A ternary metal solid solution catalyst, a preparation method and application thereof

Abstract

The present disclosure provides a ternary metal solid solution catalyst, a preparation method and application thereof, wherein Cu exists in a single atom structure, and the Cu single atom structure can produce a synergistic effect with oxygen vacancies in a ZnZrOx solid solution, thereby significantly enhancing the adsorption and activation capacity for CO2.

Description

Technical Field

[0001] This application relates to the field of catalyst technology, specifically to a ternary metal solid solution catalyst, its preparation method, and its application. Background Technology

[0002] With the continuous growth of global energy consumption and the massive use of fossil fuels, greenhouse gas emissions have increased dramatically, leading to a continuous rise in atmospheric carbon dioxide concentrations and triggering a series of ecological and environmental problems such as global warming, glacial melting, and sea-level rise. Carbon dioxide capture, utilization, and storage (CCUS) technology is a key technological path to achieving the strategic goals of "carbon peaking and carbon neutrality" and promoting green and low-carbon development. The hydrogenation of carbon dioxide to methanol not only enables the resource utilization of greenhouse gases but also yields methanol, an important clean energy source and basic chemical raw material, possessing significant economic and environmental value.

[0003] Currently, catalysts for the hydrogenation of carbon dioxide to methanol are mainly classified into Cu-based catalysts, noble metal catalysts, and metal oxide solid solution catalysts. Industrially, CuZnAl catalysts are the mainstream choice, but they suffer from low carbon dioxide conversion rates, poor methanol selectivity, and susceptibility to deactivation. While noble metal catalysts (such as Pd, Pt, and Au) exhibit good catalytic activity, their high cost makes large-scale industrial application difficult.

[0004] Among existing metal oxide solid solution catalysts, ZnZrOx solid solution catalysts exhibit high methanol selectivity, but their carbon dioxide conversion capacity is insufficient and their methanol space-time yield is low. Solid solution catalysts doped with some precious metals are limited by cost, while solid solutions containing toxic metals such as Cd do not meet green environmental protection requirements. Currently, catalysts that combine high carbon dioxide conversion, high methanol selectivity, and high methanol space-time yield, while also being low-cost and environmentally friendly, are still relatively scarce, failing to meet the needs of industrial applications of carbon dioxide hydrogenation to methanol.

[0005] Given the shortcomings of the existing technologies, developing a novel solid solution catalyst that is highly active, selective, low-cost, easy to prepare, and has directionally controllable catalytic performance has become an urgent technical problem to be solved in this field. Summary of the Invention

[0006] The purpose of this disclosure is to provide a novel solid solution catalyst that is highly active, selective, low in cost, easy to prepare, and whose catalytic performance can be directionally controlled.

[0007] To achieve the above objectives, the first aspect of this disclosure provides a ternary metal solid solution catalyst, wherein the ternary metal solid solution catalyst is a solid solution catalyst containing Cu, Zn, and Zr, wherein Cu exists as a single atom; the molar ratio of Zn to Zr is 0.05-0.2; and the molar ratio of the amount of Cu to the sum of the amounts of Zn and Zr is 0.005-0.03.

[0008] On the other hand, this disclosure provides a method for preparing the above-mentioned ternary metal solid solution catalyst, which includes the following steps: S1. Dissolve Cu salt, Zn salt, and Zr salt in deionized water and stir to obtain the first solution; S2. Dissolve the precipitant in the first solution to obtain the second solution; S3. Add the first solution and the second solution dropwise to deionized water, and perform aging and cooling treatment to obtain a suspension. S4. The suspension is separated, dried, calcined and activated. The molar ratio of Zn to Zr is 0.05-0.2; the molar ratio of Cu to the sum of Zn and Zr is 0.005-0.03. The roasting temperature is 400-600℃, and the roasting time is 3-5h.

[0009] Optionally, the Cu salt is selected from one or more of copper nitrate, copper acetate, copper chloride, and copper sulfate; the Zn salt is selected from one or more of zinc nitrate, zinc acetate, zinc chloride, and zinc sulfate; and the Zr salt is selected from one or more of zirconium nitrate, zirconium acetate, zirconium chloride, and zirconium sulfate. The precipitant is selected from one or more of nitrates, acetates, halides and sulfates.

