Fibrous rare-earth-based ceramic reforming hydrogen production catalyst as well as preparation method and application thereof

Abstract

The invention discloses a fibrous rare-earth-based ceramic reforming hydrogen production catalyst as well as a preparation method and application thereof. The catalyst takes fibrous titanium dioxide ceramic as a carrier, a composite oxide of cerium oxide and nickel oxide as an active component and a composite oxide of copper oxide and molybdenum oxide as a cocatalyst. The catalyst for hydrogen production by reforming is environment-friendly, the H2 selectivity for hydrogen production by reforming methanol at low temperature is high, the preparation process is simple, and the catalyst has a wide market application prospect.

Description

Technical Field

[0001] The invention relates to a fibrous rare earth-based ceramic reforming hydrogen production catalyst and a preparation method and application thereof, belonging to the field of energy and environmental protection. Background Art

[0002] With the global energy transition and increasing demand for clean energy, hydrogen's potential as a clean energy source is gaining increasing attention. Its combustion product is solely water, with a high energy density (142 MJ / kg), making it suitable for transportation, energy storage, and industrial decarbonization. Traditional hydrogen production from fossil fuels such as natural gas or coal produces large amounts of CO₂ (10-12 tons of CO₂ per ton of H₂), contradicting low-carbon goals. Water electrolysis requires high-purity water and renewable electricity, resulting in high costs (approximately $4-6 per kg of H₂) and only 60-70% energy efficiency. Small organic molecules not only have high hydrogen storage densities, making them easy to store and transport in liquid or solid carriers such as methanol (12.6 wt% H₂), formic acid (4.4 wt%), and ammonia (17.6 wt% H₂), but also can be catalytically reformed to release hydrogen at relatively low temperatures (200-400°C), significantly reducing energy consumption compared to water electrolysis. Furthermore, some small organic molecules can be synthesized through CO₂ hydrogenation, forming a closed carbon cycle.

[0003] In recent years, significant progress has been made in the development of catalysts for hydrogen production from organic small molecule reforming, but their catalytic performance and stability still face challenges. Researchers have developed some new catalyst systems to improve methanol conversion, hydrogen yield, and reduce the formation of by-products. (1) Metal alloy catalysts, such as alloy catalysts containing precious metals (such as platinum and palladium) and transition metals (such as copper and nickel), can not only improve the activity of hydrogen production from organic small molecules such as methanol and optimize hydrogen yield, but also reduce the preparation cost of the catalyst; (2) Nanocatalysts, such as nanometal oxide catalysts such as ZnO, NiO, and CuO, can not only make full use of the high specific surface area of ​​nanocatalysts to improve catalytic performance and reaction rate, but also composite metal oxide catalysts have a synergistic catalytic effect, which can further improve the catalytic activity of low-temperature reforming hydrogen production.

[0004] Among the above-mentioned catalyst systems, the development of new composite metal oxide catalysts has the greatest cost and technical advantages. However, in actual application, composite metal oxide catalysts will catalyze the production of carbon deposition, leading to poisoning problems. Therefore, the development of composite metal oxide catalysts with resistance to carbon deposition and long service life is one of the important directions of organic small molecule reforming hydrogen production catalysts. Summary of the Invention

[0005] The purpose of the present invention is to address the current status and existing problems of the existing organic small molecule reforming hydrogen production, and to propose a fibrous rare earth-based ceramic reforming hydrogen production catalyst and its preparation method and application.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A fibrous rare earth-based ceramic reforming hydrogen production catalyst uses a fibrous titanium dioxide ceramic as a carrier, a composite oxide of cerium oxide and nickel oxide as an active component, and a composite oxide of copper oxide and molybdenum oxide as a co-catalyst. The catalyst is prepared by a bio-template-polymer polymerization-impregnation and calcination method. The catalyst comprises, based on the mass of the carrier, 1-10% by mass of the active component, 1-10% by mass of the co-catalyst, a mass ratio of cerium oxide to nickel oxide in the active component of 1:(0.1-3), and a mass ratio of copper oxide to molybdenum oxide in the co-catalyst of 1:(0.1-3).

