Preparation method of high oxygen vacancy content Pt / CSAP-TiO2 / CeO2 coupled carbon dioxide capture hydrogenation methanol catalyst

Abstract

The invention belongs to the technical field of carbon dioxide hydrogenation catalysts, and particularly relates to a preparation method of a Pt / CSAP-TiO2 / CeO2 coupled carbon dioxide capture hydrogenation methanol catalyst with high oxygen vacancy content. The hydrodesulfurization catalyst with high oxygen vacancy content is obtained after the water-soluble Pt is highly dispersed, dehydrated and carbonized by utilizing the adsorption effect of the super absorbent resin, the soluble TiCe is secondarily impregnated, and the hydrodesulfurization catalyst is dried and calcined, so that the reaction performance can be further improved, and the prepared catalyst belongs to a uniformly supported coupling carbon dioxide hydrogenation methanol preparation catalyst.

Description

Technical Field

[0001] The present invention belongs to the technical field of carbon dioxide hydrogenation catalysts, and particularly relates to a preparation method of a Pt / C SAP -TiO2 / CeO2 coupled catalyst for carbon dioxide capture hydrogenation to methanol with a high oxygen vacancy content. Background Art

[0002] With the development of industry, a large amount of carbon dioxide emissions have led to serious greenhouse effect problems. Therefore, in addition to reducing the use of fossil fuels, various carbon dioxide capture, utilization, and storage technologies have been used to mitigate the greenhouse effect. Currently, as a common CO2 utilization technology, copper-based ternary catalysts (Cu-ZnO-Al2O3) are used industrially for the thermal catalytic production of methanol from a CO2 / H2 mixture under high temperature (>200°C) and high pressure (7-10 MPa) conditions. Researchers have increased the methanol yield and selectivity by means such as adjusting the dispersion of active metal components, adding catalyst promoters (such as doping Zr, Ti, Ce, etc.), and changing the catalyst morphology (such as doping materials like zeolites).

[0003] Unfortunately, for the traditional thermal catalytic gas-phase carbon dioxide hydrogenation to methanol, the entire process of capturing, compressing, transporting, and storing carbon dioxide is difficult to achieve energy efficiency and is not cost-effective; at the same time, due to the exothermic nature of the reaction, the high reaction temperature (>200°C) used in industrial production is not conducive to the reaction. Therefore, coupling the captured carbon dioxide to capture and convert it into other chemical materials has been identified as a new key technology for economically and effectively producing carbon dioxide-derived chemicals. Initially, homogeneous molecular catalysts for hydrogenating the captured amine CO2 to methanol were studied. In the reported homogeneous catalytic systems, practical new homogeneous catalytic systems include: Integrated capture and conversion of CO2 to methanol or methanol and glycol (Publication No. US10961173B2) and Integrated capture and conversion of CO2 to methane, methanol, or methanol and glycol (Publication No. US11492302B2), which allow the synergistic effect of amine additives. However, despite considerable achievements in this regard, expensive amines that are not for industrial applications are usually required, and the long-term stability and recycling performance of homogeneous catalysts are problematic for continuous operation, so the potential is limited.

[0004] On the other hand, heterogeneous catalysts usually exhibit improved catalyst stability, easier recovery, and / or reduced manufacturing costs, which are important for industrial applications. Importantly, monoethanolamine (MEA) and other primary and secondary amines have excellent absorption kinetics and high absorption capacity, and are efficient and economical technologies for post-combustion carbon dioxide capture in flue gases from power plants, cement, and steel industries. However, due to the challenge of hydrogenating the formed formamide intermediate to methanol, the progress of amine-based carbon dioxide capture and hydrogenation to methanol catalysts for industrial applications is limited.

