Catalyst for hydrogen production by low-temperature methanol steam reforming of copper foam and preparation method thereof

Abstract

The application discloses a foamed copper low-temperature methanol water vapor reforming hydrogen catalyst and a preparation method thereof, and belongs to the technical field.The technical scheme is as follows: including pretreatment, chemical plating reaction, impregnation, pre-copper plating, copper electroplating, calcination, hydrothermal reaction and high-temperature treatment.The foamed copper catalyst prepared by the application has the advantages of more uniform dispersion of active components, higher porosity and better stability;Al does not need to be added, and the active component is the carrier;and the preparation process is simple, convenient to operate, low in cost and obvious in industrial application value.

Description

Technical Field

[0001] This invention relates to the field of catalyst material preparation technology, specifically to a foamed copper low-temperature methanol steam reforming hydrogen production catalyst and its preparation method. Background Technology

[0002] Hydrogen, as a highly efficient and environmentally friendly secondary energy source, has become an important way to solve sustainable development issues related to society, economy, and environment. Methanol, due to its low price, ease of storage, and simple conversion equipment, has become the preferred hydrogen storage carrier.

[0003] Currently, most traditional methanol steam reforming catalysts for hydrogen production are copper-based catalysts. These catalysts suffer from a series of problems, such as low activity at low temperatures. Therefore, it is of great significance to develop a low-temperature, high-efficiency copper-based methanol reforming catalyst for hydrogen production. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a foamed copper low-temperature methanol steam reforming hydrogen production catalyst and its preparation method. The foamed copper is prepared, which makes full use of the high dispersion and high porosity of the foamed copper to improve the dispersion of Cu active centers, increase the number of active centers, and at the same time has high stability.

[0005] The technical solution of this invention is as follows:

[0006] In the first aspect, a method for preparing a foamed copper low-temperature methanol steam reforming hydrogen production catalyst is disclosed, comprising the following steps:

[0007] (1) Pretreatment of polyurethane foam substrate;

[0008] (2) The pretreated polyurethane sponge substrate is placed in a copper-containing chemical plating solution for chemical plating reaction.

[0009] (3) The chemically plated polyurethane sponge substrate is immersed in ammonium bicarbonate solution at room temperature and then dried in an oven.

[0010] (4) Immerse the dried polyurethane sponge substrate in the electroplating solution, pre-plat copper first, then electroplat copper, and then clean and dry to obtain a polyester sponge substrate foam copper with copper plating.

[0011] (5) Place the polyester sponge base copper foam into a muffle furnace and bake it.

[0012] (6) Dissolve citric acid in deionized water to form a citric acid solution. Under stirring conditions, add zinc nitrate aqueous solution to the citric acid solution. Citric acid and zinc nitrate undergo a complexation reaction to form reaction solution one.

[0013] (7) The reaction solution and the polyester sponge-based copper foam were placed in a high-pressure reactor for hydrothermal reaction. After the reaction, the mixture was naturally cooled to room temperature, aged, and then dried in an oven to obtain the zinc-loaded copper foam catalyst.

[0014] (8) The zinc-loaded copper foam catalyst is placed in a tube furnace and subjected to high-temperature treatment under a nitrogen atmosphere to obtain the zinc-loaded copper foam catalyst.

[0015] Preferably, the pretreatment in step (1) refers to the sequential processing of chemical degreasing, deionized water washing, potassium permanganate roughening, deionized water washing, oxalic acid reduction, deionized water washing, sensitization, colloidal palladium activation, and degumming, wherein the polyurethane sponge substrate has an area of ​​(2-5) × (2-5) cm. 2 It has a thickness of 2-3 mm and a porosity of over 90%.

[0016] Preferably, the copper-containing electroless plating solution in step (2) is an electroless plating solution containing 10 g / L CuSO4 (copper sulfate), 24 g / L Na3Cyt (sodium citrate), 3 g / L NiSO4 (nickel sulfate), 30 g / L H3BO3 (boric acid), 10 g / L NaOH (sodium hydroxide), and 30 g / L NaH2PO2 (sodium hypophosphite); the electroless plating reaction refers to the reaction in the above-mentioned copper-containing electroless plating solution at 50-80°C for 0.5-2 hours.

