Supported methanol steam reforming hydrogen production composite catalyst and preparation method thereof

Abstract

The invention relates to the technical field of hydrogen production catalysts, in particular to a supported composite catalyst for hydrogen production through methanol steam reforming and a preparation method thereof.The catalyst is composed of active components and a carrier, the active components are Cu and Zn metal oxides (CuO-ZnO), the carrier is copper-doped magnesium-aluminum-based hydrotalcite (Mg-Al1-x-Cux-LDH), and the carrier is a metal oxide (CuO-ZnO). The mass percentage of the active component CuO-ZnO in the composite catalyst is 90% (the mass ratio of CuO to ZnO is 2.6), the mass percentage of the carrier Mg-Al < 1-x >-Cux-LDH is 10%, and the value of the copper doping amount x in the carrier is 0.005-0.1. The copper element is doped in the magnesium-aluminum-based hydrotalcite carrier, so that the activity and selectivity of the copper-based catalyst for catalyzing the methanol steam reforming hydrogen production reaction can be remarkably improved, the copper-based composite catalyst is prepared by taking the copper-doped magnesium-aluminum-based hydrotalcite as the carrier through a reverse coprecipitation method, the preparation method is simple, the cost is low, and the copper-based composite catalyst has a good application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen production catalysts, and in particular to a supported methanol steam reforming hydrogen production composite catalyst and a preparation method thereof. Background Art

[0002] With global energy demand continuing to grow and fossil fuel depletion intensifying, the development of efficient, clean alternative energy sources has become a research priority in the energy sector. Hydrogen, due to its high calorific value (142 MJ / kg), its combustion product consisting solely of water (zero carbon emissions), and its high energy storage density, is considered an ideal secondary energy carrier for the future. However, the large-scale application of hydrogen energy is limited by storage and transportation safety and efficient production technologies, necessitating the development of low-cost, high-purity hydrogen production methods.

[0003] Among various hydrogen production technologies, methanol steam reforming (MSR) has attracted significant attention due to its physicochemical properties: low carbon content (H / C ratio of 4:1), absence of sulfur and nitrogen impurities, and a liquid state at room temperature (making storage and transportation significantly safer than gaseous or liquid hydrogen). MSR can also be produced from biomass-based feedstocks, meeting the requirements of sustainable development. The reaction can be carried out at temperatures between 200 and 280°C, reducing energy consumption by approximately 30% compared to conventional water electrolysis. Furthermore, the product gas contains a low CO content (typically <2%), simplifying subsequent purification steps and making it particularly suitable for small, mobile hydrogen production systems.

[0004] Catalyst performance is key to the industrialization of MSR technology. Layered Double Hydroxides (LDH), a type of two-dimensional nanomaterial with a layered structure, are excellent catalyst supports due to their chemical composition (e.g., Mg / Al ratio) and tunable layer cations. However, conventional MgAl-LDH-based catalysts face the following technical bottlenecks in MSR reactions: (1) low dispersion of metal active components, which are prone to agglomeration and deactivation; (2) insufficient catalytic activity at low temperatures (<300°C), resulting in low methanol conversion; and (3) the generation of byproducts (e.g., CO) during the reaction, which reduces hydrogen selectivity.

[0005] Based on this, the present invention aims to provide a methanol steam reforming hydrogen production composite catalyst and its preparation method. By optimizing the hydrotalcite carrier composition and metal-carrier interaction, high activity, high selectivity and long-term stability of the methanol steam reforming hydrogen production reaction can be achieved, providing key material support for the miniaturized application of MSR technology. Summary of the Invention

[0006] To solve the above problems, the present invention provides a supported methanol steam reforming hydrogen production composite catalyst and a preparation method thereof. The catalyst has high activity, high selectivity and good stability, and is suitable for methanol steam reforming hydrogen production reaction.

[0007] The technical solution adopted in the present invention is:

[0008] A method for preparing a supported methanol steam reforming hydrogen production composite catalyst comprises the following steps:

[0009] S1. Dissolve Al(NO3)3·9H2O, Mg(NO3)2·6H2O, Cu(NO3)2·3H2O, and urea in deionized water and stir magnetically to dissolve.