[0008] Furthermore: based on the mass of the carrier, the mass percentage of the active component is 5-10%, the mass percentage of the co-catalyst is 5-10%, the mass ratio of cerium oxide to nickel oxide in the active component is 1:(0.5-1), and the mass ratio of copper oxide to molybdenum oxide in the co-catalyst is 1:(0.5-1).

[0009] A method for preparing the above catalyst is as follows:

[0010] (1) Preparation of fiber templates by bio-template-polymer polymerization method

[0011] The sugarcane fiber template is obtained by ultrasonic extraction at a constant temperature, and the fibers obtained after filtration are dried; methyl methacrylate, benzoyl peroxide, and toluene are uniformly mixed to obtain a precursor mixed solution, and the sugarcane fiber template is then placed in the precursor mixed solution for polymerization to obtain a polymethyl methacrylate-coated sugarcane fiber template; the obtained polymethyl methacrylate-coated sugarcane fiber template is first acid-hydrolyzed and then alkaline-hydrolyzed to obtain a polymethyl methacrylate fiber template;

[0012] (2) Preparation of nanoneedle active components by impregnation and calcination

[0013] A titanium source, ethanol, acetic acid, and deionized water are uniformly mixed to obtain a mixed solution, the polymethyl methacrylate fiber template obtained in step (1) is placed in the mixed solution for hydrolysis, and then dried after the hydrolysis is completed. After drying, the first calcination is performed to obtain a fibrous titanium dioxide ceramic;

[0014] Cerium salt, nickel salt, copper salt, molybdenum salt, monohydrated citric acid and deionized water are uniformly mixed to obtain a precursor mixed solution, and then the fibrous titanium dioxide ceramic is immersed in the precursor mixed solution, dried and then calcined for a second time to obtain a catalyst.

[0015] In the above preparation method, the constant temperature ultrasonic extraction in step (1) is carried out at a temperature of 30 to 50° C. and a power of 200 to 700 W for 4 to 15 hours; preferably, the constant temperature ultrasonic extraction is carried out at a temperature of 40 to 50° C. and a power of 300 to 600 W for 6 to 12 hours;

[0016] The drying temperature is 40-50°C and the drying time is 12-24 hours.

[0017] The mass ratio of methyl methacrylate, benzoyl peroxide and toluene described in step (1) is 1: (0.03-0.06): (0.2-0.5);

[0018] The mass ratio of the sugarcane fiber template and the precursor mixed solution is 1:(1-3), the polymerization temperature is 50-80° C., and the polymerization time is 6-12 hours.

[0019] In the above preparation method: the acid used in the acid hydrolysis described in step (1) is a sulfuric acid solution with a mass fraction of 30-60%, the mass ratio of the polymethyl methacrylate-wrapped sugarcane fiber template to concentrated sulfuric acid is 1:(10-20); the acid hydrolysis temperature is 40-60°C, and the acid hydrolysis time is 12-24 hours.

[0020] In the above preparation method: the alkali hydrolysis described in step (1) uses a sodium hydroxide solution with a mass fraction of 20-40%, the mass ratio of the polymethyl methacrylate-wrapped sugarcane fiber template to the sodium hydroxide solution is 1:(10-20), the alkaline hydrolysis temperature is 40-60°C, and the alkaline hydrolysis time is 12-24h.

[0021] In the above preparation method: the titanium source described in step (2) is tetrabutyl titanate or tetraethyl titanate, and the mass ratio of the titanium source, ethanol, acetic acid, and polymethyl methacrylate fiber template is 1: (20-40): (5-10): (3-5);

[0022] The hydrolysis temperature is 40-60°C, and the hydrolysis time is 4-8 hours; the drying temperature is 80-100°C, and the drying time is 6-12 hours;

[0023] The temperature of the first roasting is 1300-1500°C and the time is 4-8 hours.

