Reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming and preparation method of reverse-phase copper-based catalyst

Abstract

The invention discloses a reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming and a preparation method of the reverse-phase copper-based catalyst, metal salt, amino acid and silica sol are used as raw materials, the solution is steamed to be colloidal, and the reverse-phase copper-based catalyst is prepared through the steps of drying, roasting and silicon removal. The reverse-phase copper-based catalyst has the advantages of being high in active component content, high in oxide dispersion, rich in metal-carrier interface and the like, the preparation process is simple and easy to operate, and the reverse-phase copper-based catalyst is environmentally friendly and free of pollution.

Description

Technical Field

[0001] The present invention relates to the technical field of catalyst preparation, and particularly relates to a reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming and a preparation method thereof. Background Art

[0002] Among various hydrogen production methods, methanol hydrogen production technology represented by methanol steam reforming has the advantages of low reaction temperature, high hydrogen purity, low investment cost, and convenient raw material transportation and storage. Currently, the catalysts reported for methanol reforming to produce hydrogen are mainly of two types: non-noble metal catalysts and noble metal catalysts. Among non-noble metal catalysts, copper-based catalysts have become the first choice for the research of methanol steam reforming hydrogen production catalysts due to their good reforming activity, high hydrogen selectivity, and low price.

[0003] Although current researchers have done a lot of research on improving the catalytic activity of copper-based catalysts, due to the limitations of the active metal loading and the content of the metal-oxide interface, ordinary copper / oxide catalysts have bottleneck problems in terms of activity and stability. Under this background, the oxide / metal reverse-phase catalyst formed by loading metal particles on oxides has an interfacial space structure different from that of traditional metal / oxide catalysts. Oxides with smaller particle sizes can expose more defect sites, thereby forming a stronger metal-support interaction with copper particles and a richer active metal-oxide interface, ultimately improving the catalyst performance. In addition, in practical applications, the cost of non-noble metals (such as Fe, Co, Ni, Cu, etc.) is basically the same as or even lower than the price of oxide supports. Therefore, the design of the reverse-phase oxide / metal structure can provide new opportunities for the preparation of efficient catalysts.

[0004] Reverse-phase catalysts require that the oxide particle size is smaller than the metal particles loading on it, and there should be a strong metal-support interaction force between the metal and the oxide, which requires relatively strict preparation methods for reverse-phase catalysts. Currently, the commonly used preparation methods for reverse-phase catalysts include microemulsion method, sol-gel method, atomic layer deposition, flame spray pyrolysis, etc. However, these preparation methods are cumbersome and complex and have high requirements for equipment, which is not conducive to practical applications. Chinese invention patent with publication number CN107497439 B discloses a preparation method of a copper-based catalyst applicable to high-temperature reverse water-gas shift reaction, which has a low copper loading, and the prepared catalyst is a traditional supported type and does not have a reverse-phase structure. Chinese patent with publication number CN 106311252 A discloses a preparation method of a porous CuO-CeO2 bimetallic oxide catalyst applicable to CO oxidation reaction, but the addition method of glycine in this preparation method is different from that of this patent, and it only plays the role of fuel, mainly relying on silica sol as a template to construct the geometric structure advantage of pores to increase the contact area, and cannot highly disperse the oxides, so it cannot form a reverse-phase catalyst structure with rich interfaces. SUMMARY OF THE INVENTION

[0005] In view of the problems existing in the prior art, the present invention provides a reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming and a preparation method thereof. The reverse-phase catalyst has the advantages of high active component content, high dispersion of components, strong interaction between metal and carrier, etc., and the preparation process is simple and easy to operate.

[0006] To achieve the above object, the technical solution of the present invention is as follows: The present invention provides a reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming. The catalyst has a MO x / Cu reverse-phase structure, and oxide MO x nanoclusters are uniformly distributed on the surface of Cu particles, where MO x is one or more of MgO, Al2O3, MnO2, TiO2, Fe2O3, ZnO, Ga2O3, La2O3, CeO2, Y2O3 and ZrO2.

[0007] Further, the mass fraction of the MO x oxide in the catalyst MO x / Cu is 5-50 wt%.