[0017] Preferably, in step (3), the concentration of the ammonium bicarbonate solution is 180-220 g / L, the immersion time is 30-60 min, and the drying refers to drying in a vacuum drying oven at 30-40°C for 1-2 h.

[0018] Preferably, the electroplating solution in step (4) contains 70 g / L CuSO4·5H2O (copper sulfate pentahydrate), 0.60 g / L NaCl (sodium chloride), 0.03 g / L polyethylene glycol, and C 12 H 25 An electroplating solution containing 0.05 g / L sodium dodecyl sulfate (SO4Na) and 25 mL / L sulfuric acid (H2SO4).

[0019] Preferably, the pre-plating in step (4) refers to electrodeposition in the above-mentioned electroplating solution at a voltage of 5V for 3-5 minutes, and the electroplating of copper refers to the plating of copper after pre-plating at an apparent current density of 0.3A / cm². 2 Under a steady current, electrodeposition is performed in the above-mentioned electroplating solution for 20-30 minutes. The drying refers to drying at 80°C in a vacuum drying oven for 22-24 hours, and the thickness of the copper plating layer is 60-110 μm.

[0020] Preferably, the roasting temperature in step (5) is 100-150°C and the time is 2-4 hours. In step (6), a constant temperature magnetic stirrer is used for stirring, and the stirring temperature is 40-80°C.

[0021] Preferably, in step (7), the hydrothermal reaction temperature is 110-130°C, the reaction time is 8-12 hours, and the aging time is 2-4 hours.

[0022] Preferably, the high-temperature treatment in step (8) refers to raising the temperature of the tube furnace from room temperature to 300-400°C under nitrogen atmosphere protection, with a heating rate of 1-3°C / min, and maintaining it for 4-8 hours.

[0023] Secondly, a foamed copper low-temperature methanol steam reforming catalyst for hydrogen production is disclosed.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] 1. This invention first prepares a foamed copper catalyst, fully utilizing its high dispersion and porosity to improve the dispersion of Cu active centers, increase the number of active centers, and thus enhance the low-temperature activity of the catalyst while maintaining high stability. Zinc, with its excellent electron transfer ability, allows for better zinc particle deposition on the porous foamed copper surface, achieving a synergistic effect between the two. This further enhances the low-temperature reaction performance of the catalyst, reduces CO production, and effectively prevents the sintering of active centers in the catalyst. 2. The composition, structure, and amount of support in the polyurethane sponge-based foamed copper catalyst prepared by this invention can be freely controlled. 3. Compared with catalysts prepared by co-precipitation, the polyurethane sponge-based foamed copper catalyst prepared by this invention exhibits more uniform dispersion of active components, higher porosity, and better stability; no Al addition is required, as the active components themselves serve as the support; and its preparation process is simple, convenient, and low-cost, possessing significant industrial application value. Detailed Implementation

[0026] Example 1

[0027] This embodiment provides a foamed copper low-temperature methanol steam reforming catalyst for hydrogen production, and the specific preparation method is as follows:

[0028] (1) Pretreatment: The area is 3×3cm 2A 2.5mm thick polyurethane sponge (weighing 65mg) was pretreated by sequentially undergoing chemical degreasing, deionized water washing, potassium permanganate roughening, deionized water washing, oxalic acid reduction, deionized water washing, sensitization, colloidal palladium activation, and degumming treatment to obtain a polyurethane sponge substrate suitable for chemical plating (Chen Wenge, Zhang Qiang. Characteristics, applications, preparation and development of foam metal [J]. Powder Metallurgy Industry, 2005(02):37-42.DOI:10.13228 / j.boyuan.issn1006-6543.2005.02.009.).

[0029] (2) After pretreatment, the polyurethane sponge is chemically plated with copper (CuSO4:10g / L, Na3Cyt:24g / L, NiSO4:3g / L, H3BO3:30g / L, NaOH:10g / L, NaH2PO2:30g / L, 45℃, 1.5h) to coat the surface of the polyurethane sponge substrate with copper foam.

[0030] (3) The chemically plated polyurethane sponge was immersed in ammonium bicarbonate solution (NH4HCO3: 200g / L) for 40 minutes at room temperature, and then dried (vacuum drying oven, 30℃, 1.5h).