[0024] In the above preparation method: the cerium salt described in step (2) is cerium nitrate hexahydrate or cerium chloride, the nickel salt is nickel nitrate hexahydrate or nickel chloride hexahydrate, the copper salt is copper nitrate or copper chloride, the molybdenum salt is ammonium molybdate, and the mass ratio of the cerium salt to citric acid monohydrate is 1:(3-5);

[0025] The drying temperature is 80-100° C., and the drying time is 6-12 hours; the second roasting temperature is 400-600° C., and the time is 2-4 hours.

[0026] In the technical solution of the present invention, the catalyst is used in the reforming of small organic molecules to produce hydrogen. Further, the small organic molecule is methanol.

[0027] The catalytic reaction conditions and results of the present invention were as follows: 1g of the reforming hydrogen production catalyst was loaded into a catalyst performance evaluation reactor and the reaction gases were introduced for activity evaluation. The concentrations of the gases were: N2 (90mL / min); H2O (0.1mL / min); and methanol (0.067mL / min). At 200°C, the catalyst exhibited H2 selectivity exceeding 90% and CO selectivity exceeding 80%. Even after 24 hours of use at 200°C, the catalyst's H2 selectivity remained unchanged.

[0028] Beneficial effects:

[0029] (1) The present invention utilizes ultrasonic constant temperature extraction to extract sugarcane juice and retain the sugarcane fiber structure, thereby avoiding the destruction of the overall structure of the sugarcane by the traditional pressing method. Then, methyl methacrylate is polymerized by solution polymerization and combined with the cut sugarcane. Then, acid hydrolysis and alkaline hydrolysis are combined to destroy the sugarcane fiber template, leaving only polymethyl methacrylate, thereby allowing fibrous pores to exist in the polymethyl methacrylate, providing a fiber template for the subsequent hydrolysis of the titanium source and preparation of the carrier.

[0030] (2) In the present invention, a titanium source is hydrolyzed and combined with polymethyl methacrylate to prepare fibrous titanium dioxide, which is then calcined at high temperature to obtain a fibrous titanium dioxide ceramic carrier, and finally a fibrous catalyst is prepared by an impregnation and calcination method;

[0031] (3) The present invention uses sugarcane fiber and polymethyl methacrylate as yin and yang templates, which not only provides a new way to utilize sugarcane bagasse as a high-value-added resource, but also makes full use of the structure of sugarcane fiber to make the reforming hydrogen production catalyst have a fibrous structure. The fibrous structure not only has a high specific surface area, which promotes the exposure of active sites, but also facilitates the rapid transmission of reactants and products on the catalyst surface, reduces the deposition of side reaction product carbon on the catalyst surface, and improves the anti-carbon deposition performance;

[0032] (4) In the present invention, a composite oxide of cerium oxide and nickel oxide is used as an active component, and a composite oxide of copper oxide and molybdenum oxide is used as a co-catalyst. The four metal oxides not only have excellent redox properties, but can also generate more L acid sites and B acid sites according to the Tanabe law, thereby promoting the improvement of low-temperature reforming hydrogen production activity;

[0033] Therefore, the catalyst prepared by the present invention not only has excellent low-temperature reforming hydrogen production performance, but also the catalyst component is environmentally friendly, has a simple preparation process, low cost, high cost performance, and has strong application and promotion value. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 H2 selectivity diagram of the catalysts prepared in Examples 1-3 and Comparative Example 1;

[0035] Figure 2 The CO selectivity graph of the catalysts prepared in Examples 1-3 and Comparative Example 1;

[0036] Figure 3 24h H2 selectivity diagram of the catalyst prepared in Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0037] The present invention will be further described below with reference to the following examples. The examples are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operating processes. However, the protection scope of the present invention is not limited to the following examples.