[0005] Therefore, it is necessary to study a preparation method of a Pt / C SAP -TiO2 / CeO2 coupled catalyst for carbon dioxide capture and hydrogenation to methanol with a high oxygen vacancy content to meet the current technical requirements. Summary of the Invention

[0006] In view of the above technical problems, the present invention provides a method for preparing a Pt / C SAP -TiO2 / CeO2 coupled catalyst for carbon dioxide hydrogenation to methanol with a high oxygen vacancy content. The present invention highly disperses water-soluble Pt by the adsorption of a superabsorbent resin, and after dehydration and carbonization, soluble TiCe is impregnated secondly. After drying and calcination, a hydrodesulfurization catalyst with a high oxygen vacancy content is obtained, which can further improve the reaction performance. The prepared catalyst belongs to a uniformly loaded coupled catalyst for carbon dioxide hydrogenation to methanol.

[0007] To achieve the above object, the present invention adopts the following technical solutions.

[0008] A preparation method of a Pt / C SAP -TiO2 / CeO2 coupled catalyst for carbon dioxide capture and hydrogenation to methanol with a high oxygen vacancy content, specifically comprising the following steps: Step 1: Dissolve platinum nitrate in deionized water to obtain a solution containing Pt ions; Step 2: Weigh superabsorbent resin (SAP) particles, slowly pour them into the solution containing Pt ions, and keep stirring until the Pt ions are completely absorbed to obtain a translucent gel; Step 3: Low-temperature dry the translucent gel obtained in Step 2 to obtain dry particles; Step 4: Calcinate the dry particles obtained in Step 3 in a certain atmosphere for a period of time to obtain once-calcined particles; Step 5: Impregnate the once-calcined particles obtained in Step 4 with a mixed solution of cerium salt and titanium salt, and perform secondary calcination under a nitrogen atmosphere to obtain a Pt / C SAP -TiO2 / CeO2 coupled catalyst for carbon dioxide hydrogenation to methanol with a high oxygen vacancy content.

[0009] Further, in Step 1, the molybdenum content in the platinum nitrate solution (based on Pt) is 0.5 wt% - 40 wt% of the total weight of the catalyst support.

[0010] Further, in Step 1, the water content in the platinum nitrate solution is 1 - 1000 times the weight of the superabsorbent resin (SAP).

[0011] Further, in Step 2, the superabsorbent resin (SAP) particles have extremely high water swelling properties, and the swelling ratio is 1 - 1000 times.

[0012] Further, in Step 2, the superabsorbent resin (SAP) particles are one of starch - based superabsorbent resins, cellulose - based superabsorbent resins, or synthetic superabsorbent resins; the synthetic superabsorbent resin is one of homopolymers (such as polyvinyl alcohol, polyacrylamide, polyacrylic salts, etc.), copolymers (such as acrylic acid - acrylamide, polyvinyl alcohol - acid anhydride cross - linked polymers), or inorganic polymers (such as hydrous silica hydrogels, high - water - content metal oxide gels).

[0013] Further, in Step 3, the low - temperature drying temperature is 0°C - 150°C.

[0014] Further, in Step 4, the atmosphere includes one or more combinations of inert gases, carbon monoxide, or hydrogen; the inert gases include nitrogen, argon, helium, neon, or krypton; the atmosphere also includes a vacuum atmosphere.

[0015] Further, in Step 4, when the atmosphere includes one or more combinations of inert gases, carbon monoxide, or hydrogen, the calcination temperature is 200°C - 1000°C; when the atmosphere is a vacuum atmosphere, the vacuum degree is - 101.325 Ka to 0, and the calcination temperature is above 80% of the boiling temperature at this vacuum degree.

[0016] Further, in Step 4, the calcination time is between 5 minutes and 24 hours.

[0017] Further, in Step 5, if the cerium salt is a water - soluble salt, such as nickel nitrate, nickel sulfate, etc., a nickel salt solution is directly formed; the proportion of cerium content (calculated as Ce) in the catalyst support is 0.5 wt% - 20 wt%.

[0018] Further, in Step 5, if the titanium salt is a hydrolyzable salt, such as titanium tetrachloride, it is dissolved using an acidic solvent (such as hydrochloric acid, etc.) to obtain a titanium salt solution; the proportion of titanium content (calculated as Ti) in the catalyst support is 0.5 wt% - 20 wt%.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows.