[0031] (4) After drying, immerse in the plating solution (CuSO4·5H2O: 70g / L, NaCl: 0.60g / L, polyethylene glycol: 0.03g / L, C 12 H 25 Pre-plating copper was carried out in SO4Na: 0.05g / L, H2SO4 25mL / L (cathode material: foamed copper, anode material: pure metal copper plate, voltage: 5V, room temperature, 3min);

[0032] Electroplated copper (cathode material: foamed copper, anode material: pure metallic copper plate, apparent current density: 0.3 A / cm²) 2 The mixture was heated at room temperature for 20 minutes, then washed (with deionized water) and dried (in a vacuum drying oven at 80°C for 6 hours) to obtain copper foam with a polyester sponge substrate.

[0033] (5) The obtained copper foam was placed in a muffle furnace and calcined (120℃, 3h). The total mass was 105mg, of which the copper foam coating was 60-110μm thick and weighed 40mg, accounting for 62% of the mass of the polyester sponge substrate.

[0034] (6) Prepare 20 mL of 5.3 g / L citric acid solution and heat it at 60°C on a constant temperature magnetic stirrer. Then, pour 20 mL of 5.2 g / L zinc nitrate aqueous solution into the above solution under certain temperature and magnetic stirring conditions to fully complex the citric acid and zinc nitrate, forming a total of 40 mL solution (the molar ratio of Zn to citric acid is 1:1). Transfer this solution together with the above-mentioned copper foam to a stainless steel autoclave lined with polytetrafluoroethylene and react at 120°C for 10 h. After the reaction is completed, allow it to cool naturally to room temperature, age for 3 h, and then dry it in a vacuum drying oven at 80°C for 6 h.

[0035] The zinc-supported copper foam catalyst was placed in a tube furnace and heated to 350°C at a rate of 10°C / min under a nitrogen atmosphere. The temperature was maintained for 1 hour, and then increased to 550°C at a rate of 10°C / min. The temperature was maintained for 3 hours to obtain the zinc-supported copper foam catalyst CAT-1, with the zinc oxide mass percentage being 30% of the finished catalyst.

[0036] Example 2

[0037] Unlike Example 1, in step (6), 20 mL of 8.3 g / L citric acid solution and 20 mL of 8.1 g / L zinc nitrate solution (the molar ratio of Zn to citric acid is 1:1) were added to finally obtain zinc-supported copper foam catalyst CAT-2, with the zinc oxide mass percentage being 40% of the finished catalyst.

[0038] Example 3

[0039] Unlike Example 1, in step (6), 20 mL of 12.4 g / L citric acid solution and 20 mL of 12.2 g / L zinc nitrate solution (the molar ratio of Zn to citric acid is 1:1) were added to finally obtain zinc-supported copper foam catalyst CAT-3, with the zinc oxide mass percentage being 50% of the finished catalyst.

[0040] Example 4

[0041] Unlike Example 1, in step (6), 20 mL of 2.65 g / L citric acid solution and 20 mL of 5.2 g / L zinc nitrate solution (the molar ratio of Zn to citric acid is 2:1) are added to finally obtain zinc-supported copper foam catalyst CAT-4, with the zinc oxide mass percentage being 30% of the finished catalyst.

[0042] Example 5

[0043] Unlike Example 1, in step (6), 20 mL of 4.15 g / L citric acid solution and 20 mL of 8.1 g / L zinc nitrate solution (the molar ratio of Zn to citric acid is 2:1) are added to finally obtain zinc-supported copper foam catalyst CAT-5, with the zinc oxide mass percentage being 40% of the finished catalyst.

[0044] Example 6

[0045] Unlike Example 1, in step (6), 20 mL of 5.53 g / L citric acid solution and 20 mL of 8.1 g / L zinc nitrate solution were added (the molar ratio of Zn to citric acid was 1.5:1), and finally zinc-supported copper foam catalyst CAT-6 was obtained, with the zinc oxide mass percentage being 40% of the finished catalyst.

[0046] Comparative Example 1

[0047] Unlike Example 1, the substrate used in step (1) has an area of ​​3×3cm. 2 A 2.5mm thick commercial 1060 pure aluminum plate (weighing approximately 6g) was used instead of polyurethane foam. Ultimately, a zinc-supported copper foam catalyst, D-CAT-1, was obtained.

