Catalyst for preparing methanol through carbon dioxide hydrogenation and preparation method thereof

Abstract

The invention relates to a catalyst for preparing methanol through hydrogenation of carbon dioxide. The catalyst comprises a hydroxide compound with a core-shell structure, the hydroxide compound with the core-shell structure is formed by taking a lamellar hydroxide as a core and coating the lamellar hydroxide with a granular hydroxide to form a shell; wherein the lamellar hydroxide and the granular hydroxide respectively and independently comprise one or more of hydroxides of copper, manganese, nickel, indium, zinc, aluminum, cerium, zirconium, cobalt, gallium and silicon, and the lamellar hydroxide and the granular hydroxide in the hydroxide compound with the same core-shell structure are different. Lamellar hydroxides in the hydroxide compounds with different core-shell structures are different. The invention further provides a preparation method of the catalyst, the preparation method is simple in process and low in cost, and the prepared catalyst is high in active element content, high in catalytic activity, high in carbon dioxide conversion rate and high in methanol yield.

Description

Technical Field

[0001] The invention belongs to catalyst preparation technology and relates to a catalyst for catalyzing the hydrogenation of carbon dioxide to produce methanol and a preparation method thereof. Background Art

[0002] Over the past few decades, researchers have developed a large number of heterogeneous catalysts for the hydrogenation of carbon dioxide to methanol, among which copper-based catalysts are the most widely used. A large number of studies have shown that the reaction occurring on copper-based catalysts is a structure-sensitive reaction, and the synergistic effect between copper and the support (strong metal-support interaction, defects, steps, etc.) plays a vital role. Despite this, there are still some problems with copper-based catalysts, including low activity at moderate temperatures (200-250°C) and rapid deactivation due to sintering caused by high loading. However, reducing the copper content means reducing the active center, and for this reason, the formation of a strong metal-support interaction interface has received widespread attention. It not only provides carbon dioxide adsorption sites, but also enhances the electron transfer efficiency between the metal and the support, promoting the activation of hydrogen.

[0003] With the advancement of characterization methods, more and more researchers believe that the presence of monovalent copper ions is beneficial to enhancing the adsorption strength of the intermediate product carbon monoxide, thereby promoting its further conversion to methanol. Based on the theory that monovalent copper ions are active sites, researchers have increased the proportion of monovalent copper ions by changing the catalyst preparation method and constructing special structures, thereby improving the activity of the catalyst. Despite this, the content of monovalent copper in existing copper-based catalysts on the contact surface with the carrier is still relatively low. In the process of catalyzing the hydrogenation of carbon dioxide to methanol, there are problems such as the low Tamman temperature of copper nanoparticles, easy sintering, and the possibility of active center reconstruction during long-term use. The conversion rate of carbon dioxide and the yield of methanol are relatively low. Therefore, there is a need to research and develop a catalyst for catalyzing the hydrogenation of carbon dioxide to methanol with a high active element content, high carbon dioxide conversion rate and high methanol yield. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to address the problems existing in the prior art by providing a catalyst for the hydrogenation of carbon dioxide to methanol. The catalyst has a high content of active elements, resulting in a high carbon dioxide conversion rate and methanol yield. The present invention also provides a novel method for preparing the catalyst. This novel method is simple and low-cost, and the prepared catalyst has a high content of active elements and high catalytic activity.

[0005] To this end, the first aspect of the present invention provides a catalyst for producing methanol by hydrogenating carbon dioxide, which comprises a hydroxide complex with a core-shell structure; the hydroxide complex with a core-shell structure is composed of a lamellar hydroxide as a core, and a granular hydroxide covering the lamellar hydroxide to form a shell; wherein the lamellar hydroxide and the granular hydroxide independently include one or more hydroxides of copper, manganese, nickel, indium, zinc, aluminum, cerium, zirconium, cobalt, gallium and silicon, the lamellar hydroxide and the granular hydroxide in the hydroxide complex with the same core-shell structure are different, and the lamellar hydroxides in hydroxide complexes with different core-shell structures are different.

[0006] Preferably, the mass fraction of the main active element in the catalyst is 1% to 40%, with the remainder being other elements; wherein the main active element includes one or more of copper, manganese, nickel, indium and zinc.