[0038] Example 1

[0039] (1) Preparation of fiber templates by bio-template-polymer polymerization method

[0040] Cut sugarcane into segments with a diameter of 5 mm and a length of 15 mm, take 80 g of the segments and place them in a beaker, add 8000 g of deionized water, place the beaker in an ultrasonic constant temperature water bath, extract the juice at a constant temperature of 40 ° C with a power of 300 W for 6 h, and then filter to obtain sugarcane fiber, which is then placed in an oven at a low temperature of 40 ° C for 12 h to obtain a sugarcane fiber template; then weigh 40 g of methyl methacrylate, 1.2 g of benzoyl peroxide, and 8 g of toluene, mix them evenly to obtain a precursor mixed solution, and then add 49.2 g of sugarcane fiber to the mixture. The fiber template is placed in a precursor mixed solution, and polymerized at a constant temperature of 50°C for 6 hours to obtain a polymethyl methacrylate-wrapped sugarcane fiber template; 50g of the polymethyl methacrylate-wrapped sugarcane fiber template is placed in 500g of 30% concentrated sulfuric acid, heated at 40°C for acid hydrolysis for 12 hours, taken out, rinsed with deionized water, and 40g is placed in 400g of 20% sodium hydroxide solution, heated at 40°C for alkaline hydrolysis for 12 hours, taken out, and rinsed with deionized water to obtain a polymethyl methacrylate fiber template;

[0041] (2) Preparation of nanoneedle active components by impregnation and calcination

[0042] 15 g of tetrabutyl titanate, 300 g of ethanol, 75 g of acetic acid, and 15 g of deionized water were weighed and mixed evenly, 45 g of the polymethyl methacrylate fiber template obtained in step (1) was placed therein, and then placed in an oven for hydrolysis at 40 ° C for 4 h, and then dried at 80 ° C for 6 h, and then placed in an atmosphere furnace for high temperature roasting at 1300 ° C for 4 h to obtain fibrous titanium dioxide ceramics; 0.252 g of cerium nitrate hexahydrate, 0.195 g of nickel nitrate hexahydrate, 0.354 g of copper nitrate, 0.204 g of ammonium molybdate, 0.756 g of citric acid monohydrate, and 10.080 g of deionized water were weighed and mixed evenly to obtain a precursor mixed solution, and then 3.000 g of fibrous titanium dioxide ceramics were immersed in the precursor mixed solution, dried at 80 ° C for 6 h, and then roasted at 400 ° C for 2 h to obtain a catalyst.

[0043] Based on the mass of the carrier, the mass percentage of the active component is 5%, the mass percentage of the co-catalyst is 10%, the mass ratio of cerium oxide to nickel oxide in the active component is 1:0.5, and the mass ratio of copper oxide to molybdenum oxide in the co-catalyst is 1:1.

[0044] (3) Catalytic activity test

[0045] The catalyst activity evaluation experimental conditions of the present invention were as follows: 1 g of the reforming hydrogen production catalyst was loaded into a catalyst performance evaluation reactor and the reaction gases were introduced for activity evaluation. The concentrations of the gases were: N2 (90 mL / min); H2O (0.1 mL / min); and methanol (0.067 mL / min). At 200°C, the catalyst exhibited H2 selectivity exceeding 90% and CO selectivity exceeding 80%. Even after 24 hours of use at 200°C, the catalyst exhibited no significant change in H2 selectivity.

[0046] Example 2

[0047] (1) Preparation of fiber templates by bio-template-polymer polymerization method

[0048] Cut sugarcane into segments with a diameter of 15 mm and a length of 20 mm, take 80 g of the segments and place them in a beaker, add 12,000 g of deionized water, and place the beaker in an ultrasonic constant-temperature water bath. Extract the juice at a constant temperature of 50°C and a power of 450 W for 9 hours, then filter to obtain sugarcane fiber, and then place it in an oven at a low temperature of 50°C for 18 hours to obtain a sugarcane fiber template; then weigh 100 g of methyl methacrylate, 5 g of benzoyl peroxide, and 30 g of toluene, mix them evenly to obtain a precursor mixed solution, and then add 67.5 g of sugarcane to the mixture. The fiber template is placed in a precursor mixed solution and polymerized at a constant temperature of 65°C for 9 hours to obtain a polymethyl methacrylate-coated sugarcane fiber template; 50g of the polymethyl methacrylate-coated sugarcane fiber template is placed in 750g of 45% concentrated sulfuric acid, heated at 50°C for acid hydrolysis for 18 hours, removed, rinsed with deionized water, and then 45g is placed in 675g of 30% sodium hydroxide solution, heated at 50°C for alkaline hydrolysis for 18 hours, removed, and rinsed with deionized water to obtain a polymethyl methacrylate fiber template;

