A method for preparing a catalyst for hydrogen production by reforming of propane and carbon dioxide

Abstract

The application discloses a preparation method of a hydrogen reforming catalyst for propane and carbon dioxide, and relates to the technical field of catalysts. The method comprises the following steps: uniformly mixing a silicon source, an aluminum source, a template agent, an alkali source, a mesoporous cerium dioxide-based oxide and water to obtain a suspension; adding a metal oxide into the suspension, uniformly stirring and mixing to obtain a gel mixture; performing hydrothermal crystallization on the gel mixture to obtain a crystallization product; and after cooling and drying the crystallization product, performing calcination to obtain a hydrogen reforming catalyst with a mesoporous cerium dioxide-based oxide and ZSM-5 molecular sieve as a composite carrier. The composite carrier formed by the mesoporous cerium dioxide-based oxide and the ZSM-5 molecular sieve is used as a skeleton of an active component of the catalyst to support the active component, so that the dispersion degree of the metal active component of the catalyst can be improved, the conversion of carbon dioxide and propane can be accelerated, the loss of the metal active component can be reduced, and then the deactivation rate of the catalyst can be reduced, and the service life of the catalyst is improved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of catalysts, in particular to a preparation method of a hydrogen catalyst for reforming of propane and carbon dioxide. BACKGROUND

[0002] The hydrogen source of the hydrogen production process by catalytic reforming is mainly methane, ethanol, methanol and the like, and these hydrogen sources are combustible, and the energy conversion route does not have added value gain, therefore, developing the hydrogen production technology by catalytic reforming of low-quality organic matters has great significance of turning waste into treasure and high added value. In recent years, the method for producing hydrogen by reforming of propane has attracted widespread attention in the research field. The method for generating synthesis gas by taking propane and carbon dioxide as raw materials is an efficient and attractive route, the reaction has high atom economy, no solvent, simple process, and does not need to use traditional fossil fuels, directly uses carbon dioxide as a chemical carbon source to synthesize hydrogen, which not only meets the concept of green and sustainable development, but also reduces the emission of carbon dioxide into the environment. The hydrogen catalyst for reforming of propane and carbon dioxide is mainly divided into two categories: the first category is a pure metal mesh or a supported noble metal catalyst taking Rh, Ru, Pd, Pt, Ir and the like as active components; and the second category is a supported catalyst taking Ni, Co, Fe and the like in group VIII transition metals as active components. The noble metal catalyst has high activity, good stability, and resistance to carbon deposition and the like, the catalytic activity of Ni in the supported catalyst is the best, close to Rh, and the price is low. However, the noble metal catalyst has too high cost and is difficult to be popularized on a large scale, and the Ni-based catalyst has the problem of deactivation caused by carbon deposition, and the service life of the catalyst is limited. Therefore, the way of loading multiple metal components on metal oxides is usually adopted to improve the activity of the catalyst, but due to the poor stability of the traditional oxide carrier and the loading of the active metal by the conventional impregnation method, the connection between the active metal and the carrier is not firm, and the metal components are prone to loss, thereby causing the short service life of the catalyst. SUMMARY

[0003] The main purpose of the application is to provide a preparation method of a hydrogen catalyst for reforming of propane and carbon dioxide, which aims to solve the technical problem that the metal active components in the catalyst are prone to deactivation.

[0004] To achieve the above-mentioned purpose, the application provides a preparation method of a hydrogen catalyst for reforming of propane and carbon dioxide, which comprises the following steps:

[0005] Mixing a silicon source, an aluminum source, a template agent, an alkali source, a mesoporous cerium dioxide-based oxide and water uniformly to obtain a suspension;

[0006] Adding a metal oxide into the suspension, stirring and mixing uniformly to obtain a gel mixture;

[0007] The gel mixture is hydrothermally crystallized to obtain a crystallization product, and the crystallization product is cooled, dried, and then calcined to obtain a reforming hydrogen production catalyst with mesoporous cerium dioxide-based oxide and ZSM-5 molecular sieve as composite carriers.