[0007] A second aspect of the present invention provides a method for preparing a catalyst for hydrogenating carbon dioxide to methanol, comprising:

[0008] Step A, adding lamellar hydroxide and granular hydroxide into deionized water according to the elemental composition of the core-shell structure hydroxide complex, adding an acid-base regulator, stirring and reacting, and then filtering, washing with water, and drying to obtain a catalyst precursor;

[0009] Step B, calcining the catalyst precursor to obtain a catalyst for hydrogenating carbon dioxide to methanol;

[0010] The lamellar hydroxide and the granular hydroxide independently include one or more hydroxides of copper, manganese, nickel, indium, zinc, aluminum, cerium, zirconium, cobalt, gallium and silicon.

[0011] In some embodiments of the present invention, in step A, the mass ratio of deionized water to the lamellar hydroxide and the granular hydroxide is 100-200:1.

[0012] In some embodiments of the present invention, in step A, the pH is 5-9.

[0013] In some embodiments of the present invention, in step A, the reaction temperature is 30-100° C., and the reaction time is 0.5-72 hours.

[0014] According to the present invention, the calcination temperature is 200 to 500° C., and the calcination time is 1 to 10 hours.

[0015] In the present invention, the acid-base regulator includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate and ammonia water.

[0016] In some embodiments of the present invention, the mass fraction of the hydroxide of the main active element in the catalyst is 1% to 40%, and the remainder is hydroxides of other elements; wherein the main active element includes one or more of copper, manganese, nickel, indium and zinc.

[0017] In some embodiments of the present invention, in step A, lamellar hydroxide and granular hydroxide are added to deionized water in sequence according to the elemental composition of the hydroxide complex with a core-shell structure.

[0018] The third aspect of the present invention provides use of the catalyst for producing methanol from carbon dioxide hydrogenation as described in the first aspect of the present invention or the catalyst for producing methanol from carbon dioxide hydrogenation as described in the second aspect of the present invention in producing methanol from carbon dioxide hydrogenation.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] 1. The catalyst synthesized by the present invention has the following characteristics: (1) The catalyst synthesized by the wet kneading method has a high proportion of active elements (e.g., copper), which is conducive to enhancing the adsorption and further hydrogenation of the intermediate carbon monoxide, thereby promoting its further conversion to methanol. (2) The catalyst is relatively stable, and its unique core-shell structure gives the catalyst high stability.

[0021] 2. The raw materials used in the preparation process of the present invention are relatively low in price and the preparation process is simple.

[0022] 3. This patent develops a new type of catalytic material. A catalyst that can be cross-deposited on the catalyst surface to form a core-shell structure is synthesized by wet kneading method, and is applied to the hydrogenation of carbon dioxide to methanol. The catalyst preparation method is simple and low in cost, providing a new option for the hydrogenation of carbon dioxide to methanol. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The present invention will be further described in detail below with reference to the accompanying drawings:

[0024] Figure 1 This is a model diagram of the catalyst synthesis process;

[0025] Figure 2 SEM images (a–b) of the copper-zinc-aluminum catalyst synthesized by the wet kneading method and SEM images (c–d) of the copper-zinc-aluminum catalyst synthesized by the co-precipitation method in the present invention;

[0026] Figure 3 (a) HR-TEM image, (b) STEM image, and corresponding (c–f) EDS elemental analysis images of the CuZnAl catalyst synthesized by wet kneading method;

[0027] Figure 4(a) HR-TEM image, (b) STEM image, and corresponding (c–f) EDS elemental analysis images of the CuZnAl catalyst synthesized by co-precipitation method;

[0028] Figure 5 Schematic diagram of the micro fixed bed reaction device in the present invention. DETAILED DESCRIPTION

[0029] To facilitate understanding of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and examples. However, before describing the present invention in detail, it should be understood that the present invention is not limited to the specific embodiments described. It should also be understood that the terminology used herein is for the purpose of describing specific embodiments only and is not intended to be limiting.