[0010] S2. The solution obtained in step S1 is transferred to a container and placed in an oven;

[0011] S3. The material obtained in step S2 was separated into a slurry by centrifugation, and then the product was rinsed with deionized water and air-dried overnight to obtain a sample of Mg-Al 1-x -Cu x -LDH, where the value of x is 0.005-0.1;

[0012] S4. Dissolve Cu(NO3)2·3H2O and Zn(NO3)2·6H2O in deionized water to obtain solution A, dissolve ammonium carbonate in deionized water, and then add the Mg-Al obtained in step S3. 1-x -Cu x -LDH sample and disperse it evenly to obtain suspension B;

[0013] S5. The suspension B was placed in a water bath, stirred at a constant temperature, and then solution A was added dropwise to the suspension B for precipitation. After the precipitation was completed, the mixture was stirred at a constant temperature and then aged at room temperature;

[0014] S6. The aging mixture is filtered and washed, and then placed in an oven for thorough drying to obtain a precursor. The obtained precursor is placed in a tubular furnace and calcined under an Ar atmosphere. After calcination, it is naturally cooled to room temperature. Then, a H2 / Ar mixed gas is introduced into a fixed-bed reactor, and the temperature is raised from room temperature to 300°C for activation. The catalyst is kept at this temperature for 90 minutes to obtain a methanol steam reforming hydrogen production catalyst.

[0015] Furthermore, in step S1, the molar ratio of Mg:Al:Cu is 2:0.995-0.9:0.005-0.1, and the total molar ratio of urea to metal ions in the carrier is 3:1.

[0016] Furthermore, in step S2, the product is placed in an oven at 100° C. for 48 hours.

[0017] Furthermore, in step S3, the slurry is separated by centrifugation at 10,000 rpm for 10 minutes.

[0018] Further, in step S4, ammonium carbonate, Mg-Al 1-x -Cu x -LDH was dissolved in deionized water and stirred. After ammonium carbonate was dissolved, ultrasonic treatment was performed for 30 minutes to obtain suspension B.

[0019] Furthermore, in step S5, the temperature of the water bath is set to 65° C., and the stirring speed is set to 400 rpm.

[0020] Furthermore, in step S5, solution A is added dropwise to suspension B for precipitation at a dropping rate of 1 drop / s. After precipitation is completed, constant temperature stirring is continued for 4 hours, and ultrasonic treatment is performed for 30 minutes after the constant temperature stirring is completed.

[0021] Furthermore, in step S6, the temperature for sufficient drying in the oven is 60-70°C; the calcination temperature in the tubular furnace is set to 350-450°C, the heating rate is 2°C / min, and the calcination time is 4-6h; in the H2 / Ar mixed gas introduced into the fixed bed reactor, the volume fraction of H2 is 9.74%, and the flow rate of the introduced mixed gas is 40mL / min.

[0022] Based on the same inventive concept, the present application also provides a supported methanol steam reforming hydrogen production composite catalyst prepared by the above-mentioned preparation method, the catalyst is composed of an active component and a carrier, the active component is Cu and Zn metal oxides CuO-ZnO, the carrier is copper-doped magnesium-aluminum-based hydrotalcite Mg-Al 1-x -Cu x -LDH, wherein the value of the doping amount x is 0.005-0.1.

[0023] Furthermore, the mass percentage of the active component CuO-ZnO in the catalyst is 90%, and the mass ratio of CuO / ZnO is 2.6; the carrier Mg-Al 1-x -Cu x The mass percentage of -LDH is 10%.

[0024] The beneficial effects of the present invention are as follows:

[0025] The supported methanol steam reforming hydrogen production composite catalyst provided by the present invention comprises an active component CuO-ZnO and a carrier Mg-Al 1-x -Cu x-LDH composition, wherein the hydrotalcite carrier has a unique layered structure and adjustable chemical composition, which can effectively inhibit the occurrence of side reactions in the methanol steam reforming reaction, reduce the generation of by-products, and improve the selectivity of the target product hydrogen. At the same time, CuO-ZnO is used as the active component. By using cheap copper as the active component and combining it with a simple and easy-to-operate preparation process, the preparation cost of the catalyst is greatly reduced, and it has high economic efficiency. The present invention significantly improves the activity of the catalyst by doping copper in the hydrotalcite carrier, can effectively promote the progress of the methanol steam reforming reaction, and improve the hydrogen generation rate. At the same time, the present invention performs CuO-ZnO deposition by a reverse coprecipitation method. 2+ 、Zn 2+ Precipitation, the precipitation process is carried out in alkaline solution, the pH value is from high to low, which can make Cu 2+ 、Zn 2+ At the same time, they precipitate evenly to form a co-precipitate in which the Cu and Zn components are evenly dispersed with each other, so that the prepared Cu-based catalyst has high activity, is active in a lower temperature range, and maintains good activity and stability in long-term test reactions. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The XRD patterns of the catalysts prepared in Examples 1-4 of the present invention in the unreduced activated state are shown;