[0048] Comparative Example 2

[0049] Unlike Example 1, the substrate used in step (1) has an area of ​​1×1cm. 2 A 2.5 mm thick polyurethane foam (weighing approximately 7.5 mg) was used. Ultimately, a zinc-supported copper foam catalyst, D-CAT-2, was obtained.

[0050] Comparative Example 3

[0051] Unlike Example 1, this example does not include step (3) "immersing the chemically plated polyurethane sponge in ammonium bicarbonate solution (NH4HCO3: 200g / L) at room temperature for 40 minutes, and then drying it (vacuum drying oven, 30℃, 1.5h)", nor does it include step (5) "calcining the obtained copper foam in a muffle furnace (120℃, 3h)". Finally, zinc-supported copper foam catalyst D-CAT-3 is obtained.

[0052] Comparative Example 4

[0053] Unlike Example 1, this method does not include the step (6) of "heating and stirring 20 mL of 5.3 g / L citric acid solution at 60°C on a constant temperature magnetic stirrer, and then pouring 20 mL of 5.2 g / L zinc nitrate aqueous solution into the above solution under certain temperature and magnetic stirring conditions, so that citric acid and zinc nitrate can fully complex and form a total of 40 mL solution (the molar ratio of Zn to citric acid is 1:1)". Instead, 40 mL of zinc nitrate solution (Zn(NO3)2:50 g / L) and the above-mentioned copper foam are directly transferred to a stainless steel autoclave lined with polytetrafluoroethylene, and the reaction is carried out at 120°C for 10 h. After the reaction is completed, the mixture is naturally cooled to room temperature, aged for 3 h, and dried in a vacuum drying oven at 80°C for 6 h to obtain zinc-supported copper foam catalyst D-CAT-4.

[0054] Comparative Example 5

[0055] Unlike Example 1, step (5) is not included, which involves "calcining the obtained copper foam in a muffle furnace (120°C, 3h). Weighing the samples yields a total mass of 105mg, of which the copper foam coating is 60-110μm thick and weighs 40mg, accounting for 62% of the mass of the polyester sponge substrate." This yields zinc-loaded copper foam catalyst D-CAT-5.

[0056] Comparative Example 6

[0057] Unlike Example (1), in step (6), the reaction was naturally cooled to room temperature, aged for 3 hours, and naturally dried without using a vacuum drying oven to obtain zinc-supported copper foam catalyst D-CAT-6.

[0058] Comparative Example 7

[0059] Unlike Example (1), step (3) "immerses the chemically plated polyurethane sponge in ammonium bicarbonate solution (NH4HCO3: 200g / L) at room temperature for 40 minutes, and then dries it (vacuum drying oven, 30℃, 1.5h)", which is placed after copper electroplating in step (4) to obtain zinc-loaded copper foam catalyst D-CAT-7.

[0060] Comparative Example 8

[0061] An industrial methanol-to-hydrogen catalyst based on the CuZnAl system was used, denoted as D-CAT-8.

[0062] Example 7

[0063] Example 7 is an example of evaluating the catalyst activity using the foamed copper catalysts prepared in Examples 1-6 and Comparative Examples 1-8. The specific method is as follows:

[0064] Catalyst performance was tested in a self-made 304 stainless steel fixed-bed reactor. The catalyst loading was 1.0 g, with 2.0 g of quartz sand added above and below. Leakage was checked using N2 after loading. During testing, N2 was continuously introduced into the reactor at a rate of 40 mL / min. The total flow rate of the product gas was calculated by analyzing the volume fraction of N2 in the outlet gas. The system pressure was maintained at 0.3 MPa using a back pressure valve. The reactor was heated to 210 °C at a rate of 5 °C / min and then held at that temperature. A pre-prepared methanol-water solution with a ratio of n(H2O):n(CH3OH) = 1:1 was used as the reaction feedstock and pumped into the reactor using a metering pump. The WHSV was 3.0 g-feed / (g-cat·h) (i.e., 3.0 g of feedstock was processed per gram of catalyst per hour). The reaction products were analyzed online using gas chromatography. The conversion rate of methane and the selectivity of CO were calculated using the following formulas. The specific results are shown in Table 1.