[0049] (2) Preparation of nanoneedle active components by impregnation and calcination

[0050] 15 g of tetrabutyl titanate, 600 g of ethanol, 150 g of acetic acid, and 45 g of deionized water were weighed and mixed evenly, 60 g of the polymethyl methacrylate fiber template obtained in step (1) was placed therein, and then placed in an oven for hydrolysis at 50 ° C for 6 h, and then dried at 90 ° C for 8 h, and then placed in an atmosphere furnace for high temperature roasting at 1400 ° C for 6 h to obtain fibrous titanium dioxide ceramics; 0.215 g of cerium chloride, 0.477 g of nickel chloride hexahydrate, 0.169 g of copper chloride, 0.068 g of ammonium molybdate, 0.860 g of citric acid monohydrate, and 10.750 g of deionized water were weighed and mixed evenly to obtain a precursor mixed solution, and then 3.000 g of fibrous titanium dioxide ceramics were immersed in the precursor mixed solution, dried at 90 ° C for 9 h, and then roasted at 500 ° C for 3 h to obtain a catalyst.

[0051] Based on the mass of the carrier, the mass percentage of the active component is 10%, the mass percentage of the co-catalyst is 5%, the mass ratio of cerium oxide to nickel oxide in the active component is 1:1, and the mass ratio of copper oxide to molybdenum oxide in the co-catalyst is 1:0.5.

[0052] (3) Catalytic activity test

[0053] The catalyst activity evaluation experimental conditions of the present invention were as follows: 1 g of the reforming hydrogen production catalyst was loaded into a catalyst performance evaluation reactor and the reaction gases were introduced for activity evaluation. The concentrations of the gases were: N2 (90 mL / min); H2O (0.1 mL / min); and methanol (0.067 mL / min). At 200°C, the catalyst exhibited H2 selectivity exceeding 90% and CO selectivity exceeding 80%. Even after 24 hours of use at 200°C, the catalyst exhibited no significant change in H2 selectivity.

[0054] Example 3

[0055] (1) Preparation of fiber templates by bio-template-polymer polymerization method

[0056] Cut sugarcane into segments with a diameter of 20 mm and a length of 30 mm, take 80 g of the segments and place them in a beaker, add 16000 g of deionized water, place the beaker in an ultrasonic constant temperature water bath, extract the juice at a constant temperature of 50 ° C with a power of 600 W for 12 h, then filter to obtain sugarcane fiber, and then place it in an oven at a low temperature of 50 ° C for 24 h to obtain a sugarcane fiber template; then weigh 100 g of methyl methacrylate, 6 g of benzoyl peroxide, and 50 g of toluene and mix them evenly to obtain a precursor mixed solution, and then add 52 g of sugarcane fiber to the mixture. The fiber template is placed in a precursor mixed solution and polymerized at a constant temperature of 80°C for 12 hours to obtain a polymethyl methacrylate-wrapped sugarcane fiber template; 50g of the polymethyl methacrylate-wrapped sugarcane fiber template is placed in 1000g of 60% concentrated sulfuric acid, heated at 60°C for acid hydrolysis for 24 hours, taken out, rinsed with deionized water, and 45g is placed in 900g of 40% sodium hydroxide solution, heated at 60°C for alkaline hydrolysis for 24 hours, taken out, and rinsed with deionized water to obtain a polymethyl methacrylate fiber template;

[0057] (2) Preparation of nanoneedle active components by impregnation and calcination