[0008] The present invention provides a preparation method of the reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming, comprising the following steps: S1: Weigh a certain amount of copper metal salt, M metal salt and amino acid, pour them into water and mix and dissolve to obtain solution A; S2: Add silica sol to solution A obtained in step S1 to obtain sol B; S3: Heat and evaporate sol B obtained in step S2 to a viscous state, put it into an oven to initiate combustion to obtain solid C; S4: Calcinate solid C obtained in step S3 in a muffle furnace to obtain solid D; S5: Treat solid D in step S4 with NaOH solution to remove silicon dioxide, then wash with deionized water, filter by suction and dry to obtain the reverse-phase copper-based catalyst.

[0009] Further, in step S1, the copper metal salt is one or more of nitrates, chlorides and sulfates, and the precursor metal salt of MO x is one or more of nitrates, chlorides and sulfates; the amino acid is one or more of glycine, alanine and valine; the molar ratio of the sum of amino acid and metal salt is 1-6:1.

[0010] Further, in step S2, the size of the silicon dioxide nanoparticles in the silica sol is 10-50 nm, and the molar ratio of silicon dioxide to metal salt is 1-4:1.

[0011] Further, in step S3, the drying temperature in the oven is 160 - 240 °C.

[0012] Further, in step S4, the calcination temperature is 450 - 750 °C; the calcination time is 2 - 8 h.

[0013] Further, in step S5, the concentration of the NaOH solution is 2 - 5 mol / L, the treatment temperature is 60 - 100 °C, and the treatment time is 1 - 6 h.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: 1) Through the combustion of the colloidal solution in the present invention, the addition sequence of amino acids is optimized. Using the carboxyl group and amino group in the amino acid molecule as fixed anchor points to fix metal ions and silica respectively is conducive to improving the dispersion degree of each component, solving the disadvantages such as uneven distribution and large particle size of conventional nano-oxides in the past, and enabling the catalyst to have a richer metal - support interface; 2) Compared with the microemulsion method, the preparation method of the present invention greatly simplifies the method for preparing the inverse catalyst; compared with the flame spray pyrolysis method, it avoids the dependence on large-scale equipment and facilitates the industrial application of the inverse catalyst; 3) Under the condition that the reaction temperature is 250 °C in the present invention, the prepared inverse CeO2 / Cu catalyst is used in the methanol steam reforming for hydrogen production reaction, and its activity and stability are both superior to those of the commercial CuZnAl catalyst, and its activity is nearly twice that of RK-5 under the same conditions. Description of the Drawings

[0015] Figure 1 It is a comparison chart of the catalytic performance of inverse copper - cerium catalysts with different raw material ratios; Figure 2 It is an XRD comparison chart of inverse copper - cerium catalysts with different raw material ratios. Detailed Embodiments

[0016] The present invention will be further described below in conjunction with the drawings and embodiments, but the scope protected by the present invention is not limited to the described scope. Example 1

[0017] Weigh 4.13 g of copper nitrate, 1.26 g of cerium nitrate, and 4.51 g of glycine and place them in a 250 ml beaker. Add 90 ml of deionized water, completely dissolve them, and then ultrasonicate for 20 min. Subsequently, add 8.17 g of silica sol and ultrasonicate for another 20 min. Place the above solution in an 88 °C constant temperature water bath and evaporate it to a gel state. Then, take out the sample and place it on a watch glass and put it into an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to magnetically stir at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash it with deionized water and ethanol, and put the obtained filter cake into an oven at 110 °C to dry for 8 h to obtain a reverse-phase copper-cerium catalyst. Example 2

[0018] Weigh 4.35 g of copper nitrate, 0.87 g of cerium nitrate, and 4.51 g of glycine and place them in a 250 ml beaker. Add 90 ml of deionized water, completely dissolve them, and then ultrasonicate for 20 min. Subsequently, add 8.17 g of silica sol and ultrasonicate for another 20 min. Place the above solution in an 88 °C constant temperature water bath and evaporate it to a gel state. Then, take out the sample and place it on a watch glass and put it into an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to magnetically stir at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash it with deionized water and ethanol, and put the obtained filter cake into an oven at 110 °C to dry for 8 h to obtain a reverse-phase copper-cerium catalyst. Example 3