[0030] Where a range of values ​​is provided, it is understood that each intervening value between the upper and lower limits of the range and any other specified or intervening values ​​in the specified range is encompassed within the present invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the present invention, subject to any express exclusions in the specified range. Where a specified range includes one or both limits, ranges excluding either or both of those included limits are also encompassed within the present invention.

[0031] Unless otherwise defined, all terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, preferred methods and materials are now described.

[0032] I. Terminology

[0033] The term "silicon hydroxide" as used in the present invention refers to silicon dioxide.

[0034] The term "hydroxides of other elements" as used in the present invention refers to the hydroxide of the main active element in the catalyst; in the present invention, the lamellar hydroxide and the granular hydroxide independently include one or more hydroxides of copper, manganese, nickel, indium, zinc, aluminum, cerium, zirconium, cobalt, gallium and silicon. When the main active element includes one or more of copper, manganese, nickel, indium and zinc, the rest are "hydroxides of other elements"; for example, when the main active element is copper, manganese, nickel, indium, zinc, aluminum, cerium, zirconium, cobalt, gallium and silicon are "hydroxides of other elements".

[0035] The term "water" in the present invention, unless otherwise specified or limited, refers to deionized water, distilled water or ultrapure water.

[0036] II. Implementation Plan

[0037] As previously mentioned, the content of monovalent copper in existing copper-based catalysts on the contact surface with the support is still relatively low. This leads to problems such as the low Tammann temperature of copper nanoparticles, sintering, and the potential for active center remodeling over long-term use during the catalytic CO2 hydrogenation to methanol reaction. This results in low CO2 conversion and methanol yields. In light of this, the present inventors have conducted extensive research on catalytic technologies for CO2 hydrogenation to methanol.

[0038] The inventors have found that during the wet kneading process, due to the introduction of multiple hydroxides, the change in the pH of the solution promotes the dissolution of the hydroxide surface, and the mutual etching between copper and other metal precursors. Subsequently, driven by the surface charge, cross-deposition occurs (zinc and aluminum species are slowly deposited on the surface of copper species, while the other two species are slowly deposited on the surface of zinc or aluminum) to form a core-shell structure. The catalyst synthesis process model is shown in the figure below. Figure 1 As shown. This structure can, on the one hand, increase the proportion of monovalent copper, promote further hydrogenation of the intermediate carbon monoxide to produce methanol, thereby improving the selectivity of methanol; on the other hand, it can balance the hydrogen dissociation rate and the carbon monoxide adsorption rate, thereby further stimulating the positive transition of the reaction equilibrium, avoiding excessive hydrogen adsorption and dissociation and desorption of carbon monoxide, and ultimately improving the carbon dioxide conversion rate and methanol yield, thereby obtaining the present invention.

[0039] To this end, the present invention adopts a wet kneading method to synthesize a catalyst for hydrogenating carbon dioxide to methanol, and the specific operation is as follows:

[0040] Step A: adding lamellar hydroxide and granular hydroxide to deionized water simultaneously according to the elemental composition of the core-shell structure hydroxide complex, adding an acid-base regulator to adjust the pH to 5-9, stirring and reacting at 30-100° C. for 0.5-72 hours, and then filtering, washing with water, and drying to obtain a catalyst precursor;

[0041] Step B, calcining the catalyst precursor at 200-500° C. for 1-10 hours to obtain a catalyst for hydrogenating carbon dioxide to methanol;

[0042] The lamellar hydroxide and the granular hydroxide independently include one or more hydroxides of copper, manganese, nickel, indium, zinc, aluminum, cerium, zirconium, cobalt, gallium and silicon.

[0043] In the above step A, the mass ratio of deionized water to the total amount of the lamellar hydroxide and the granular hydroxide is 100-200:1.

[0044] In the present invention, the acid-base regulator includes but is not limited to one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate and ammonia water.

[0045] In some embodiments of the present invention, the mass fraction of the hydroxide of the main active element in the catalyst is 1% to 40%, and the balance is hydroxides of other elements; wherein the main active element includes one or more of copper, manganese, nickel, indium and zinc; preferably, when the catalyst contains hydroxides of two or more other elements, the molar ratio between the hydroxides of each other element is 1:1.