[0010] Optionally, in step S3, the dropping rate of the first solution and the second solution is 0.1-3 mL / min; The aging temperature is 50-90℃, and the aging time is 1-5 h.

[0011] Optionally, in step S4, the drying temperature is 80-150℃, the drying time is 4-12 h, the calcination heating rate is 2-10℃ / min, and the calcination atmosphere is one or more of air, oxygen, or nitrogen. The activation atmosphere is hydrogen, argon, carbon monoxide, or a mixture of carbon dioxide and hydrogen; the volume percentage of hydrogen in the mixture is 30-60%; the activation temperature is 300-400℃, the activation time is 1-5h, the activation pressure is atmospheric pressure; the activation gas flow rate is 2-30 mL / min, and the activation heating rate is 1-10℃ / min.

[0012] On the other hand, this disclosure provides the application of the above-mentioned ternary metal solid solution catalyst in the hydrogenation of carbon dioxide to methanol.

[0013] The reaction conditions for the hydrogenation of carbon dioxide to methanol include: a reaction pressure of 2-5 MPa, a reaction temperature of 200-340℃, and a reaction space velocity of 6000-24000 mL / (g). h); the raw material gas molar ratio n (H2):n (CO2) = 3:1.

[0014] Optionally, the catalyst is activated with an activating gas before the carbon dioxide hydrogenation to methanol reaction; The activating gas is selected from one or more of hydrogen, carbon monoxide, carbon dioxide or argon.

[0015] Through the above technical solution, this disclosure provides a ternary metal solid solution catalyst, its preparation method and application. In this catalyst, Cu exists in a single-atom structure. This single-atom Cu structure can produce a synergistic effect with the oxygen vacancies in the ZnZrOx solid solution, significantly enhancing the adsorption and activation capacity of CO2.

[0016] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Attached Figure Description

[0017] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings: Figure 1 Cu1ZnZrO x Cu1ZrO x and Cu1ZnO x XRD pattern of the catalyst; Figure 2 A comparison of the catalytic performance of Cu-based single-atom catalysts under different atmospheres; Figure 3 The space-time yield diagrams of Cu-based single-atom catalysts under different atmospheres are shown. Figure 4 EPR spectra and X-ray photoelectron spectra of Cu-based single-atom catalysts under different atmospheres; Figure 5 The Zn XPS spectrum and Zn LMM energy spectrum of Cu-based single-atom catalysts under different atmospheres are shown. Figure 6 XAS spectra and R-space EXAFS spectra of Cu-based single-atom catalysts under different atmospheres; Figure 7Cu1ZnZrO is a solid solution catalyst. x Transmission electron microscope image with spherical aberration. Detailed Implementation

[0018] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of this disclosure.

[0019] The first aspect of this disclosure provides a ternary metal solid solution catalyst, wherein the ternary metal solid solution catalyst is a solid solution catalyst containing Cu, Zn and Zr, wherein Cu exists as a single atom; the molar ratio of Zn to Zr is 0.05-0.2; and the molar ratio of the amount of Cu to the sum of the amounts of Zn and Zr is 0.005-0.03.

[0020] On the other hand, this disclosure provides a method for preparing the above-mentioned ternary metal solid solution catalyst, which includes the following steps: S1. Dissolve Cu salt, Zn salt, and Zr salt in deionized water and stir to obtain the first solution; S2. Dissolve the precipitant in the first solution to obtain the second solution; S3. Add the first solution and the second solution dropwise to deionized water, and perform aging and cooling treatment to obtain a suspension. S4. The suspension is separated, dried, calcined and activated. The molar ratio of Zn to Zr is 0.05-0.2; the molar ratio of Cu to the sum of Zn and Zr is 0.005-0.03. The roasting temperature is 400-600℃, and the roasting time is 3-5h.

[0021] Optionally, the Cu salt is selected from one or more of copper nitrate, copper acetate, copper chloride, and copper sulfate; the Zn salt is selected from one or more of zinc nitrate, zinc acetate, zinc chloride, and zinc sulfate; and the Zr salt is selected from one or more of zirconium nitrate, zirconium acetate, zirconium chloride, and zirconium sulfate. The precipitant is selected from one or more of nitrates, acetates, halides and sulfates.

[0022] Optionally, in step S3, the dropping rate of the first solution and the second solution is 0.1-3 mL / min; The aging temperature is 50-90℃, and the aging time is 1-5 h.