[0008] Optionally, the silicon source is one or more of silica sol, active silicon dioxide, and tetraethyl orthosilicate.

[0009] Optionally, the aluminum source is one or more of pseudo-boehmite, aluminum isopropoxide, aluminum hydroxide, sodium metaaluminate, and active alumina.

[0010] Optionally, the template agent is one or two of n-butylamine, tetrapropylammonium hydroxide, tetrapropylammonium bromide, n-propylamine, tetraethylammonium hydroxide, tetraethylammonium bromide, hexamethyleneimine, and triethylamine.

[0011] Optionally, the alkali source is one or two of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

[0012] Optionally, the mesoporous cerium dioxide-based oxide is one or more of CeO2, CeO2-ZrO2, CeO2-ZrO2-Al2O3, CeO2-CaO, and CeO2-La2O3.

[0013] Optionally, the step of mixing the silicon source, the aluminum source, the template agent, the alkali source, the mesoporous cerium dioxide-based oxide, and water uniformly to obtain a suspension comprises:

[0014] The silicon source, the aluminum source, the template agent, the alkali source, the mesoporous cerium dioxide-based oxide, and water are mixed uniformly at a molar ratio of 1:(0.1-0.2):(0.06-0.4):(0-0.2):(1-20):(5-100) to obtain a suspension.

[0015] Optionally, the step of adding a metal oxide to the suspension and stirring to obtain a gel mixture comprises:

[0016] A metal oxide is added to the suspension, and stirring is performed at 50-80°C for 8-24h to obtain a gel mixture.

[0017] The metal element in the metal oxide accounts for 5%-25% of the mass of the silicon element in the silicon source, and the metal oxide is one or two of La2O3, CuO, NiO, Na2O, and Li2O.

[0018] Optionally, the step of hydrothermally crystallizing the gel mixture to obtain a crystallization product comprises:

[0019] The gel mixture is placed in a high-pressure reactor, and after being sealed, is placed at 200-250 DEG C for hydrothermal crystallization for 48-120 hours.

[0020] Optionally, after the crystallization product is cooled and dried, the step of calcining to obtain the reforming hydrogen production catalyst with the mesoporous ceria-based oxide and ZSM-5 molecular sieve as the composite carrier includes:

[0021] The crystallization product is quenched to room temperature, and after being dried, is placed in a muffle furnace and calcined at 500-750 DEG C for 8-20 hours to obtain the reforming hydrogen production catalyst with the mesoporous ceria-based oxide and ZSM-5 molecular sieve as the composite carrier.

[0022] The present application is based on the problem that the conventional oxide carrier has poor stability, the connection between the active metal and the carrier is not firm, and the metal component is prone to loss. The hydrothermal crystallization method is used to improve the catalyst oxide carrier, and the carrier is formed by the composite of the mesoporous ceria-based oxide and ZSM-5 molecular sieve to strengthen the connection between the metal active component and the composite carrier. The ZSM-5 molecular sieve has high thermal stability and is not prone to carbon deposition. The mesoporous ceria-based oxide and ZSM-5 molecular sieve are used as the composite carrier, which has low cost and can improve and maintain the dispersion of the metal active component of the catalyst, accelerate the conversion of carbon dioxide and propane, reduce the loss of the metal active component, and thus reduce the deactivation rate of the catalyst. Moreover, under relatively mild process conditions, high selectivity of hydrogen and carbon monoxide can be obtained, the conversion and utilization of carbon dioxide and propane are realized, and the catalyst obtained by the hydrothermal crystallization method has a core-shell structure, which can make the connection between the metal active component and the composite carrier of the catalyst more firm, so that under a lower load of the metal active component, a higher low-carbon alkane conversion rate can be achieved at a lower reaction temperature, the loss of the metal active component is reduced, and the service life of the catalyst is improved. The efficient conversion of carbon dioxide and propane is realized, the generated hydrogen can be used as a raw material for fuel cells, and the development trend of hydrogen energy is met. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0024] Currently, catalysts for hydrogen production from propane and carbon dioxide reforming are mainly divided into two categories: the first category is pure metal mesh or supported noble metal catalysts with Rh, Ru, Pd, Pt, Ir, etc. as active components; the second category is supported catalysts with Ni, Co, Fe, etc. VIII group transition metals as active components. The noble metal catalysts have high activity, good stability, and resistance to carbon deposition, etc. The catalytic activity of Ni in the supported catalysts is the best, close to Rh, and the price is low. However, the cost of the noble metal catalysts is too high, which is difficult to be popularized on a large scale. The Ni-based catalysts also have the problem of deactivation caused by carbon deposition, and the service life of the catalysts is limited. Therefore, the method of loading multiple metal components on metal oxides is usually used to improve the activity of the catalysts. However, due to the poor stability of the traditional oxide carriers and the use of conventional impregnation method to load active metals, the connection between the active metals and the carriers is not firm, which easily causes the loss of metal components, thereby leading to a short service life of the catalysts.