[0027] Figure 2 Activity test graphs of the catalysts prepared in Examples 1-3 and Comparative Examples 1-2 of the present invention;

[0028] Figure 3 Activity test graphs of the catalysts prepared in Examples 4-6 of the present invention and Comparative Examples 1-2;

[0029] Figure 4 These are SEM and TEM images of the catalyst prepared in Example 2 of the present invention in an unreduced activated state. DETAILED DESCRIPTION

[0030] To facilitate understanding of the present invention, the present invention will be described more fully below through examples, with preferred embodiments of the present invention provided below. However, the present invention can be implemented in a variety of different forms and is not limited to the embodiments described herein. Any other embodiments obtained by modifying or equivalently replacing the technical solution of the present invention without inventive results are within the scope of protection of the present invention.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0032] The numerical values disclosed in the embodiments of the present application are approximate values, and are not definite values. All values within the error range are included without being limited to the specific numerical values disclosed in the embodiments of the present application, if the error or experimental condition permits.

[0033] Unless otherwise specifically indicated, all raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or prepared by existing methods.

[0034] It should be noted that in the following embodiments, in the preparation process of the catalyst, the Cu source in the active ingredient is copper nitrate trihydrate, the Zn source is zinc nitrate hexahydrate, the Al source is aluminum nitrate nonahydrate, and the Mg source is magnesium nitrate hexahydrate. The urea is a pore-forming agent, the ammonium carbonate is a precipitating agent, and the solvent is deionized water.

[0035] In the following examples and comparative examples, a fixed bed reactor is used to test the performance of the catalyst, and a GC2060 gas chromatograph from Shanghai Sensi Instrument Co., Ltd. is used to analyze the gas phase products to obtain the conversion rate and selectivity.

[0036] The following are specific embodiments

[0037] Example 1

[0038] The present embodiment provides a preparation method of a supported methanol steam reforming hydrogen production composite catalyst, comprising the following steps:

[0039] S1. Dissolve 2.781 g of Al(NO3)3·9H2O, 4.29 g of Mg(NO3)2·6H2O, 0.199 g of Cu(NO3)2·3H2O and 4.9 g of urea in 50 mL of deionized water, and magnetically stir to dissolve;

[0040] S2. Transfer the solution obtained in step S1 to a polytetrafluoroethylene container, and place it in an oven at 100°C for 48 h;

[0041] S3. Separate the slurry obtained in step S2 by centrifugation at 10,000 rpm for 10 min, then rinse the product with deionized water and air dry overnight. The sample obtained in this step is named Mg-Al 1-x -Cu x -LDH;

[0042] S4. Dissolve 3.926 g of Cu(NO3)2·3H2O and 1.837 g of Zn(NO3)2·6H2O in 100 mL of deionized water, and magnetically stir to dissolve to obtain solution A; dissolve 2.170 g of ammonium carbonate in deionized water, and then add the Mg-Al 1-x -Cux -LDH 0.2 g was evenly dispersed in 100 mL of deionized water and sonicated for 30 min to obtain suspension B;

[0043] S5. The suspension B obtained in step S4 was placed in a water bath, set at 65°C and 400 rpm, and the solution A obtained in step S4 was added dropwise to the suspension B for precipitation; after precipitation was complete, the mixture was stirred at constant temperature for 4 h; after the constant temperature stirring was completed, the mixture was ultrasonically treated again for 30 min, and then the mixture was aged at room temperature for 18 h;

[0044] S6. The aged mixed solution obtained in step S5 is added to a Buchner funnel for suction filtration and washing; after completion, the mixture is placed in a 65°C oven for thorough drying to obtain a precursor; the obtained precursor is placed in a tube furnace, and calcined under an Ar atmosphere at a temperature of 350°C and a heating rate of 2°C / min for 4 hours. After calcination, it is naturally cooled to room temperature to obtain an unactivated methanol steam reforming hydrogen production catalyst. A sample of 200 mg is taken, mixed with 800 mg of quartz sand, and loaded into a quartz tube with an inner diameter of 10 mm, an outer diameter of 20 mm, and a length of 50 cm. The catalyst is activated in a fixed bed reactor, and a H2 / Ar (H2: 9.74%) mixed gas is introduced at a flow rate of 40 mL / min. The temperature is raised from room temperature to 300°C and kept at this temperature for 90 minutes for reduction to obtain a composite catalyst 1 (CuO-ZnO / Mg-Al 1-x -Cu x -LDH, x=0.1).