[0058] 10 g of tetraethyl titanate, 400 g of ethanol, 100 g of acetic acid, and 30 g of deionized water were weighed and mixed evenly, 50 g of the polymethyl methacrylate fiber template obtained in step (1) was placed therein, and then placed in an oven for hydrolysis at 60 ° C for 8 h, dried at 100 ° C for 12 h, and then placed in an atmosphere furnace for high-temperature roasting at 1500 ° C for 8 h to obtain fibrous titanium dioxide ceramics; 0.215 g of cerium chloride, 0.477 g of nickel chloride hexahydrate, 0.254 g of copper chloride, 0.204 g of ammonium molybdate, 1.075 g of citric acid monohydrate, and 12.900 g of deionized water were weighed and mixed evenly to obtain a precursor mixed solution, and then 3.000 g of fibrous titanium dioxide ceramics were immersed in the precursor mixed solution, dried at 100 ° C for 12 h, and then roasted at 600 ° C for 4 h to obtain a catalyst.

[0059] Based on the mass of the carrier, the mass percentage of the active component is 10%, the mass percentage of the co-catalyst is 10%, the mass ratio of cerium oxide to nickel oxide in the active component is 1:1, and the mass ratio of copper oxide to molybdenum oxide in the co-catalyst is 1:1.

[0060] (3) Catalytic activity test

[0061] The catalyst activity evaluation experimental conditions of the present invention were as follows: 1 g of the reforming hydrogen production catalyst was loaded into a catalyst performance evaluation reactor and the reaction gases were introduced for activity evaluation. The concentrations of the gases were: N2 (90 mL / min); H2O (0.1 mL / min); and methanol (0.067 mL / min). At 200°C, the catalyst exhibited H2 selectivity exceeding 90% and CO selectivity exceeding 80%. Even after 24 hours of use at 200°C, the catalyst exhibited no significant change in H2 selectivity.

[0062] Comparative Example 1

[0063] (1) Catalyst preparation

[0064] Except that the ultrasonic constant temperature extraction was replaced with the pressing method to prepare sugarcane fiber during catalyst preparation, other conditions were the same as those in Example 1;

[0065] (2) Catalytic activity test

[0066] A reforming hydrogen production catalyst (1g) was loaded into a catalyst performance evaluation reactor and the reaction gases were introduced for activity evaluation. The concentrations of the gases were: N2 (90mL / min); H2O (0.1mL / min); and methanol (0.067mL / min). At 200°C, the catalyst exhibited a H2 selectivity of only 57.2% and a CO selectivity of only 49.8%. The catalyst exhibited a significant decrease in H2 selectivity after 24 hours of use at 200°C.

[0067] (3) Contrast effect

[0068] Compared with Example 1, during catalyst preparation, ultrasonic constant temperature extraction was replaced with a pressing method to prepare sugarcane fiber. This traditional mechanical extrusion method would destroy the structure of the sugarcane fiber, resulting in a worse effect of the solution polymerization method for polymerizing methyl methacrylate, and a decrease in the hydrolysis of the titanium source and the performance of the carrier preparation in providing a fiber template, ultimately leading to a significant decrease in the catalytic activity of the prepared catalyst.

Claims

1. A fibrous rare earth-based ceramic reforming hydrogen production catalyst, characterized by: The catalyst uses fibrous titanium dioxide ceramic as a carrier, a composite oxide of cerium oxide and nickel oxide as an active component, and a composite oxide of copper oxide and molybdenum oxide as a co-catalyst. It is prepared by a bio-template-polymer polymerization-impregnation and calcination method. The mass percentage of the active component is 1-10%, the mass percentage of the co-catalyst is 1-10%, the mass ratio of cerium oxide to nickel oxide in the active component is 1:(0.1-3), and the mass ratio of copper oxide to molybdenum oxide in the co-catalyst is 1:(0.1-3).

2. The fibrous rare earth-based ceramic reforming hydrogen production catalyst according to claim 1, characterized in that: Based on the mass of the carrier, the mass percentage of the active component is 5-10%, the mass percentage of the co-catalyst is 5-10%, the mass ratio of cerium oxide to nickel oxide in the active component is 1:(0.5-1), and the mass ratio of copper oxide to molybdenum oxide in the co-catalyst is 1:(0.5-1).