[0019] Weigh 4.59 g of copper nitrate, 0.43 g of cerium nitrate, and 4.51 g of glycine and place them in a 250 ml beaker. Add 90 ml of deionized water, completely dissolve them, and then ultrasonicate for 20 min. Subsequently, add 8.17 g of silica sol and ultrasonicate for another 20 min. Place the above solution in an 88 °C constant temperature water bath and evaporate it to a gel state. Then, take out the sample and place it on a watch glass and put it into an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to magnetically stir at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash it with deionized water and ethanol, and put the obtained filter cake into an oven at 110 °C to dry for 8 h to obtain a reverse-phase copper-cerium catalyst. Example 4

[0020] Weigh 4.35 g of copper nitrate, 0.87 g of cerium nitrate, and 4.51 g of glycine and place them in a 250 ml beaker. Add 90 ml of deionized water, completely dissolve them, and then sonicate for 20 min. Subsequently, add 8.17 g of silica sol and sonicate for another 20 min. Place the above solution in a constant temperature water bath at 88 °C and evaporate it to a gel state. Then, take out the sample and place it on a watch glass and put it into an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 450 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to magnetically stir at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash with deionized water and ethanol, and put the obtained filter cake into an oven at 110 °C to dry for 8 h to obtain a reverse-phase copper-cerium catalyst. Example 5

[0021] Weigh 4.35 g of copper nitrate, 0.87 g of cerium nitrate, and 4.51 g of glycine and place them in a 250 ml beaker. Add 90 ml of deionized water, completely dissolve them, and then sonicate for 20 min. Subsequently, add 8.17 g of silica sol and sonicate for another 20 min. Place the above solution in a constant temperature water bath at 88 °C and evaporate it to a gel state. Then, take out the sample and place it on a watch glass and put it into an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 750 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to magnetically stir at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash with deionized water and ethanol, and put the obtained filter cake into an oven at 110 °C to dry for 8 h to obtain a reverse-phase copper-cerium catalyst. Example 6

[0022] Weigh 4.35 g of copper nitrate, 0.87 g of cerium nitrate, and 4.51 g of alanine and place them in a 250 ml beaker. Add 90 ml of deionized water, completely dissolve them, and then sonicate for 20 min. Subsequently, add 8.17 g of silica sol and sonicate for another 20 min. Place the above solution in a constant temperature water bath at 88 °C and evaporate it to a gel state. Then, take out the sample and place it on a watch glass and put it into an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to magnetically stir at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash with deionized water and ethanol, and put the obtained filter cake into an oven at 110 °C to dry for 8 h to obtain a reverse-phase copper-cerium catalyst. Example 7

[0023] Weigh 4.35 g of copper nitrate, 0.87 g of cerium nitrate, and 4.51 g of valine and place them in a 250 ml beaker. Add 90 ml of deionized water, and after complete dissolution, sonicate for 20 min; then add 8.17 g of silica sol and sonicate for another 20 min. Place the above solution in a constant temperature water bath at 88 °C and evaporate it to a gel state. Subsequently, take out the sample and place it on a watch glass, then put it in an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to stir magnetically at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash with deionized water and ethanol, and put the obtained filter cake in an oven at 110 °C to dry for 8 h to obtain the inverse copper-cerium catalyst. Example 8

[0024] Weigh 4.35 g of copper nitrate, 0.86 g of zirconium nitrate, and 4.51 g of glycine and place them in a 250 ml beaker. Add 90 ml of deionized water, and after complete dissolution, sonicate for 20 min; then add 8.17 g of silica sol and sonicate for another 20 min. Place the above solution in a constant temperature water bath at 88 °C and evaporate it to a gel state. Subsequently, take out the sample and place it on a watch glass, then put it in an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to stir magnetically at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash with deionized water and ethanol, and put the obtained filter cake in an oven at 110 °C to dry for 8 h to obtain the inverse copper-cerium catalyst. Example 9

[0025] Weigh 4.35 g of copper nitrate, 0.36 g of manganese nitrate, and 4.51 g of glycine and place them in a 250 ml beaker. Add 90 ml of deionized water, and after complete dissolution, sonicate for 20 min; then add 8.17 g of silica sol and sonicate for another 20 min. Place the above solution in a constant temperature water bath at 88 °C and evaporate it to a gel state. Subsequently, take out the sample and place it on a watch glass, then put it in an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to stir magnetically at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash with deionized water and ethanol, and put the obtained filter cake in an oven at 110 °C to dry for 8 h to obtain the inverse copper-cerium catalyst. Example 10

[0026] Weigh 4.35 g of copper nitrate, 0.65 g of lanthanum nitrate, and 4.51 g of glycine and place them in a 250 ml beaker. Add 90 ml of deionized water, and after complete dissolution, ultrasonicate for 20 min; then add 8.17 g of silica sol and ultrasonicate for another 20 min. Place the above solution in an 88 °C constant temperature water bath and evaporate it to a gel state. Then take out the sample and place it on a watch glass and put it in an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to magnetically stir at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash with deionized water and ethanol, and place the filter cake in an 110 °C oven to dry for 8 h to obtain the inverse copper-cerium catalyst.