[0020] Similar catalyst technologies all directly use existing metal oxide carriers and then prepare catalysts by impregnation. Although they have some methanol yield and high selectivity, they cannot meet actual needs. The present invention uses the three-dimensional pore structure of a highly absorbent resin to efficiently adsorb water-soluble components in a hydrodesulfurization catalyst. Through secondary impregnation, a coupled carbon dioxide hydrogenation to methanol catalyst rich in oxygen vacancies can be obtained, which can further improve the performance of the reaction.

[0021] Since conventional metal oxide carriers lack oxygen vacancies on their surfaces, if the catalyst is prepared by direct impregnation or coprecipitation, the activity of the catalyst is not very high; this is because there is a lack of sites that can adsorb, stabilize and activate key formamide intermediates during the reaction, making it difficult to achieve selective production of methanol. The present invention uses a water-absorbent resin material to prepare a carbon-metal oxide composite material, and by doping other metal ions and non-metallic components to change the oxygen vacancies in the carrier, the catalyst is not very active. 2- The periodic sequence stimulates the formation of oxygen vacancies on the catalyst surface. In the present invention, the high water absorption of the super absorbent resin is utilized to highly disperse the first metal component (platinum) in the carbon precursor through a water-soluble metal salt, and then carbonized under an inert atmosphere, followed by impregnation and secondary calcination of the remaining metal components, thereby obtaining a higher coupled carbon dioxide capture hydrogenation to methanol reaction performance than the conventional 5wt% Pt / TiO2 catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Pt / TiO2, Pt / TiO2-CeO2 and Example 1 Pt / C SAP -CO2-TPD curve of TiO2 / CeO2 catalyst.

[0023] Figure 2 The O 1s XPS spectra of Pt / TiO2, Pt / TiO2-CeO2 and Pt / CSAP-TiO2 / CeO2 catalysts in Example 1 are shown. DETAILED DESCRIPTION

[0024] In order to facilitate the understanding of the present invention, the technical solution of the present invention will be fully described below in conjunction with specific implementation methods and drawings, but the embodiments described below are part of the embodiments of the present invention, rather than all of the embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0025] A Pt / C with high oxygen vacancy content SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, which specifically comprises the following steps: Step 1: Dissolve platinum nitrate in deionized water to obtain a solution containing Pt ions; Step 2: Weigh superabsorbent polymer (SAP) particles and slowly pour them into the solution containing Pt ions, and keep stirring until the Pt ions are completely absorbed to obtain a translucent gel; Step 3: Perform low-temperature drying on the translucent gel obtained in Step 2 to obtain dry particles; Step 4: Calcinate the dry particles obtained in Step 3 in a certain atmosphere for a period of time to obtain once-calcined particles; Step 5: Impregnate the once-calcined particles obtained in Step 4 with a mixed solution of cerium salt and titanium salt and perform secondary calcination under a nitrogen atmosphere to obtain Pt / C SAP -TiO2 / CeO2 coupled catalyst for hydrogenation of carbon dioxide to methanol.

[0026] Further, in Step 1, the molybdenum content (based on Pt) in the platinum nitrate solution is 0.5 wt% - 40 wt% of the total weight of the catalyst support, preferably 5 wt% - 10 wt%.

[0027] Further, in Step 1, the water content in the platinum nitrate solution is 1 - 1000 times the weight of the superabsorbent polymer (SAP), preferably 5 - 500 times, more preferably 10 - 200 times.

[0028] Further, in Step 2, the superabsorbent polymer (SAP) particles have ultra-high water swelling properties, and the swelling ratio is 1 - 1000 times, preferably 5 - 500 times, more preferably 10 - 200 times.

[0029] Further, in Step 2, the superabsorbent polymer (SAP) particles are one of starch-based superabsorbent polymers, cellulose-based superabsorbent polymers or synthetic superabsorbent polymers; the synthetic superabsorbent polymer is one of homopolymers (such as polyvinyl alcohol, polyacrylamide, polyacrylate, etc.), copolymers (such as acrylic acid - acrylamide, polyvinyl alcohol - acid anhydride cross-linked polymer) or inorganic polymers (such as hydrosilicagel, high-water-content metal oxide gel).