[0023] Optionally, in step S4, the drying temperature is 80-150℃ and the drying time is 4-12 h; The calcination heating rate is 2-10℃ / min; the calcination includes static calcination or flowing atmosphere calcination, and the calcination equipment includes a muffle furnace or a tube furnace; the calcination atmosphere is one or more of air, oxygen or nitrogen. The activation atmosphere is hydrogen, argon, carbon monoxide, or a mixture of carbon dioxide and hydrogen; the volume percentage of hydrogen in the mixture is 30-60%; the activation temperature is 300-400℃, the activation time is 1-5h, the activation pressure is atmospheric pressure; the activation gas flow rate is 2-30 mL / min, and the activation heating rate is 1-10℃ / min.

[0024] On the other hand, this disclosure provides the application of the ternary metal solid solution catalyst described in the first aspect of this disclosure in the production of methanol by hydrogenation of carbon dioxide.

[0025] Optionally, the reaction conditions for the hydrogenation of carbon dioxide to methanol include: a reaction pressure of 2-5 MPa, a reaction temperature of 200-340℃, and a reaction space velocity of 6000-24000 mL / (g). h); the raw material gas molar ratio n (H2):n (CO2) = 3:1.

[0026] Optionally, the catalyst is activated with an activating gas before the carbon dioxide hydrogenation to methanol reaction; The activating gas is selected from one or more of hydrogen, carbon monoxide, carbon dioxide or argon, preferably argon.

[0027] The inventors of this disclosure unexpectedly discovered that the pretreatment atmosphere of the catalyst significantly affects the Zn-O coordination structure, thereby regulating the concentration of oxygen vacancies on its surface. Oxygen vacancies are key active sites for carbon dioxide adsorption and activation, and their concentration directly determines the catalyst's performance in CO2 conversion. Through a systematic comparison of the effects of different pretreatment atmospheres on catalyst performance, it was found that the catalyst pretreated with argon (Ar) exhibited the highest oxygen vacancy concentration and the best CO2 conversion rate compared to the Cu1ZnZrOx catalyst activated with hydrogen (H2). This indicates that Ar atmosphere pretreatment helps promote the generation of oxygen vacancies on the catalyst surface, further enhancing its CO2 activation ability and significantly improving the catalyst's conversion performance.

[0028] The present disclosure is further described in detail below through examples. All raw materials used in the examples are commercially available.

[0029] Example 1 Weigh 0.0144 g of Cu(NO3)2·3H2O, 0.2310 g of Zn(NO3)2·6H2O, and 2.2349 g of Zr(NO3)2·5H2O into a 500 mL beaker, add 200 mL of deionized water, and stir until dissolved (solution A). Separately weigh 1.2813 g of (NH4)2CO3 into a 500 mL beaker, add 500 mL of deionized water, and stir until dissolved (solution B). Slowly add solutions A and B simultaneously to a round-bottom flask containing 100 mL of deionized water. Under 80°C water bath heating conditions, use magnetic stirring at 600 rpm and a dropping rate of 0.3 mL / min. After the addition is complete, maintain the 80°C water bath conditions and allow to stand for 2 h for aging. Then cool to room temperature and centrifuge at 10000 rpm for 5 min to obtain a white gel solid. The resulting precipitate was washed three times with deionized water and dried in an oven at 110℃ for 12 h. The resulting white solid was then ground into powder in an agate mortar. The white powder precursor was weighed and calcined in a muffle furnace at 500℃ for 3 h at a heating rate of 2℃ / min. The catalyst obtained after calcination was Cu1ZnZrOx. x The solid solution catalyst is a ternary metal solid solution catalyst of Cu, Zn, and Zr, in which Cu exists in the form of Cu single-atom structure, the atomic ratio of Zn atoms to Zr atoms is Zn / Zr is 8:92, and the sum of the atomic percentages of Cu atoms in Zn atoms and Zr atoms, Cu / (Zn+Zr), is 1%. The Cu1ZnZrOx solid solution catalyst was pressed into tablets (8 MPa, 5 min), crushed, and screened with 40-60 mesh catalyst for catalytic performance evaluation.