[0027] Comparative Example 1 Weigh 1.21 g of copper nitrate, 6.51 g of cerium nitrate, and 4.51 g of glycine and place them in a 250 ml beaker. Add 90 ml of deionized water, and after complete dissolution, ultrasonicate for 20 min; then add 8.17 g of silica sol and ultrasonicate for another 20 min. Place the above solution in an 88 °C constant temperature water bath and evaporate it to a gel state. Then take out the sample and place it on a watch glass and put it in an oven. The oven is heated from room temperature to 200 °C and maintained for 4 h to completely combust the glycine, obtaining a black solid powder. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h. Subsequently, use 2 mol / L NaOH solution to magnetically stir at a constant temperature of 80 °C for 4 h to remove the silica sol template, filter and wash with deionized water and ethanol, and place the filter cake in an 110 °C oven to dry for 8 h to obtain the inverse copper-cerium catalyst.

[0028] Comparative Example 2 Weigh 4.35 g of copper nitrate and 0.87 g of cerium nitrate, add 90 ml of deionized water to a 250 ml beaker to dissolve, and co-precipitate with Na2CO3 in a 70 °C water bath, adjust the pH value to 7, and age for 2 h after co-precipitation. Filter and wash the precipitate, and then place it in an 110 °C oven to dry for 8 h. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h to obtain the catalyst.

[0029] Comparative Example 3 Weigh 4.35 g of copper nitrate, 0.87 g of cerium nitrate, and 8.41 g of oxalic acid and place them in a 250 ml beaker. Add 90 ml of deionized water, and after complete dissolution, ultrasonicate for 20 min; place the above solution in an 80 °C constant temperature water bath and evaporate it to a gel state. Then take out the sample and place it on a watch glass and put it in a 120 °C oven to dry for 24 h. Place the precursor in a muffle furnace and calcine it at a rate of 5 °C / min to 600 °C for 4 h to obtain the inverse copper-cerium catalyst.

[0030] Comparative Example 4 0.5 g of cerium nitrate, 1.5 g of copper nitrate, and 2 g of colloidal silica particles were separately dissolved in 5 ml of deionized water, heated to 150 °C, and then 400 mg of glycine was added. After the reaction ended, it was cooled and washed with deionized water multiple times to obtain a CuO-CeO2 bimetallic oxide containing a silica template. The CuO-CeO2 bimetallic oxide containing the silica template was dispersed in a 2 mol / L sodium hydroxide solution, stirred at 80 °C for 8 h, centrifuged and simply rinsed, and then the silica template was etched again with a 2 mol / L sodium hydroxide solution. After the reaction ended, it was washed with deionized water and ethanol, and dried to obtain a porous CuO-CeO2 bimetallic oxide catalyst with a pore size of 50 nm and a molar ratio of CuO to CeO2 of 84:16.

[0031] The preparation conditions and performance parameters of the copper-based catalysts in Comparative Examples 1-4 and Examples 1-10 are compared in Table 1.

[0032] Table 1 Preparation conditions and performance parameters of copper-based catalysts

[0033] By comparing Examples 1-3, it was found that the raw material ratio directly affected parameters such as the methanol conversion rate and stability of the catalyst. Appropriately increasing the content of supported copper (Example 2) was beneficial to the high dispersion of the oxide, increasing the content of the active component and the number of interface sites, and significantly improving the catalytic activity. And from Figure 2 it can be observed that the XRD diffraction peaks of cerium oxide in the catalysts prepared by the colloidal solution combustion method are very broad, proving that it is in a highly dispersed state.

[0034] By comparing Examples 2, 4, and 5, it was found that the calcination temperature affected the catalytic activity of the inverse copper-cerium catalyst. When the calcination temperature was too low, the interaction was weak and the activity was poor; when the calcination temperature was too high, the interaction was too strong, which was not conducive to the reduction of the active component and led to a decrease in catalytic activity, indicating that the catalytic activity of the catalyst was affected by the interaction between the metal and the support. Therefore, it was necessary to appropriately enhance the interaction between the metal and the support.