[0025] In view of the technical problems existing in the above-mentioned existing catalysts for hydrogen production from propane and carbon dioxide reforming, the embodiments of the present application provide a preparation method of a catalyst for hydrogen production from propane and carbon dioxide reforming, comprising the following steps:

[0026] Mixing a silicon source, an aluminum source, a template agent, an alkali source, a mesoporous ceria-based oxide, and water uniformly to obtain a suspension;

[0027] Adding a metal oxide into the suspension, stirring and mixing uniformly to obtain a gel mixture;

[0028] Performing hydrothermal crystallization on the gel mixture to obtain a crystallization product, and then cooling, drying, and calcining the crystallization product to obtain a reforming hydrogen production catalyst with a mesoporous ceria-based oxide and ZSM-5 molecular sieve as a composite carrier.

[0029] The application is based on the problem that the conventional oxide carrier has poor stability, the connection between the active metal and the carrier is not firm, and the metal component is prone to loss. The oxide carrier of the catalyst is improved by a hydrothermal crystallization method to form a carrier composed of mesoporous ceria-based oxide and ZSM-5 molecular sieve to strengthen the connection between the metal active component and the composite carrier. The ZSM-5 molecular sieve has high thermal stability and is not prone to carbon deposition. The mesoporous ceria-based oxide and the ZSM-5 molecular sieve are used as the composite carrier, which has low cost and can improve and maintain the dispersion of the metal active component of the catalyst, accelerate the conversion of carbon dioxide and propane, reduce the loss of the metal active component, and thus reduce the deactivation rate of the catalyst. Moreover, high selectivity of hydrogen and carbon monoxide can be obtained under relatively mild process conditions, realizing the conversion and utilization of carbon dioxide and propane. The catalyst obtained by the hydrothermal crystallization method has a core-shell structure, which can make the connection between the metal active component of the catalyst and the composite carrier more firm, so that the catalyst can realize high low-carbon alkane conversion rate at a lower reaction temperature under a lower metal active component loading, reduce the loss of the metal active component, and improve the service life of the catalyst. The efficient conversion of carbon dioxide and propane is realized, and the generated hydrogen can be used as a raw material for fuel cells, which meets the current trend of hydrogen energy development.

[0030] As an implementable manner of the application, the silicon source is one or more of silica sol, active silicon dioxide and tetraethyl orthosilicate.

[0031] The application forms a composite carrier composed of mesoporous ceria-based oxide and ZSM-5 molecular sieve. The silicon source is selected from silica sol, active silicon dioxide and tetraethyl orthosilicate. The silicon source and the aluminum source are used to form ZSM-5 molecular sieve with a high silicon-aluminum ratio.

[0032] As an implementable manner of the application, the aluminum source is one or more of pseudo-boehmite, aluminum isopropoxide, aluminum hydroxide, sodium metaaluminate and active alumina.