[0030] 0.1 g of the selected catalyst was weighed and loaded into a reaction tube with an inner diameter of 8 mm. Reduction was carried out at 350 °C for 3 h under normal pressure and a pure H2 atmosphere at a flow rate of 30 mL / min. Then, a feed gas with an n(H2):n(CO2) ratio of 3 was introduced, and the reaction was carried out at 5 MPa, 200-340 °C, and a reaction space velocity of 24000 mL / g. -1 h -1 Catalytic performance was evaluated under the specified conditions.

[0031] Example 2 The catalyst preparation method in this embodiment is the same as in Example 1. 0.1 g of the screened catalyst was weighed and loaded into a reaction tube with an inner diameter of 8 mm. Activation was performed at 350 °C for 3 h under normal pressure and a pure Ar atmosphere at a flow rate of 30 mL / min. Then, a feed gas with n(H2):n(CO2) = 3 was introduced, and the reaction was carried out at 5 MPa, 200-340 °C, and a reaction space velocity of 24000 mL / g. -1 h -1 Catalytic performance was evaluated under the specified conditions.

[0032] Example 3 The catalyst preparation method in this embodiment is the same as in Example 1. 0.1 g of the screened catalyst was weighed and loaded into a reaction tube with an inner diameter of 8 mm. Activation was performed at 350 °C for 3 h under normal pressure and a CO atmosphere at a flow rate of 30 mL / min. Then, a feed gas with n(H2):n(CO2) = 3 was introduced, and the reaction was carried out at 5 MPa, 200-340 °C, and a reaction space velocity of 24000 mL / g. -1 h -1 Catalytic performance was evaluated under the specified conditions.

[0033] Example 4 The catalyst preparation method in this embodiment is the same as in Example 1. 0.1 g of the screened catalyst was weighed and loaded into a reaction tube with an inner diameter of 8 mm. Activation was performed at 350 °C for 3 h in an atmosphere of atmospheric pressure and a mixture of CO2 and H2 (with hydrogen comprising 75% of the mixture by volume), at a flow rate of 30 mL / min. Then, a feed gas with n(H2):n(CO2) = 3 was introduced, and the reaction was carried out at 5 MPa, 200-340 °C, and a reaction space velocity of 24000 mL / g. -1 h -1 Catalytic performance was evaluated under the specified conditions.

[0034] Example 5 The metal salts used in the catalyst preparation were 0.0144 g Cu(NO3)2·3H2O and 2.5504 g Zr(NO3)2·5H2O, and the precipitant used was 1.374 g (NH4)2CO3. The resulting catalyst was denoted as Cu1ZrOx. Other preparation and evaluation steps were the same as in Example 1.

[0035] Example 6 In this embodiment, the metal salts used in the catalyst preparation were 0.0144g Cu(NO3)2·3H2O and 1.7670g Zn(NO3)2·6H2O, and the precipitant used was 0.6956g (NH4)2CO3. The resulting catalyst was denoted as Cu1ZnOx. Other preparation and evaluation steps were the same as in Example 1.

[0036] Test Implementation Examples The XRD patterns of the catalysts obtained in Examples 1 and 5-6 are as follows: Figure 1As shown, Cu1ZnZrOx and Cu1ZrOx exhibit similar diffraction peaks at 2θ = 30.6°, 35.4°, 50.9°, and 60.4°, which correspond to the characteristic diffraction peaks of tetragonal ZrO2 (t-ZrO2, ICSD 81-1550). The Cu1ZnOx sample, however, displays characteristic diffraction peaks of ZnO at 2θ = 31.8°, 34.5°, 36.5°, 47.6°, 56.8°, and 63.1°. Figure 1 (A)). Notably, no detectable diffraction peaks were observed at the corresponding diffraction positions of metallic Cu. Figure 1 (B)). The absence of this Cu signal indicates that the Cu species are highly dispersed on the support surface or exist in single-atom form, with a content below the detection limit of XRD.