[0046] The inventors have found that in step A, lamellar hydroxide and granular hydroxide are added to deionized water in sequence according to the elemental composition of the core-shell structure hydroxide complex. For example, the order of adding the materials is any one of copper-zinc-aluminum, copper-zinc followed by aluminum, copper-aluminum followed by zinc, and zinc-aluminum followed by copper. The prepared catalyst has higher activity and better stability.

[0047] The study found that the catalyst for producing methanol from carbon dioxide hydrogenation prepared by the above-mentioned preparation method comprises a hydroxide complex with a core-shell structure; the hydroxide complex with a core-shell structure is composed of a lamellar hydroxide as a core, and a granular hydroxide coating the lamellar hydroxide to form a shell; wherein the lamellar hydroxide and the granular hydroxide independently include one or more hydroxides of copper, manganese, nickel, indium, zinc, aluminum, cerium, zirconium, cobalt, gallium and silicon, the lamellar hydroxide and the granular hydroxide in the hydroxide complex with the same core-shell structure are different, and the lamellar hydroxides in the hydroxide complexes with different core-shell structures are different.

[0048] Further research has found that when the mass fraction of the main active elements such as copper, manganese, nickel, indium and zinc in the catalyst is 1% to 40%, and the balance is other elements, the catalytic activity of the catalyst is higher.

[0049] For example, in a specific example, a catalyst for producing methanol from carbon dioxide hydrogenation prepared with copper-zinc-aluminum hydroxide may include a copper-zinc-aluminum hydroxide complex having a core-shell structure composed of a lamellar copper hydroxide core and a shell formed by zinc hydroxide particles and aluminum hydroxide particles coated on the surface of the lamellar copper hydroxide core (referred to as copper core / (aluminum + zinc) shell in the present invention), a zinc-copper-aluminum hydroxide complex having a core-shell structure composed of a lamellar zinc hydroxide core and a shell formed by copper hydroxide particles and aluminum hydroxide particles coated on the surface of the lamellar zinc hydroxide core (referred to as zinc core / (copper + aluminum) shell in the present invention), and an aluminum-copper-zinc hydroxide complex having a core-shell structure composed of a lamellar aluminum hydroxide core and a shell formed by copper hydroxide particles and zinc hydroxide particles coated on the surface of the lamellar aluminum hydroxide core (referred to as aluminum core / (copper + zinc) shell in the present invention).

[0050] Those skilled in the art should understand that the catalyst for producing methanol by hydrogenation of carbon dioxide provided by the present invention needs to be pretreated in situ by passing hydrogen before use to obtain a reduced catalyst for producing methanol by hydrogenation of carbon dioxide.

[0051] For example, in a specific example, a catalyst for the hydrogenation of carbon dioxide to produce methanol prepared from copper-zinc-aluminum hydroxide is first introduced with hydrogen when used, and then subjected to in-situ reduction pretreatment at 300° C. in a reactor for 1 hour to obtain a reduced catalyst. The catalyst may include a copper-zinc-aluminum oxide composite having a core-shell structure composed of a lamellar copper core and a shell formed by composite zinc-aluminum oxide particles coated on the surface of the lamellar copper core (referred to as copper core / (aluminum + zinc) shell in the present invention), a zinc-copper-aluminum oxide composite having a core-shell structure composed of a lamellar zinc oxide core and a shell formed by copper-aluminum oxide particles coated on the surface of the lamellar zinc oxide core (referred to as zinc core / (copper + aluminum) shell in the present invention), and an aluminum-copper-zinc oxide composite having a core-shell structure composed of a lamellar aluminum oxide core and a shell formed by composite copper-zinc oxide particles coated on the surface of the lamellar aluminum oxide core (referred to as aluminum core / (copper + zinc) shell in the present invention); preferably, the mass fraction of the copper element is 1% to 40%.

[0052] The use of the catalyst for producing methanol from carbon dioxide hydrogenation provided by the present invention in producing methanol from carbon dioxide hydrogenation can be understood as a method for producing methanol from carbon dioxide hydrogenation catalyzed by the catalyst for producing methanol from carbon dioxide hydrogenation.