[0033] The application forms a composite carrier composed of mesoporous ceria-based oxide and ZSM-5 molecular sieve. Pseudo-boehmite, aluminum isopropoxide, aluminum hydroxide, sodium metaaluminate or active alumina is preferably used as the aluminum source to form ZSM-5 molecular sieve with a high silicon-aluminum ratio with the silicon source.

[0034] As an implementable manner of the application, the template agent is one or two of n-butylamine, tetrapropylammonium hydroxide, tetrapropylammonium bromide, n-propylamine, tetraethylammonium hydroxide, tetraethylammonium bromide, hexamethyleneimine and triethylamine.

[0035] The present application is to promote the formation of the nuclear structure of the catalyst in the preparation process of the catalyst, by increasing the organic template agent, to promote the formation of the pore material in the composite carrier of the mesoporous ceria-based oxide and ZSM-5 molecular sieve, preferably, the template agent is selected as n-butylamine.

[0036] As an implementable manner of the present application, the alkali source is one or two of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. Sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate all have alkalinity, and the addition of the alkali source in the preparation process of the catalyst makes the pH weakly alkaline, which can promote the formation of the gel mixture.

[0037] As an implementable manner of the present application, the mesoporous ceria-based oxide is one or more of CeO2, CeO2-ZrO2, CeO2-ZrO2-Al2O3, CeO2-CaO and CeO2-La2O3.

[0038] In order to form the composite carrier of the mesoporous ceria-based oxide and ZSM-5 molecular sieve, and support the active component as the skeleton of the catalyst active component, the mesoporous ceria-based oxide of the present application is selected as CeO2, CeO2-ZrO2, CeO2-ZrO2-Al2O3, CeO2-CaO and CeO2-La2O3, which can all provide a larger specific surface area, provide enough reaction active sites for the catalytic reaction, make the active component fully dispersed on the composite carrier, and also increase the strength of the catalyst.

[0039] As an implementable manner of the present application, the step of mixing the silicon source, the aluminum source, the template agent, the alkali source, the mesoporous ceria-based oxide and water uniformly to obtain a suspension includes:

[0040] The silicon source, the aluminum source, the template agent, the alkali source, the mesoporous ceria-based oxide and water are mixed uniformly in a proportion of 1:(0.1-0.2):(0.06-0.4):(0-0.2):(1-20):(5-100) in mole ratio to obtain a suspension.

[0041] By controlling the addition ratio of the silicon source, the aluminum source, the template agent, the alkali source, the mesoporous ceria-based oxide and water, the composite carrier of the mesoporous ceria-based oxide and ZSM-5 molecular sieve can be formed, preferably, the silicon source, the aluminum source, the template agent, the alkali source, the mesoporous ceria-based oxide and water are mixed in a proportion of 1:0.15:0.2:0.1:10:55 in mole ratio.

[0042] As an implementable manner of the present application, the step of adding metal oxide into the suspension and stirring uniformly to obtain a gel mixture includes:

[0043] adding metal oxide into the suspension, stirring at 50-80℃ for 8-24h to obtain a gel mixture;

[0044] The metal element in the metal oxide accounts for 5-25% of the mass of the silicon element in the silicon source, and the metal oxide is one or two of La2O3, CuO, NiO, Na2O and Li2O.

[0045] In specific applications, the metal oxides La2O3, CuO, NiO, Na2O and Li2O are used as metal active components, which have high activity and stable catalytic effect. Specifically, the mass percentage of the metal active component in the catalyst is 1-6%, and the rest is the composite carrier of the catalyst. By improving the catalyst carrier and strengthening the connection between the metal active component and the composite carrier, the catalyst can still achieve high conversion rate with a small amount of metal elements as active components.

[0046] As an implementable manner of the present application, the step of hydrothermally crystallizing the gel mixture to obtain a crystalline product comprises:

[0047] The gel mixture is placed in a high-pressure reaction kettle, sealed and subjected to hydrothermal crystallization at 200-250℃ for 48-120h.