[0030] Further, in Step 3, the low-temperature drying temperature is 0°C - 150°C, preferably 1°C - 99°C, most preferably room temperature - 80°C.

[0031] Further, in Step 4, the atmosphere includes one or a combination of an inert gas, carbon monoxide or hydrogen; the inert gas includes nitrogen, argon, helium, neon or krypton; the atmosphere also includes a vacuum atmosphere.

[0032] Further, in Step 4, when the atmosphere includes one or more combinations of inert gas, carbon monoxide, or hydrogen, the calcination temperature is 200°C - 1000°C, preferably 300°C - 900°C, and most preferably 400°C - 800°C; when the atmosphere is a vacuum atmosphere, the vacuum degree is -101.325 Ka to 0, and the calcination temperature is above 80% of the boiling point temperature at this vacuum degree.

[0033] Further, in Step 4, the calcination time is between 5 minutes and 24 hours, preferably 10 minutes - 12 hours, and most preferably 20 minutes - 8 hours.

[0034] Further, in Step 5, if the cerium salt is a water-soluble salt, such as nickel nitrate, nickel sulfate, etc., a nickel salt solution is directly formed; the proportion of cerium content (calculated as Ce) in the catalyst support is 0.5 wt% - 20 wt%, preferably 1 wt% - 10 wt%.

[0035] Further, in Step 5, if the titanium salt is a hydrolyzable salt, such as titanium tetrachloride, it is dissolved in an acidic solvent (such as hydrochloric acid, etc.) to obtain a titanium salt solution; the proportion of titanium content (calculated as Ti) in the catalyst support is 0.5 wt% - 20 wt%, preferably 1 wt% - 10 wt%.

[0036] Example 1.

[0037] Dissolve platinum nitrate in deionized water to prepare a platinum nitrate solution. The molybdenum content (based on Pt) in the platinum nitrate solution is 5 wt% of the weight of the catalyst support, and the water content in the platinum nitrate solution is in a weight ratio of 50:1 to the starch-based superabsorbent resin (SAP); slowly pour the starch-based superabsorbent resin into the platinum nitrate solution, keep stirring, so that the water-soluble Pt ions absorb all the solution to obtain a translucent gel; keep the translucent gel at 60°C for 24 hours to obtain dry particles, allowing the water to volatilize without generating cracks; calcine the dry particles from room temperature to 600°C for 4 hours in a nitrogen atmosphere to obtain primary calcined particles; impregnate the primary calcined particles with a mixed solution of cerium nitrate and titanium tetrachloride, where the proportion of cerium content (calculated as Ce) in the catalyst support is 20 wt%, and the proportion of titanium content (calculated as Ti) in the catalyst support is 5 wt%; dry the impregnated primary calcined particles in an 80°C oven overnight, and then calcine them from room temperature to 540°C for 4 hours in a nitrogen atmosphere to obtain the finished catalyst Pt / C SAP -TiO2 / CeO2.

[0038] Example 2.

[0039] Dissolve platinum nitrate in deionized water to prepare a platinum nitrate solution. The molybdenum content in the platinum nitrate solution (based on Pt) is 5 wt% of the weight of the catalyst support, and the water content in the platinum nitrate solution is in a weight ratio of 50:1 to the starch-based superabsorbent resin (SAP). Slowly pour the starch-based superabsorbent resin into the platinum nitrate solution while keeping stirring. Let the water-soluble Pt ions absorb all the solution to obtain a translucent gel. Keep the translucent gel at 60 °C for 24 hours to obtain dry particles, allowing the water to evaporate without generating cracks. Calcinate the dry particles in a nitrogen atmosphere from room temperature to 600 °C for 4 hours to obtain the once-calcined particles. Impregnate the once-calcined particles with a mixed solution of cerium nitrate and titanium tetrachloride, where the cerium content (calculated as Ce) in the catalyst support is 40 wt%, and the titanium content (calculated as Ti) in the catalyst support is 10 wt%. Dry the impregnated once-calcined particles in an 80 °C oven overnight, and then calcinate them in a nitrogen atmosphere from room temperature to 540 °C for 4 hours to obtain the finished catalyst Pt / C SAP -TiO2 / CeO2.