[0045] Example 2

[0046] This embodiment provides a method for preparing a supported composite catalyst for hydrogen production from methanol steam reforming, which differs from Example 1 in that:

[0047] In step S1, 2.9355 g of Al(NO3)3·9H2O, 4.29 g of Mg(NO3)2·6H2O, 0.1 g of Cu(NO3)2·3H2O and 4.9 g of urea were dissolved in 50 mL of deionized water and magnetically stirred to dissolve them.

[0048] The composite catalyst 2 (CuO-ZnO / Mg-Al 1-x -Cu x -LDH, x=0.05).

[0049] Example 3

[0050] This embodiment provides a method for preparing a supported composite catalyst for hydrogen production from methanol steam reforming, which differs from Example 1 in that:

[0051] In step S1, 2.9355 g of Al (NO3) 3 ·9H2O, 4.29 g of Mg (NO3) 2 ·6H2O, 0.0605 g of Cu (NO3) 2 ·3H2O and 4.9 g of urea were dissolved in 50 mL of deionized water, and magnetic stirring was performed to dissolve them.

[0052] The composite catalyst 3 (CuO-ZnO / Mg-Al 1-x -Cu x -LDH, x = 0.03) prepared in this example.

[0053] Example 4

[0054] The present example provides a preparation method of a supported methanol steam reforming hydrogen production composite catalyst, which is different from that of Example 1 in that:

[0055] In step S1, 0.3117 g of Al (NO3) 3 ·9H2O, 4.29 g of Mg (NO3) 2 ·6H2O, 0.01 g of Cu (NO3) 2 ·3H2O and 4.9 g of urea were dissolved in 50 mL of deionized water, and magnetic stirring was performed to dissolve them.

[0056] The composite catalyst 4 (CuO-ZnO / Mg-Al 1-x -Cu x -LDH, x = 0.005) prepared in this example.

[0057] Example 5

[0058] The present example provides a preparation method of a supported methanol steam reforming hydrogen production composite catalyst, which is different from that of Example 1 in that:

[0059] In step S1, 2.9355 g of Al (NO3) 3 ·9H2O, 4.29 g of Mg (NO3) 2 ·6H2O, 0.1 g of Cu (NO3) 2 ·3H2O and 4.9 g of urea were dissolved in 50 mL of deionized water, and magnetic stirring was performed to dissolve them.

[0060] In step S6, the obtained precursor was placed in a tube furnace, and calcination was performed under an Ar atmosphere at a temperature of 350°C for 6 h at a temperature increase rate of 2°C / min, and after the calcination was completed, natural cooling was performed to room temperature.

[0061] The composite catalyst 5 (CuO-ZnO / Mg-Al 1-x -Cu x -LDH, x = 0.05) prepared in this example.

[0062] Example 6

[0063] (CuO-ZnO / Mg-Al1-x -Cu x -LDH x = 0.05 450℃ / 4h)

[0064] The embodiment provides a preparation method of a supported methanol steam reforming hydrogen composite catalyst, which is different from the embodiment 1.

[0065] In step S1, 2.9355 g of Al (NO3) 3·9H2O, 4.29 g of Mg (NO3) 2·6H2O, 0.1 g of Cu (NO3) 2·3H2O and 4.9 g of urea are dissolved in 50 mL of deionized water, and magnetic stirring is performed to dissolve the mixture.

[0066] In step S6, the obtained precursor is placed in a tube furnace, calcination is performed under an Ar atmosphere, at a temperature of 450℃, for 4 h, at a temperature rising rate of 2℃ / min, and after the calcination is completed, the mixture is naturally cooled to room temperature.

[0067] The composite catalyst 6 (CuO-ZnO / Mg-Al 1-x -Cu x -LDH, x = 0.05) prepared in the embodiment.

[0068] Comparative example 1

[0069] The comparative example provides a supported methanol steam reforming hydrogen composite catalyst and a preparation method thereof, which is different from the embodiment 1.

[0070] In step S1, 3.09 g of Al (NO3) 3·9H2O, 4.29 g of Mg (NO3) 2·6H2O and 4.9 g of urea are dissolved in 50 mL of deionized water, and magnetic stirring is performed to dissolve the mixture.

