, which can effectively improve methanol selectivity.

[0060] More specifically, the methanol catalyst proposed in this invention can provide more oxygen vacancies and more h-In2O3(104) hexagonal crystal planes. Not only can it more stably adsorb CO2 and H2 at 200℃~300℃, but more importantly, this surface can stabilize the key reaction intermediate CH3O (methoxy radical) in the methanol generation process, and then hydrogenate it to form methanol, exhibiting higher methanol selectivity, thus having good hydrogenation reaction activity and methanol yield.

[0061] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A methanol catalyst, characterized in that, It includes indium oxide, cerium oxide and an additive, wherein the molar ratio of the indium oxide, the cerium oxide and the additive is (55-75):(20-40):(0-10), the molar mass of the additive is greater than 0, and the additive includes at least one of Au, Ag, Co, Ni, Ir, Ru, Rh, Pt and Pd.

2. A method for preparing a methanol catalyst, characterized in that, The catalyst can be selectively used to prepare the methanol catalyst of claim 1, comprising the following steps: Catalyst raw materials are prepared by weighing and mixing indium salt, cerium salt and additives in a first molar ratio to obtain a first material. The first material is dissolved in demineralized water with citric acid in a second molar ratio to obtain a second material. The second material is heated and stirred to obtain a foamy gel-like third material. Drying: The third material is dried to obtain the fourth material; Grinding: The fourth material is ground to obtain the fifth material; roasting; In a near-vacuum environment, the fifth material is calcined to obtain the sixth material; Molding: The sixth material is granulated, mixed with a release agent, and then compressed into tablets to obtain the target catalyst.

3. The method for preparing a methanol catalyst according to claim 2, characterized in that, In the step of preparing the catalyst raw materials, the first molar ratio is (55-75):(20-40):(0-10), and the molar mass of the auxiliary agent is greater than 0.

4. The method for preparing a methanol catalyst according to claim 2, characterized in that, In the step of preparing the catalyst feedstock, the second molar ratio is 1:(1 to 1.5).

5. The method for preparing a methanol catalyst according to claim 2, characterized in that, In the step of preparing the catalyst feedstock, the indium salt is indium nitrate trihydrate, and / or the cerium salt is cerium nitrate hexahydrate.

6. The method for preparing a methanol catalyst according to claim 2, characterized in that, In the step of preparing the catalyst raw materials, the auxiliary agent is at least one of palladium nitrate dihydrate, rhodium nitrate dihydrate, chloroauric acid tetrahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and chloroplatinic acid hexahydrate.

7. The method for preparing a methanol catalyst according to claim 2, characterized in that, In the step of preparing the catalyst feedstock, the auxiliary agent is at least one selected from Au salt, Ag salt, Co salt, Ni salt, Ir salt, Ru salt, Rh salt, Pt salt, and Pd salt.

8. The method for preparing a methanol catalyst according to claim 2, characterized in that, In the step of preparing the catalyst raw materials, the heating and stirring temperature is 90℃~150℃, or the heating and stirring temperature is 90℃, 100℃, 120℃, 130℃ or 150℃.

9. The method for preparing a methanol catalyst according to claim 2, characterized in that, In the calcination step, the vacuum-like environment is 0.5 Torr to 10.0 Torr, or the vacuum-like environment is 0.5 Torr, 0.8 Torr, 1.0 Torr, 2.0 Torr, 3.0 Torr, 4.0 Torr, 5.0 Torr, 6.0 Torr, 7.0 Torr, 8.0 Torr, 9.0 Torr, or 10.0 Torr, and / or the calcination temperature is 400℃ to 600℃, or the calcination temperature is 400℃, 425℃, 450℃, 475℃, 500℃, 525℃, 550℃, 575℃, or 600℃.

10. The application of the methanol catalyst according to claim 1 or the methanol catalyst prepared by the method according to any one of claims 2 to 9, characterized in that, It is used in the reaction of hydrogenating carbon dioxide to produce methanol.

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