[0053] In some specific embodiments of the present invention, the Figure 5 The method for producing methanol based on carbon dioxide hydrogenation in a micro-fixed bed reactor equipped with temperature and pressure sensors and condensation includes the following steps:

[0054] (1) 0.3 g of granulated catalyst (40 to 60 mesh) and 10 g of quartz sand (40 to 60 mesh) were mixed evenly and then loaded into the reaction tube;

[0055] (2) introducing hydrogen and pre-treating the reaction in situ at 300°C for 1 hour in a microreactor with a heating rate of 5°C per minute;

[0056] (3) After cooling to room temperature, the pressure is raised again to 4.5 MPa and 250°C, and carbon dioxide feed gas is introduced to produce methanol.

[0057] The carbon dioxide raw gas composition is 24% carbon dioxide, 72% hydrogen, 4% argon, and the space velocity is 4000 per hour.

[0058] III. Examples

[0059] The present invention is described in detail below through specific examples. The experimental methods described below, unless otherwise specified, are all routine laboratory methods. The experimental materials described below, unless otherwise specified, can all be obtained from commercial channels.

[0060] The effects of reaction conditions on the prepared catalysts and their catalytic performance are investigated below through Examples 1-57.

[0061] (1) The catalyst is prepared by wet kneading method. The specific preparation method is as follows:

[0062] Various metal hydroxides were added to deionized water in varying orders, along with an acid-base modifier. The mass ratio of deionized water to solid powder was 100-200, and the mixture was stirred at 30-100°C and a pH of 5-9 for 0.5-72 hours. The mixture was then filtered, washed, dried, and calcined at 200-500°C for 1-10 hours to obtain a catalyst. Comparative samples included catalysts without the acid-base modifier and catalysts obtained by conventional co-precipitation.

[0063] (2) The catalyst prepared by the present invention is used to catalyze the hydrogenation of carbon dioxide to methanol, and the specific steps are as follows:

[0064] The performance of the catalyst was tested in a micro fixed bed reactor equipped with temperature, pressure sensors and condensation Figure 5 The experimental process is as follows: first, 0.3 g of the granulated catalyst (40 to 60 mesh) is mixed evenly with 10 g of quartz sand (40 to 60 mesh) and then loaded into the reaction tube; secondly, hydrogen is introduced and pre-treated in situ at 300 ° C in a micro-reaction for 1 hour with a heating rate of 5 degrees per minute. Finally, after cooling to room temperature, the pressure is re-raised to 4.5 MPa and 250 ° C, and carbon dioxide feed gas is introduced to evaluate the catalyst activity. The feed gas composition consists of 24% carbon dioxide, 72% hydrogen, and 4% argon. The space velocity is 4000 per hour. The carbon dioxide conversion rate is obtained by measuring the gas composition before and after the reaction, and the reactor outlet gas is analyzed by a gas chromatograph equipped with a TCD detector. The selectivity of the condensed liquid product is obtained by analyzing the internal standard method on a gas chromatograph equipped with an FID detector.

[0065] The reaction conditions for preparing the catalysts in Examples 1-57, as well as the carbon dioxide conversion rate and methanol selectivity for catalytic hydrogenation of carbon dioxide to methanol using the catalysts are shown in Tables 1-3 below.

[0066] Table 1

[0067]

[0068]

[0069] The effects of varying conditions on CO2 conversion and methanol selectivity were investigated. Results showed that simultaneous addition of copper, zinc, and aluminum resulted in generally higher CO2 conversion and methanol selectivity compared to examples with different addition sequences. Examples using sodium hydroxide exhibited higher CO2 conversion and methanol selectivity, particularly when adding aluminum after copper and zinc, while the opposite was true under ammonia conditions. Furthermore, a higher solution-to-solid powder mass ratio correlated with higher methanol selectivity. This suggests that varying the wet kneading conditions can further enhance the activity of the copper-zinc-aluminum catalyst. A comparative co-precipitated copper-zinc-aluminum catalyst, calcined at 500°C for 5 hours and with a copper mass fraction of 29.5%, exhibited CO2 conversion of 20% and methanol selectivity of 50%, respectively, significantly lower than the copper-zinc-aluminum catalyst synthesized by the wet kneading method.