[0040] Example 3.

[0041] Dissolve platinum nitrate in deionized water to prepare a platinum nitrate solution. The molybdenum content in the platinum nitrate solution (based on Pt) is 5 wt% of the weight of the catalyst support, and the water content in the platinum nitrate solution is in a weight ratio of 50:1 to the starch-based superabsorbent resin (SAP). Slowly pour the starch-based superabsorbent resin into the platinum nitrate solution while keeping stirring. Let the water-soluble Pt ions absorb all the solution to obtain a translucent gel. Keep the translucent gel at 60 °C for 24 hours to obtain dry particles, allowing the water to evaporate without generating cracks. Calcinate the dry particles in a nitrogen atmosphere from room temperature to 600 °C for 4 hours to obtain the once-calcined particles. Impregnate the once-calcined particles with a mixed solution of cerium nitrate and titanium tetrachloride, where the cerium content (calculated as Ce) in the catalyst support is 10 wt%, and the titanium content (calculated as Ti) in the catalyst support is 2.5 wt%. Dry the impregnated once-calcined particles in an 80 °C oven overnight, and then calcinate them in a nitrogen atmosphere from room temperature to 540 °C for 4 hours to obtain the finished catalyst Pt / C SAP -TiO2 / CeO2.

[0042] Comparative Example 1: Preparation of supported Pt / TiO2 by impregnation method.

[0043] Prepare a platinum nitrate solution, impregnate the titanium dioxide support with the platinum nitrate solution, keeping the platinum nitrate (based on Pt) at 5 wt% of the weight of the catalyst support, and then calcinate it in air from room temperature to 540 °C for 4 hours to obtain the finished catalyst Pt / TiO2.

[0044] Comparative Example 2: Preparation of supported Pt / TiO2-CeO2 by impregnation method.

[0045] Prepare a platinum nitrate solution, impregnate the TiO2-CeO2 composite support with the platinum nitrate solution, and maintain platinum nitrate (based on Pt) at 5 wt% of the weight in the catalyst support. Then, calcine it in air from room temperature to 540 °C for 4 hours to obtain the finished catalyst Pt / TiO2-CeO2.

[0046] Table 1 shows the effect of coupling carbon dioxide capture and hydrogenation to methanol.

[0047] As can be seen from Table 1, compared with the Pt / TiO2 catalyst with a low oxygen vacancy content prepared by the simple impregnation method, the Pt / C catalyst prepared by the impregnation method using a support with a high oxygen vacancy content SAP has a reaction activity 1.35 times that of the reference Pt / TiO2 catalyst. The Pt / C SAP -TiO2 / CeO2 catalyst prepared by the method of this patent has a reaction activity 1.29 times that of the reference Pt / TiO2 catalyst.

[0048] Figure 1 shows the CO2-TPD curves of Pt / TiO2, Pt / TiO2-CeO2, and Example 1 Pt / C SAP -TiO2 / CeO2 catalysts. As can be seen from Figure 1 it, in the CO2-TPD curve of Example 1 Pt / C SAP -TiO2 / CeO2, two different CO2 desorption peaks are observed in the temperature ranges of 50-150 °C and 400-550 °C, corresponding to the weak basic sites and strong basic sites on the TiO2 support of the reference catalyst Pt / TiO2. In addition, at a temperature of 250-450 °C, for the Example 1 Pt / C SAP -TiO2 / CeO2 catalyst, a new and obvious CO2 desorption peak is observed, corresponding to a large number of oxygen vacancy sites formed on the catalyst surface.

[0049] Figure 2 is the O 1s XPS spectrum of Pt / TiO2, Pt / TiO2-CeO2, and Example 1 Pt / CSAP-TiO2 / CeO2 catalysts. As Figure 2 shown, the XPS spectrum of O 1s can be fitted into two sub-bands of O α and O β , and these two sub-bands can be attributed to lattice oxygen and surface adsorbed oxygen respectively. Consistent with the CO2-TPD experiment, the carbon-metal oxide composite catalyst Pt / C SAP -TiO2 / CeO2 (Example 1) with an additional SAP carbon skeleton shows the highest number of oxygen vacancy sites, O βThe proportion is 0.89.