[0065] Methane conversion rate (X):

[0066]

[0067] CO selectivity (S) CO ):

[0068]

[0069] In the formula: F R The total flow rate of the product gas under standard conditions (mL / min) is calibrated using N2; F is the methanol solution feed rate (mL / min); ρ is the density of the methanol solution (g / mL); ω is the molar ratio of water to alcohol. The volume fraction (%) of the gas.

[0070] The specific surface area of ​​the copper foam catalysts prepared in Examples 1-6 and Comparative Examples 1-8 should be determined. The specific method is as follows: N2 adsorption characterization: First, 100 mg of sample was degassed at 200 °C for 6 h, followed by adsorption-desorption experiments in liquid nitrogen at -196 °C. Data was automatically recorded by computer. When the relative pressure was between 0.05 and 0.30, the BET (specific surface area) was calculated using the adsorption data, as shown in Table 1.

[0071] The dispersion of active sites in the foamed copper catalysts prepared in Examples 1-6 and Comparative Examples 1-8 was determined using the following method: For H2-TPD, 30 mg of catalyst was first placed in a quartz tube and heated to 400 °C in an H2 atmosphere. Reduction was carried out at 400 °C for 6 hours. After reduction, the temperature was lowered to room temperature. The H2 atmosphere was then switched to Ar gas, and the tube was purged for 30 minutes. Subsequently, the temperature was increased to 800 °C at a rate of 10 °C / min in an Ar atmosphere. The exhaust gas was detected using a TCD. The dispersion of copper species was calculated using the following formula: Dispersity (%) = Surface copper atomic mass / Total copper atoms × 100, as shown in Table 1.

[0072] catalyst <![CDATA[BET(m 2 / g)]]> Dispersion (%) Methanol conversion rate (%) CO selective Example 1 CAT-1 268 20 95.23 1.22 Example 2 CAT-2 279 26 98.27 0.95 Example 3 CAT-3 248 23 96.55 1.39 Example 4 CAT-4 256 19 95.01 1.34 Example 5 CAT-5 261 22 96.78 1.54 Example 6 CAT-6 236 21 97.02 1.33 Comparative Example 1 D-CAT-1 1.21 0.33 15.44 1.72 Comparative Example 2 D-CAT-2 29.78 16 72.35 3.97 Comparative Example 3 D-CAT-3 143 9 68.85 5.88 Comparative Example 4 D-CAT-4 176 11 71.38 4.24 Comparative Example 5 D-CAT-5 151 8 66.59 5.73 Comparative Example 6 D-CAT-6 221 18 84.63 2.89 Comparative Example 7 D-CAT-7 149 9 67.56 5.81 Comparative Example 8 D-CAT-8 172 12 76.36 4.85

[0073] Analysis of the data in the table above shows that using polyurethane sponge as a substrate and removing it by calcination in subsequent operations plays a crucial role in pore formation and providing specific surface area for this catalyst. The catalyst prepared using this method possesses a large specific surface area and dispersion, exhibiting a methanol conversion rate far exceeding that of existing CuZnAl-based industrial catalysts and catalysts using other substrates. Furthermore, it exhibits low CO generation and excellent performance. Using polyurethane sponge as a substrate, impregnating the catalyst with ammonium bicarbonate solution after copper electroplating, and then calcining the catalyst after chemical copper plating to decompose the ammonium bicarbonate for pore formation, can also significantly increase catalytic performance. The specific surface area of ​​the catalyst is increased, thereby improving the conversion rate and reducing the amount of CO generated. In the hydrothermal reaction step, the molar ratio of Zn to citric acid is 1:1, and the zinc oxide content in the resulting catalyst is 40%, resulting in the highest catalyst activity and the best performance in all aspects. Excessive zinc loading will reduce the dispersion of the active components of the catalyst, thus affecting the conversion rate and selectivity. Citric acid plays a good binder role in the zinc loading step of the hydrothermal reaction, which is beneficial to the loading of zinc and thus improves the catalyst performance. Whether vacuum drying is used after the hydrothermal reaction has little impact on the overall performance of the catalyst.