[0048] The present application uses water as the reaction medium and heats the high-pressure reaction kettle in a sealed high-pressure reaction kettle to create a high-temperature and high-pressure reaction environment, so that difficultly soluble or insoluble substances are dissolved and recrystallized to form dispersed nanocrystalline nuclei. High-temperature calcination is not required, which avoids the formation of hard agglomerates of powders during the process, so that the active components of the catalyst are uniformly loaded on the composite carrier with good dispersibility.

[0049] As an implementable manner of the present application, the step of cooling, drying and calcining the crystalline product to obtain a reforming hydrogen production catalyst with mesoporous ceria-based oxide and ZSM-5 molecular sieve as composite carrier comprises:

[0050] The crystalline product is quenched to room temperature, dried and then placed in a muffle furnace and calcined at 500-750℃ for 8-20h to obtain a reforming hydrogen production catalyst with mesoporous ceria-based oxide and ZSM-5 molecular sieve as composite carrier.

[0051] The crystallization product after hydrothermal crystallization is quenched and dried, then calcined, so as to remove the residual water and other volatile components on the crystallization product, and the properties of the crystallization product are more stable after calcination, thereby obtaining a reforming hydrogen catalyst with stable chemical properties, good dispersion of active ingredients, and mesoporous ceria-based oxide and ZSM-5 molecular sieve as composite carrier.

[0052] The above technical solutions of the present application will be described in detail below in combination with specific examples.

[0053] Example 1

[0054] A preparation method of a propane and carbon dioxide reforming hydrogen catalyst, comprising the following steps:

[0055] 12.43 g of silica sol, 1.33 g of active alumina, 20.833 g of n-butylamine, 2.12 g of sodium hydroxide, 6.34 g of CeO2 and 50.12 g of deionized water were uniformly mixed to obtain a suspension;

[0056] 1% of La2O3 by mass fraction of silica sol was added to the suspension, and stirring was performed at 65°C for 16 h to obtain a gel mixture;

[0057] The gel mixture was placed in a high-pressure reaction kettle, sealed, and subjected to hydrothermal crystallization at 200°C for 120 h, then the crystallization product was quenched to room temperature, and then dried at 120°C for 5 h, and then placed in a muffle furnace and calcined at 520°C for 8 h to obtain a reforming hydrogen catalyst with mesoporous ceria-based oxide and ZSM-5 molecular sieve as composite carrier, denoted as Cat1.

[0058] Example 2

[0059] A preparation method of a propane and carbon dioxide reforming hydrogen catalyst, comprising the following steps:

[0060] 11.57 g of silica, 2.54 g of pseudoboehmite, 20.833 g of n-butylamine, 3.21 g of sodium carbonate, 7.21 g of CeO2-ZrO2 and 62 g of deionized water were uniformly mixed to obtain a suspension;

[0061] 1.5% of La2O3 by mass fraction of silica was added to the suspension, and stirring was performed at 50°C for 24 h to obtain a gel mixture;

[0062] The gel mixture was placed in a high-pressure reaction kettle, sealed, and subjected to hydrothermal crystallization at 250°C for 48 h, then the crystallization product was quenched to room temperature, and then dried at 110°C for 6 h, and then placed in a muffle furnace and calcined at 500°C for 10 h to obtain a reforming hydrogen catalyst with mesoporous ceria-based oxide and ZSM-5 molecular sieve as composite carrier, denoted as Cat2.