[0035] By comparing Comparative Example 1 and Example 1, it was found that under the same reaction conditions, the catalytic activity of the inverse copper-based catalyst was much better than that of the traditional supported copper-based catalyst, which was due to the high content of the active component in the inverse catalyst and the high dispersion of the supported phase oxide, so it had a rich metal-support interface.

[0036] By comparing Comparative Examples 2 and 3 with Example 2, it can be found that different preparation methods affect the catalytic activity of the reverse-phase copper catalyst. This is because the colloidal solution combustion method enables high dispersion and small particle size of CeO2, resulting in more CeO2 having strong interaction with Cu species. Thus, more active components can be reduced and there is a rich metal-support interface. However, for the precipitation method, since CeO2 cannot be highly dispersed, even when the content of the active component is very high, the catalyst performance is still poor.

[0037] By comparing Example 2 with Examples 8 - 10, it can be found that among many oxides (such as cerium oxide, zirconium oxide, manganese oxide, and lanthanum oxide), cerium oxide as a support has more excellent activity than zirconium oxide.

[0038] By comparing Example 1 with Comparative Example 4, it can be known that when the molar ratio of copper oxide to cerium oxide is similar, comparing the particle size of CeO2, the CuCeO catalyst prepared by the method adopted in the present invention x has a particle size (2.8 nm) superior to that of the CuO-CeO2 bimetallic oxide catalyst prepared by the novel combustion method disclosed in Comparative Example 4 (4.1 nm), which can provide more metal-support interfaces and is beneficial to improving the catalytic performance.

Claims

1. An inverse copper-based catalyst for hydrogen production by methanol steam reforming, characterized in that The catalyst has an MO x / Cu inverse structure, and the oxide MO x nanoclusters are uniformly distributed on the surface of Cu particles, where MO x is one or more of MgO, Al2O3, MnO2, TiO2, Fe2O3, ZnO, Ga2O3, La2O3, CeO2, Y2O3, and ZrO2.

2. The inverse copper catalyst for hydrogen production by methanol steam reforming according to claim 1, characterized in that The catalyst MO x / Cu, where the mass fraction of MO x oxide is 5 to 50 wt%.

3. A preparation method of a reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming according to any one of claims 1-2, characterized in that It includes the following steps: S1: Weigh a certain amount of copper metal salt, M metal salt and amino acid, pour them into water and mix and dissolve to obtain solution A; S2: Add silica sol to solution A obtained in step S1 to obtain sol B; S3: Heat and evaporate sol B obtained in step S2 to a viscous state, put it into an oven to initiate combustion to obtain solid C; S4: Calcinate solid C obtained in step S3 in a muffle furnace to obtain solid D; S5: Treat solid D in step S4 with NaOH solution to remove silicon dioxide, then wash with deionized water, filter by suction and dry to obtain a reverse-phase copper-based catalyst.

4. The preparation method of a reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming according to claim 3, characterized in that In step S1, the copper metal salt is one or more of nitrates, chlorides, and sulfates, and the precursor metal salt of MO x is one or more of nitrates, chlorides, and sulfates; the amino acid is one or more of glycine, alanine, and valine; the molar ratio of the sum of the amino acid and the metal salt is 1 to 6:

1.

5. The preparation method of an inverse copper-based catalyst for methanol steam reforming to produce hydrogen according to claim 3, characterized in that In step S2, the size of the silicon dioxide nanoparticles in the silica sol is 10 - 50 nm, and the molar ratio of silicon dioxide to metal salt is 1 - 4:

1.

6. The preparation method of a reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming according to claim 3, characterized in that In step S3, the drying temperature of the oven is 160 - 240 °C.

7. The preparation method of a reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming according to claim 3, characterized in that In step S4, the calcination temperature is 450 - 750 °C; the calcination time is 2 - 8 h.

8. The preparation method of a reverse-phase copper-based catalyst for hydrogen production by methanol steam reforming according to claim 3, characterized in that In step S5, the concentration of the NaOH solution is 2 - 5 mol / L, the treatment temperature is 60 - 100 °C, and the treatment time is 1 - 6 h.

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