[0071] The composite catalyst prepared in the comparative example is a supported methanol steam reforming hydrogen copper-based composite catalyst, which is denoted as comparative example 1 (CuO-ZnO / Mg-Al 1-x -Cu x -LDH, x = 0).

[0072] Comparative example 2

[0073] The comparative example provides a supported methanol steam reforming hydrogen composite catalyst and a preparation method thereof, which is different from the embodiment 1.

[0074] The steps S1-S3 are not performed on the catalyst Mg-Al 1-x -Cu x-LDH carrier preparation; in step S4, 3.926g Cu(NO3)2·3H2O, 1.837g Zn(NO3)2·6H2O and 1.47g Al(NO3)3·9H2O were dissolved in 100mL deionized water and magnetically stirred to dissolve them to obtain solution A; 2.72g ammonium carbonate was dissolved in 100mL deionized water and ultrasonicated for 30min to obtain solution B.

[0075] The supported copper-based composite catalyst for hydrogen production from methanol steam reforming was prepared in this comparative example, which is recorded as comparative example 2 (CuO-ZnO-Al2O3).

[0076] The catalysts prepared in the above examples and comparative examples were tested for performance, and the test results are as follows:

[0077] See also Figure 1 The XRD pattern shows characteristic peaks at 2θ = 32°, 34°, 36°, 47°, and 56° that fully match those of a ZnO standard card (PDF#89-0510), confirming the presence of a ZnO phase in the catalyst. Furthermore, peaks at 2θ = 38°, 48°, and 58° match those of a CuO standard card (PDF#45-0937), indicating the coexistence of a CuO crystalline phase in the catalyst system. The profiles and relative intensities of the diffraction peaks do not change significantly with increasing Cu content in the support, indicating that the main crystalline structures of ZnO and CuO remain stable. No other diffraction peaks were detected in the pattern, further demonstrating that changes in the Cu doping level in the support do not introduce additional phases, and that the catalyst's phase composition remains stable.

[0078] See also Figure 2 and Figure 3 From the catalyst activity images, it can be seen that the catalytic performance of the catalysts in Examples 1-4 is significantly better than that in Examples 5-6. By comparing the experimental conditions, it was found that Examples 1-4 adopted the process parameters of calcination at 350°C for 4 hours, while the activity of Example 5 (calcination at 350°C for 6 hours) and Example 6 (calcination at 450°C for 4 hours) decreased. It can be inferred that the condition of calcination at 350°C for 4 hours is more conducive to the improvement of catalytic activity. It is worth noting that Example 2 showed a catalytic activity significantly higher than that of other samples in the low temperature range of 220-260°C, which indicates that when x=0.05, the active component distribution ratio of the catalyst reaches the optimal state.

[0079] See also Figure 4 The SEM and TEM images of the unactivated sample in Example 2 show that the high-resolution images show that the support surface has obvious concave-convex and microporous structures. This feature is the three-dimensional porous structure formed by the release of CO2 during the calcination process, which is conducive to the adsorption and diffusion of reactant molecules. CuO and ZnO are evenly dispersed in the Mg-Al 1-x -Cu xNo obvious agglomerates were observed on the surface of the -LDH support. This highly dispersed microstructure can effectively increase the exposure of the catalyst's active sites, providing a structural basis for improving the low-temperature catalytic performance of copper-based composite catalysts.

[0080] In summary, the Mg-Al prepared by the present invention 1-x -Cu x -LDH carrier has a unique layered structure and adjustable chemical composition, which can effectively inhibit the occurrence of side reactions, reduce the generation of by-products, and improve the selectivity of the target product hydrogen. Using cheap copper as the active component, combined with a simple and easy preparation process, greatly reduces the preparation cost of the catalyst, with high economic efficiency. By doping copper in the hydrotalcite carrier, the activity of the catalyst is significantly improved, which can effectively promote the methanol reforming reaction and increase the hydrogen generation rate. 2+ 、Zn 2+ Precipitation, the precipitation process is carried out in alkaline solution, the pH value is from high to low, which can make Cu 2+ 、Zn 2+ At the same time, they precipitate evenly to form a co-precipitate in which the Cu and Zn components are evenly dispersed with each other, so that the prepared Cu-based catalyst has high activity, is active in a lower temperature range, and maintains good activity and stability in long-term test reactions.