[0063] Example 3

[0064] A method for preparing a hydrogen reforming catalyst for propane and carbon dioxide, comprising the following steps:

[0065] Mixing tetraethyl orthosilicate 11.57 g, sodium aluminate 2.54 g, n-butylamine 19.87 g, potassium carbonate 3.21 g, CeO2-ZrO2-Al2O3 11.20 g and deionized water 81 g to obtain a suspension;

[0066] Adding 2% tetraethyl orthosilicate mass fraction of NiO to the suspension, stirring at 80℃ for 8h to obtain a gel mixture;

[0067] Placing the gel mixture in a high-pressure reaction kettle, and after being sealed, placing it at 250℃ for hydrothermal crystallization for 120h, then quenching the crystallization product to room temperature, and then drying at 100℃ for 6h, and then placing it in a muffle furnace and calcining at 750℃ for 8h to obtain a hydrogen reforming catalyst with mesoporous ceria-based oxide and ZSM-5 molecular sieve as composite carrier, denoted as Cat3.

[0068] Example 4

[0069] A method for preparing a hydrogen reforming catalyst for propane and carbon dioxide, comprising the following steps:

[0070] Mixing tetraethyl orthosilicate 11.57 g, sodium aluminate 2.54 g, n-butylamine 19.87 g, potassium carbonate 3.21 g, CeO2-ZrO2-Al2O3 11.20 g and deionized water 81 g to obtain a suspension;

[0071] Adding 3% tetraethyl orthosilicate mass fraction of NiO to the suspension, stirring at 80℃ for 8h to obtain a gel mixture;

[0072] Placing the gel mixture in a high-pressure reaction kettle, and after being sealed, placing it at 250℃ for hydrothermal crystallization for 120h, then quenching the crystallization product to room temperature, and then drying at 100℃ for 6h, and then placing it in a muffle furnace and calcining at 750℃ for 8h to obtain a hydrogen reforming catalyst with mesoporous ceria-based oxide and ZSM-5 molecular sieve as composite carrier, denoted as Cat4.

[0073] Example 5

[0074] A method for preparing a hydrogen reforming catalyst for propane and carbon dioxide, comprising the following steps:

[0075] Mixing tetraethyl orthosilicate 11.57 g, sodium aluminate 2.54 g, n-butylamine 19.87 g, potassium carbonate 3.21 g, CeO2-ZrO2-Al2O3 11.20 g and deionized water 81 g to obtain a suspension;

[0076] Adding 2.5% CuO by mass fraction of tetraethyl orthosilicate to the suspension, stirring at 80℃ for 8h to obtain a gel mixture;

[0077] Placing the gel mixture in a high-pressure reaction kettle, and after being sealed, placing it in a hydrothermal crystallization at 250℃ for 120h, then quenching the crystallization product to room temperature, and then drying at 100℃ for 6h, and then placing it in a muffle furnace and calcining at 750℃ for 8h to obtain a reforming hydrogen production catalyst with mesoporous ceria-based oxide and ZSM-5 molecular sieve as composite carriers, denoted as Cat5.

[0078] Example 6

[0079] A method for preparing a propane and carbon dioxide reforming hydrogen production catalyst, comprising the following steps:

[0080] Mixing tetraethyl orthosilicate 11.57 g, sodium aluminate 2.54 g, n-butylamine 19.87 g, potassium carbonate 3.21 g, CeO2-ZrO2-Al2O3 11.20 g and deionized water 81 g to obtain a suspension;

[0081] Adding 1.5% CuO by mass fraction of tetraethyl orthosilicate to the suspension, stirring at 80℃ for 8h to obtain a gel mixture;

[0082] Placing the gel mixture in a high-pressure reaction kettle, and after being sealed, placing it in a hydrothermal crystallization at 250℃ for 120h, then quenching the crystallization product to room temperature, and then drying at 100℃ for 6h, and then placing it in a muffle furnace and calcining at 750℃ for 8h to obtain a reforming hydrogen production catalyst with mesoporous ceria-based oxide and ZSM-5 molecular sieve as composite carriers, denoted as Cat6.

[0083] Experimental Example

[0084] Test the reaction activity loss rate of the reforming hydrogen production catalysts obtained in Examples 1-6, and evaluate the propane and carbon dioxide reforming hydrogen production reaction of the catalysts obtained in the above examples in a fixed bed evaluation device, the catalyst loading amount is 5g, the reaction temperature is 580℃, the feed is 50% CO2+30% C3H8+20% N2, and the total feed volume space velocity is 1000h-1. -1 The evaluation results after 12 hours of reaction are shown in Table 1.