[0050] By comparing Example 1 with the comparative example, it is found that the method of the present invention can utilize a water-absorbing resin to prepare a carbon-metal oxide composite catalyst, form a highly efficient oxygen-vacancy-rich catalyst for coupling carbon dioxide capture and hydrogenation to methanol, and achieve a high degree of dispersion of multi-component active components; the obtained highly active hydrodesulfurization catalyst is stronger than the Pt / TiO2 catalyst with a low oxygen vacancy content prepared by the traditional impregnation method.

Claims

1. A Pt / C with high oxygen vacancy content SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: The specific steps include: Step 1, dissolving platinum nitrate in deionized water to obtain a solution containing Pt ions; Step 2, weighing super absorbent resin particles, slowly pouring them into the solution containing Pt ions, and keeping stirring until the Pt ions are completely absorbed to obtain a translucent gel; Step 3, low-temperature drying the translucent gel of step 2 to obtain dry particles; Step 4, calcining the dried particles in step 3 in a certain atmosphere for a period of time to obtain primary calcined particles; Step 5: impregnate the primary calcined particles in step 4 with a mixed solution of cerium salt and titanium salt, and perform secondary calcination under a nitrogen atmosphere to obtain a Pt / C with a high oxygen vacancy content. SAP -TiO2 / CeO2 coupled catalyst for carbon dioxide hydrogenation to methanol.

2. The Pt / C with high oxygen vacancy content according to claim 1 SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: In step 1, the molybdenum content in the platinum nitrate solution is 0.5 wt%-40 wt% of the total weight of the catalyst carrier.

3. The Pt / C with high oxygen vacancy content according to claim 1 SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: In the step 1, the water content in the platinum nitrate solution is 1-1000 times the weight of the super absorbent resin.

4. The Pt / C with high oxygen vacancy content according to claim 1 SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: In the step 2, the super absorbent resin particles have super high water swelling property, and the swelling ratio is 1-1000 times.

5. The Pt / C with high oxygen vacancy content according to claim 1 SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: In step 2, the super absorbent resin particles are one of starch-based super absorbent resin, cellulose-based super absorbent resin or synthetic super absorbent resin; the synthetic super absorbent resin is one of homopolymers, copolymers or inorganic polymers.

6. The Pt / C with high oxygen vacancy content according to claim 1 SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: In step 3, the low-temperature drying temperature is 0°C-150°C.

7. The Pt / C with high oxygen vacancy content according to claim 1 SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: In step 4, the atmosphere includes one or more combinations of inert gas, carbon monoxide or hydrogen; the inert gas includes nitrogen, argon, helium, neon or krypton; the atmosphere also includes a vacuum atmosphere.

8. The Pt / C with high oxygen vacancy content according to claim 1 SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: In step 4, when the atmosphere includes one or more combinations of inert gas, carbon monoxide or hydrogen, the calcination temperature is 200°C-1000°C; when the atmosphere is a vacuum atmosphere with a vacuum degree of -101.325Ka to 0, the calcination temperature is above 80% of the boiling point temperature of the vacuum degree.

9. The Pt / C with high oxygen vacancy content according to claim 1 SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: In step 4, the calcination time is between 5 minutes and 24 hours.

10. The Pt / C with high oxygen vacancy content according to claim 1 SAP - A method for preparing a catalyst for producing methanol by coupling carbon dioxide capture and hydrogenation with TiO2 / CeO2, characterized in that: In step 5, if the cerium salt is a water-soluble salt, a nickel salt solution is directly formed, and the proportion of cerium content in the catalyst carrier is 0.5 wt%-20 wt%; if the titanium salt is an easily hydrolyzed salt, an acidic solvent is used for dissolution to obtain a titanium salt solution, and the proportion of titanium content in the catalyst carrier is 0.5 wt%-20 wt%.

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