[0081] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A method for preparing a supported methanol steam reforming hydrogen production composite catalyst, characterized in that: The steps include: S1. Dissolve Al(NO3)3·9H2O, Mg(NO3)2·6H2O, Cu(NO3)2·3H2O, and urea in deionized water and stir magnetically to dissolve. S2. The solution obtained in step S1 is transferred to a container and placed in an oven; S3. The material obtained in step S2 was separated into a slurry by centrifugation, and then the product was rinsed with deionized water and air-dried overnight to obtain a sample of Mg-Al 1-x -Cu x -LDH, where the value of x is 0.005-0.1; S4. Dissolve Cu(NO3)2·3H2O and Zn(NO3)2·6H2O in deionized water to obtain solution A, dissolve ammonium carbonate in deionized water, and then add the Mg-Al obtained in step S3. 1-x -Cu x -LDH sample and disperse it evenly to obtain suspension B; S5. The suspension B was placed in a water bath, stirred at a constant temperature, and then solution A was added dropwise to the suspension B for precipitation. After the precipitation was completed, the mixture was stirred at a constant temperature and then aged at room temperature; S6. The aging mixture is filtered and washed, and then placed in an oven for thorough drying to obtain a precursor. The obtained precursor is placed in a tubular furnace and calcined under an Ar atmosphere. After calcination, it is naturally cooled to room temperature. Then, a H2 / Ar mixed gas is introduced into a fixed-bed reactor, and the temperature is raised from room temperature to 300°C for activation. The catalyst is kept at this temperature for 90 minutes to obtain a methanol steam reforming hydrogen production catalyst.

2. The method for preparing a supported composite catalyst for methanol steam reforming to produce hydrogen according to claim 1, wherein: In step S1, the molar ratio of Mg:Al:Cu is 2:0.995-0.9:0.005-0.1, and the total molar ratio of urea to metal ions is 3:

1.

3. The method for preparing a supported composite catalyst for methanol steam reforming to produce hydrogen according to claim 1, wherein: In step S2, the product is placed in an oven at 100° C. for 48 hours.

4. The method for preparing a supported composite catalyst for hydrogen production by methanol steam reforming according to claim 1, wherein: In step S3, the slurry was separated by centrifugation at 10,000 rpm for 10 minutes.

5. The method for preparing a supported composite catalyst for methanol steam reforming to produce hydrogen according to claim 1, wherein: In step S4, ammonium carbonate, Mg-Al 1-x -Cu x -LDH was dissolved in deionized water and stirred. After ammonium carbonate was dissolved, ultrasonic treatment was performed for 30 minutes to obtain suspension B.

6. The method for preparing a supported composite catalyst for hydrogen production by methanol steam reforming according to claim 1, wherein: In step S5, the temperature of the water bath is set to 65° C., and the stirring speed is set to 400 rpm.

7. The method for preparing a supported composite catalyst for hydrogen production by methanol steam reforming according to claim 1, wherein: In step S5, solution A is added dropwise to suspension B for precipitation at a dropping rate of 1 drop / s. After precipitation is completed, constant temperature stirring is continued for 4 hours. After the constant temperature stirring is completed, ultrasonic treatment is performed for 30 minutes.

8. The method for preparing a supported composite catalyst for hydrogen production by methanol steam reforming according to claim 1, wherein: In step S6, the temperature for sufficient drying in the oven is 60-70°C; the calcination temperature in the tubular furnace is set to 350-450°C, the heating rate is 2°C / min, and the calcination time is 4-6h; in the H2 / Ar mixed gas introduced into the fixed bed reactor, the volume fraction of H2 is 9.74%, and the flow rate of the introduced mixed gas is 40mL / min.

9. A supported methanol steam reforming hydrogen production composite catalyst prepared by the preparation method according to any one of claims 1 to 8, characterized in that: The catalyst is composed of active components and a carrier. The active components are Cu and Zn metal oxides CuO-ZnO, and the carrier is copper-doped magnesium-aluminum hydrotalcite Mg-Al 1-x -Cu x -LDH, wherein the value of the doping amount x is 0.005-0.

1.

10. The supported composite catalyst for hydrogen production from methanol steam reforming according to claim 9, characterized in that The mass percentage of the active component CuO-ZnO in the catalyst is 90%, and the mass ratio of CuO / ZnO is 2.6; the carrier Mg-Al 1-x -Cu x The mass percentage of -LDH is 10%.

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