[0085] Table 1

[0086]

[0087]

[0088] As shown in Table 1, at a reaction temperature of 580℃, the conversion rate of carbon dioxide can reach more than 90% and the conversion rate of propane can reach more than 86% by using the catalyst of the present application. After 12 hours of reaction, the loss rate of the active component of the catalyst is the highest of 25.3% and the lowest of 7.5%, indicating that the service life of the catalyst can be up to 156 hours.

[0089] The above description is only optional embodiments of the present application, and does not limit the patent scope of the present application. Any equivalent structural transformation, direct / indirect application in other related technical fields, or direct / indirect application in other related technical fields based on the inventive concept of the present application are included in the patent protection scope of the present application.

Claims

1. The application of a reforming catalyst in the reforming of propane and carbon dioxide to produce hydrogen, characterized in that, The preparation method of the reforming hydrogen production catalyst includes the following steps: A suspension is obtained by mixing silicon source, aluminum source, template agent, alkali source, mesoporous cerium dioxide-based oxide and water. A metal oxide is added to the suspension and stirred until homogeneous to obtain a gel mixture; the metal oxide is La2O3 or CuO; the mass percentage of La2O3 or CuO in the reforming hydrogen production catalyst is 1% to 6%; The gel mixture was subjected to hydrothermal crystallization to obtain a crystalline product. The crystalline product was then cooled, dried, and calcined to obtain a reforming hydrogen production catalyst with mesoporous cerium dioxide-based oxide and ZSM-5 molecular sieve as a composite support. The silicon source is one or more of silica sol, active silica, and tetraethyl orthosilicate; the alkali source is one or two of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; the mesoporous cerium dioxide-based oxide is one or more of CeO2, CeO2-ZrO2, CeO2-ZrO2-Al2O3, CeO2-CaO, and CeO2-La2O3. The step of mixing silicon source, aluminum source, template agent, alkali source, mesoporous cerium dioxide-based oxide and water to obtain a suspension includes: mixing silicon source, aluminum source, template agent, alkali source, mesoporous cerium dioxide-based oxide and water in a molar ratio of 1:(0.1-0.2):(0.06-0.4):(0.1-0.2):(1-20):(5-100) to obtain a suspension.

2. The application according to claim 1, characterized in that, The aluminum source is one or more of boehmite, aluminum isopropoxide, aluminum hydroxide, sodium aluminate, and activated alumina.

3. The application according to claim 1, characterized in that, The template agent is one or two of the following: n-butylamine, tetrapropylammonium hydroxide, tetrapropylammonium bromide, n-propylamine, tetraethylammonium hydroxide, tetraethylammonium bromide, hexamethyleneimine, and triethylamine.

4. The application according to claim 1, characterized in that, The step of adding a metal oxide to the suspension and stirring to obtain a gel mixture includes: adding a metal oxide to the suspension and stirring at 50℃-80℃ for 8h-24h to obtain a gel mixture.

5. The application according to claim 1, characterized in that, The step of hydrothermally crystallizing the gel mixture to obtain a crystalline product includes: placing the gel mixture in a high-pressure reactor, sealing it, and then subjecting it to hydrothermal crystallization at 200℃-250℃ for 48h-120h.

6. The application according to claim 1, characterized in that, The step of cooling and drying the crystallized product and then calcining it to obtain a reforming hydrogen production catalyst with mesoporous cerium dioxide-based oxide and ZSM-5 molecular sieve as a composite support includes: rapidly cooling the crystallized product to room temperature, drying it, and then placing it in a muffle furnace and calcining it at 500℃-750℃ for 8h-20h to obtain a reforming hydrogen production catalyst with mesoporous cerium dioxide-based oxide and ZSM-5 molecular sieve as a composite support.

Images