[0037] The catalysts obtained in Examples 1-6 were used in the carbon dioxide hydrogenation to methanol reaction, and their catalytic activities were compared. The test results are as follows: Figure 2-3 As shown in the figure. The results indicate that the sample pretreated with H2 still exhibits the highest methanol space-time yield (STY), significantly better than the sample treated under Ar atmosphere. Regarding CO2 conversion, the catalyst performance order is: Ar > H2 > CO2 + H2 > CO. Meanwhile, comparing the catalytic performance of physically mixed or layered packings of Cu1ZnOx and Cu1ZrOx, all three catalysts were evaluated using hydrogen reduction, similar to Example 1. The results show that physically mixed or layered packings of Cu1ZnOx and Cu1ZrOx cannot replicate the strong synergistic effect established at the atomic scale in Cu1ZnZrOx. Figure 2 and Figure 3 In the context of Cu1ZnOx / Cu1ZrOx, Cu1ZnOx and Cu1ZrOx are packed in layers, with Cu1ZnOx on the top layer and Cu1ZrOx on the bottom layer. Correspondingly, Cu1ZrOx / Cu1ZnOx means that Cu1ZrOx is on the top layer and Cu1ZnOx is on the bottom layer. Physical mix refers to the evaluation of the packing after the physical mixing of Cu1ZnOx and Cu1ZrOx.

[0038] Oxygen vacancies (Ov) play a crucial role in CO2 adsorption and activation, combining with electron paramagnetic resonance (EPR)... Figure 4 (A) and X-ray photoelectron spectroscopy (XPS, Figure 4(B) Oxygen vacancy concentration analysis was performed on Cu1ZnZrOx pretreated under different atmospheres; a significant signal appeared in the EPR spectrum at g≈2.003, which is characterized by the unpaired electrons in the surface oxygen vacancies; the signal intensity of the samples treated with different atmospheres changed significantly: the Ov signal of the Ar-treated sample was the strongest, followed by H2, CO, and the mixture. This trend is consistent with the results of O1s XPS, that is, the proportion of oxygen vacancy peak area also increases in the same order.

[0039] To further investigate the changes in the surface composition of Zn species under different atmospheres, Zn 2p XPS analysis was performed on the samples. Figure 5 (A)). The results show that Zn exists mainly in the oxidized state in all samples, and the Zn LMM energy spectrum ( Figure 5 (B) A characteristic peak appears at approximately 991 eV, indicating that the Zn species has undergone partial reduction.

[0040] Zn δ+ Speciation is typically accompanied by a decrease in the coordination number of Zn species. To further verify the relationship between structure and performance, Zn K-edge X-ray absorption fine structure (XAFS) tests were performed on Cu1ZnZrOx catalysts pretreated with different atmospheres. XAFS spectra were obtained from... Figure 6 (A) shows that the absorption edge positions of all samples are between those of the Zn metal foil and the ZnO standard, but closer to the absorption edge of ZnO, indicating that the Zn species underwent partial reduction. In the corresponding R-space EXAFS spectra (…),… Figure 6 In (B), all samples exhibited a significant peak corresponding to Zn-O scattering, while no coordination peaks attributable to Zn-Zn or Zn-O-Zn were detected. This absence of secondary coordination peaks indicates that Zn species exist as isolated single atoms, rather than forming bulk ZnO or metallic Zn clusters. Furthermore, the Zn-O coordination number of all samples was approximately 3, further demonstrating that Zn atoms achieved a highly dispersed single-atom distribution on the support surface. Based on the EXAFS fitting results, the oxygen vacancy (Ov) concentration of the samples was estimated, and the results are shown in Table 1.

[0041] Table 1. Oxygen vacancy concentration and Zn concentration of Cu1ZnZrOx catalyst activated under different atmospheres δ+ Proportion

[0042] As can be seen from the data in Table 1, the oxygen vacancy concentration of the samples shows the following trend with the change of the pretreatment atmosphere: CO2 + H2 < CO < H2 < Ar-treated samples. This indicates that the Cu1ZnZrOx catalysts activated by different atmospheres induce the reconstruction of Zn sites, resulting in differences in the Zn-O coordination number and causing differences in the oxygen vacancy concentration. These oxygen vacancies are very likely to serve as active sites for CO2 adsorption, promoting its activation and conversion to generate intermediates in the methanol synthesis reaction, thereby effectively improving the catalytic performance of CO2 hydrogenation to methanol.

[0043] AC-TEM (Aberration-Corrected Transmission Electron Microscopy) was used to directly observe the dispersion state of Cu species in the synthesized catalysts, as Figure 7 shown. Isolated bright spots marked by circles can be clearly seen on the lattice background. These bright spots belong to single Cu atoms dispersed on the surface of the oxide support, confirming the atomic-level dispersion characteristics of Cu species in all Cu-based catalysts. It can be seen from the figure that Cu exists in the form of Cu single-atom structures.