[0070] Table 2 No acid-base regulator

[0071]

[0072]

[0073] When no acid hydrolysis regulator is added, it can be found that the methanol selectivity of the embodiment ranges from approximately 50% to 70%. When an acid-base regulator is added (taking sodium hydroxide as an example), the methanol selectivity ranges from approximately 49% to 80%. In general, the addition of an acid-base regulator seems to have a positive effect on improving the methanol selectivity, but the specific effect may depend on the type of regulator used and other experimental conditions.

[0074] Table 3

[0075]

[0076]

[0077] The copper-zinc-aluminum catalyst synthesized by the wet kneading method of the present invention is compared with the copper-zinc-aluminum catalyst synthesized by the coprecipitation method. Figure 2 SEM images (a–b) of the copper-zinc-aluminum catalyst synthesized by the wet kneading method and SEM images (c–d) of the copper-zinc-aluminum catalyst synthesized by the co-precipitation method in the present invention; Figure 3 (a) HR-TEM image, (b) STEM image, and corresponding (c–f) EDS elemental analysis images of the CuZnAl catalyst synthesized by wet kneading method; Figure 4 (a) HR-TEM image, (b) STEM image, and corresponding (c–f) EDS elemental analysis images of the CuZnAl catalyst synthesized by co-precipitation method.

[0078] pass Figure 2-4It can be seen from Table 3 that the wet kneading method has good universality and can still have good catalytic performance when applied to a variety of copper-based and non-copper-based catalysts.

[0079] It should be noted that the embodiments described above are only preferred embodiments of the present invention and are used for illustration to facilitate understanding of the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A catalyst for producing methanol from carbon dioxide hydrogenation, comprising a core-shell structured hydroxide complex; the core-shell structured hydroxide complex comprises a lamellar hydroxide as a core and a granular hydroxide covering the lamellar hydroxide to form a shell; wherein: The lamellar hydroxide and the granular hydroxide independently include one or more hydroxides of copper, manganese, nickel, indium, zinc, aluminum, cerium, zirconium, cobalt, gallium and silicon. The lamellar hydroxide and the granular hydroxide in the hydroxide complex with the same core-shell structure are different, and the lamellar hydroxide in the hydroxide complexes with different core-shell structures are different.

2. The catalyst according to claim 1, characterized in that The mass fraction of the main active element in the catalyst is 1% to 40%, and the balance is other elements; wherein the main active element includes one or more of copper, manganese, nickel, indium and zinc.

3. A method for preparing a catalyst for hydrogenating carbon dioxide to methanol, comprising: Step A, adding lamellar hydroxide and granular hydroxide into deionized water according to the elemental composition of the core-shell structure hydroxide complex, adding an acid-base regulator, stirring and reacting, and then filtering, washing with water, and drying to obtain a catalyst precursor; Step B, calcining the catalyst precursor to obtain a catalyst for hydrogenating carbon dioxide to methanol; The lamellar hydroxide and the granular hydroxide independently include one or more hydroxides of copper, manganese, nickel, indium, zinc, aluminum, cerium, zirconium, cobalt, gallium and silicon.

4. The preparation method according to claim 3, characterized in that In step A, the mass ratio of deionized water to the lamellar hydroxide and the granular hydroxide is 100 to 200:1; and / or, the pH is 5 to 9; And / or, the reaction temperature is 30-100° C., and the reaction time is 0.5-72 hours.

5. The preparation method according to claim 3, characterized in that The calcination temperature is 200-500° C., and the calcination time is 1-10 hours.

6. The method according to claim 3, characterized in that The acid-base regulator includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate and ammonia water.

7. The method according to claim 3, characterized in that The mass fraction of the hydroxide of the main active element in the catalyst is 1% to 40%; wherein the main active element includes one or more of copper, manganese, nickel, indium and zinc.

8. The method according to any one of claims 3 to 7, characterized in that In step A, lamellar hydroxide and granular hydroxide are added to deionized water in sequence according to the elemental composition of the hydroxide complex with a core-shell structure.

9. Use of the catalyst for producing methanol from carbon dioxide by hydrogenation according to claim 1 or 2 or the catalyst for producing methanol from carbon dioxide by hydrogenation according to any one of claims 3 to 8 in producing methanol from carbon dioxide by hydrogenation.

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