3. A method for preparing the catalyst according to claim 1, characterized in that: The preparation method of the catalyst is as follows: (1) Preparation of fiber templates by bio-template-polymer polymerization method The sugarcane fiber template is obtained by ultrasonic extraction at a constant temperature, and the fibers obtained after filtration are dried; methyl methacrylate, benzoyl peroxide, and toluene are uniformly mixed to obtain a precursor mixed solution, and the sugarcane fiber template is then placed in the precursor mixed solution for polymerization to obtain a polymethyl methacrylate-coated sugarcane fiber template; the obtained polymethyl methacrylate-coated sugarcane fiber template is first acid-hydrolyzed and then alkaline-hydrolyzed to obtain a polymethyl methacrylate fiber template; (2) Preparation of nanoneedle active components by impregnation and calcination A titanium source, ethanol, acetic acid, and deionized water are uniformly mixed to obtain a mixed solution, the polymethyl methacrylate fiber template obtained in step (1) is placed in the mixed solution for hydrolysis, and then dried after the hydrolysis is completed. After drying, the first calcination is performed to obtain a fibrous titanium dioxide ceramic; Cerium salt, nickel salt, copper salt, molybdenum salt, monohydrated citric acid and deionized water are uniformly mixed to obtain a precursor mixed solution, and then the fibrous titanium dioxide ceramic is immersed in the precursor mixed solution, dried and then calcined for a second time to obtain a catalyst.

4. The preparation method according to claim 2, wherein: The conditions for constant temperature ultrasonic extraction in step (1) are: 30-50° C., ultrasonic power of 200-700W for 4-15 hours; the drying temperature is 40-50° C., and the drying time is 12-24 hours; preferably: the conditions for constant temperature ultrasonic extraction are: 40-50° C., ultrasonic power of 300-600W for 6-12 hours; The mass ratio of methyl methacrylate, benzoyl peroxide and toluene described in step (1) is 1: (0.03-0.06): (0.2-0.5); The mass ratio of the sugarcane fiber template and the precursor mixed solution is 1:(1-3), the polymerization temperature is 50-80° C., and the polymerization time is 6-12 hours.

5. The preparation method according to claim 2, wherein: The acid used in the acid hydrolysis in step (1) is a sulfuric acid solution with a mass fraction of 30-60%, and the mass ratio of the polymethyl methacrylate-wrapped sugarcane fiber template to concentrated sulfuric acid is 1:(10-20); the acid hydrolysis temperature is 40-60° C., and the acid hydrolysis time is 12-24 hours.

6. The preparation method according to claim 2, wherein: The alkaline hydrolysis in step (1) uses a sodium hydroxide solution with a mass fraction of 20-40%, the mass ratio of the polymethyl methacrylate wrapped sugarcane fiber template to the sodium hydroxide solution is 1: (10-20), the alkaline hydrolysis temperature is 40-60° C., and the alkaline hydrolysis time is 12-24 hours.

7. The preparation method according to claim 2, wherein: The titanium source described in step (2) is tetrabutyl titanate or tetraethyl titanate, and the mass ratio of the titanium source, ethanol, acetic acid, and polymethyl methacrylate fiber template is 1: (20-40): (5-10): (3-5); The hydrolysis temperature is 40-60°C, and the hydrolysis time is 4-8 hours; the drying temperature is 80-100°C, and the drying time is 6-12 hours; The temperature of the first roasting is 1300-1500°C and the time is 4-8 hours.

8. The preparation method according to claim 2, wherein: The cerium salt described in step (2) is cerium nitrate hexahydrate or cerium chloride, the nickel salt is nickel nitrate hexahydrate or nickel chloride hexahydrate, the copper salt is copper nitrate or copper chloride, the molybdenum salt is ammonium molybdate, and the mass ratio of the cerium salt to citric acid monohydrate is 1:(3-5); The drying temperature is 80-100° C., and the drying time is 6-12 hours; the second calcination temperature is 400-600° C., and the time is 2-4 hours.

9. Use of the catalyst according to claim 1 in hydrogen production by reforming small organic molecules.

10. The use according to claim 9, characterized in that The organic small molecule is methanol.

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