[0044] The preferred embodiments of the present disclosure have been described in detail above. However, the present disclosure is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0045] In addition, it should be noted that, in the case of no contradiction, the various specific technical features described in the above specific embodiments can be combined in any appropriate manner. To avoid unnecessary repetition, the present disclosure will not separately describe various possible combination methods.

[0046] Furthermore, any combination can be made between various different embodiments of the present disclosure, as long as it does not violate the idea of the present disclosure, and it should also be regarded as the content disclosed by the present disclosure.

[0047] The preferred embodiments of the present disclosure have been described in detail above. However, the present disclosure is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0048] In addition, it should be noted that, in the case of no contradiction, the various specific technical features described in the above specific embodiments can be combined in any appropriate manner. To avoid unnecessary repetition, the present disclosure will not separately describe various possible combination methods.

[0049] Furthermore, any combination can be made between various different embodiments of the present disclosure, as long as it does not violate the idea of the present disclosure, and it should also be regarded as the content disclosed by the present disclosure.

Claims

1. A ternary metal solid solution catalyst, characterized in that, The ternary metal solid solution catalyst is a solid solution catalyst containing Cu, Zn, and Zr, wherein Cu exists as a single atom; the molar ratio of Zn to Zr is 0.05-0.2; and the molar ratio of the amount of Cu to the sum of the amounts of Zn and Zr is 0.005-0.

03.

2. A method for preparing a ternary metal solid solution catalyst, characterized in that, The preparation method includes the following steps: S1. Dissolve Cu salt, Zn salt, and Zr salt in deionized water and stir to obtain the first solution; S2. Dissolve the precipitant in the first solution to obtain the second solution; S3. Add the first solution and the second solution dropwise to deionized water, and perform aging and cooling treatment to obtain a suspension. S4. The suspension is separated, dried, calcined and activated. The molar ratio of Zn to Zr is 0.05-0.2; the molar ratio of Cu to the sum of Zn and Zr is 0.005-0.

03. The roasting temperature is 400-600℃, and the roasting time is 3-5h.

3. The preparation method according to claim 2, wherein, The Cu salt is selected from one or more of copper nitrate, copper acetate, copper chloride, and copper sulfate; the Zn salt is selected from one or more of zinc nitrate, zinc acetate, zinc chloride, and zinc sulfate; and the Zr salt is selected from one or more of zirconium nitrate, zirconium acetate, zirconium chloride, and zirconium sulfate. The precipitant is selected from one or more of nitrates, acetates, halides and sulfates.

4. The preparation method according to claim 2, wherein, In step S3, the dropping rate of the first solution and the second solution is 0.1-3 mL / min; The aging temperature is 50-90℃, and the aging time is 1-5 h.

5. The preparation method according to claim 2, wherein, In step S4, the drying temperature is 80-150℃ and the drying time is 4-12 h.

6. The preparation method according to claim 2, wherein, In step S4, the calcination heating rate is 2-10℃ / min; the calcination atmosphere is one or more of air, oxygen, or nitrogen.

7. The preparation method according to claim 2, wherein, In step S4, the activation atmosphere is hydrogen, argon, carbon monoxide, or a mixture of carbon dioxide and hydrogen; the volume percentage of hydrogen in the mixture is 30-60%; the activation temperature is 300-400℃, the activation time is 1-5h, the activation pressure is atmospheric pressure; the activation gas flow rate is 2-30 mL / min, and the activation heating rate is 1-10℃ / min.

8. The application of the ternary metal solid solution catalyst of claim 1 in the hydrogenation of carbon dioxide to methanol.

9. The application according to claim 8, wherein, The reaction conditions for the hydrogenation of carbon dioxide to methanol include: a reaction pressure of 2-5 MPa, a reaction temperature of 200-340℃, and a reaction space velocity of 6000-24000 mL / (g). h); the raw material gas molar ratio n(H2):n(CO2)=3:

1.

10. The application according to claim 8, wherein, Before the carbon dioxide hydrogenation to methanol reaction, the catalyst is activated with an activating gas; The activating gas is selected from one or more of hydrogen, carbon monoxide, carbon dioxide or argon.

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