[0074] This invention first prepares a foamed copper catalyst, fully utilizing its high dispersion and porosity to enhance the dispersion of Cu active centers, increase the number of active centers, and thus improve the low-temperature activity of the catalyst while maintaining high stability. Zinc, with its excellent electron transfer ability, allows for better zinc particle deposition on the porous foamed copper surface, achieving a synergistic effect between the two. This further enhances the low-temperature reaction performance of the catalyst, reduces CO production, and effectively prevents the sintering of active centers. The composition, structure, and amount of support in the polyurethane sponge-based foamed copper catalyst prepared by this invention can be freely controlled. Compared with catalysts prepared by co-precipitation, the polyurethane sponge-based foamed copper catalyst prepared by this invention exhibits more uniform dispersion of active components, higher porosity, and better stability; no Al addition is required, as the active component itself serves as the support; and its preparation process is simple, convenient, and low-cost, demonstrating significant industrial application value.

[0075] Although the present invention has been described in detail with reference to preferred embodiments, it is not limited thereto. Various equivalent modifications or substitutions can be made to the embodiments of the present invention by those skilled in the art without departing from the spirit and essence of the invention, and such modifications or substitutions should all be within the scope of the present invention. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should also be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a foamed copper low-temperature methanol steam reforming hydrogen production catalyst, characterized in that, Includes the following steps: (1) Pretreatment of polyurethane foam substrate; (2) The pretreated polyurethane sponge substrate is placed in a copper-containing chemical plating solution for chemical plating reaction. (3) The chemically plated polyurethane sponge substrate is immersed in ammonium bicarbonate solution at room temperature and then dried in an oven. (4) Immerse the dried polyurethane sponge substrate in the electroplating solution, pre-plat copper first, then electroplat copper, and then clean and dry to obtain a polyester sponge substrate foam copper with copper plating. (5) Place the polyester sponge base copper foam into a muffle furnace and bake it. (6) Dissolve citric acid in deionized water to form a citric acid solution. Under stirring conditions, add zinc nitrate aqueous solution to the citric acid solution. Citric acid and zinc nitrate undergo a complexation reaction to form reaction solution one. (7) The reaction solution and the polyester sponge-based copper foam were placed in a high-pressure reactor for hydrothermal reaction. After the reaction, the mixture was naturally cooled to room temperature, aged, and then dried in an oven to obtain the zinc-loaded copper foam catalyst. (8) The zinc-supported copper foam catalyst was placed in a tube furnace and subjected to high-temperature treatment under a nitrogen atmosphere to obtain a copper foam low-temperature methanol steam reforming hydrogen production catalyst. The copper-containing electroless plating solution in step (2) is an electroless plating solution containing 10 g / L CuSO4, 24 g / L sodium citrate, 3 g / L NiSO4, 30 g / L H3BO3, 10 g / L NaOH and 30 g / L NaH2PO2; the electroless plating reaction refers to the reaction in the above-mentioned copper-containing electroless plating solution at 50-80°C for 0.5-2 hours; In step (3), the concentration of the ammonium bicarbonate solution is 180–220 g / L, and the immersion time is 30 minutes. 60 min, the drying refers to drying in a vacuum drying oven at 30-40℃ for 1-2 hours; In step (4), the electroplating solution contains 70 g / L CuSO4·5H2O, 0.60 g / L NaCl, 0.03 g / L polyethylene glycol, and C. 12 H 25 An electroplating solution containing 0.05 g / L SO4Na and 25 mL / L H2SO4.

2. The preparation method of the foamed copper low-temperature methanol steam reforming hydrogen production catalyst as described in claim 1, characterized in that: The pretreatment mentioned in step (1) refers to the sequential chemical degreasing, deionized water washing, potassium permanganate roughening, deionized water washing, oxalic acid reduction, deionized water washing, sensitization, colloidal palladium activation, and degumming treatment; the area of ​​the polyurethane sponge substrate is (2-5) × (2-5) cm. 2 It has a thickness of 2-3 mm and a porosity of over 90%.

3. The preparation method of the foamed copper low-temperature methanol steam reforming hydrogen production catalyst as described in claim 1, characterized in that: The pre-plating mentioned in step (4) refers to electrodeposition in the above-mentioned electroplating solution at a voltage of 5V for 3-5 minutes. The electroplating of copper refers to the process after pre-plating, where the apparent current density is 0.3A / cm². 2 Under a steady current, electrodeposition is performed in the above-mentioned electroplating solution for 20-30 minutes. The drying refers to drying at 80°C in a vacuum drying oven for 22-24 hours, and the thickness of the copper plating layer is 60-110 μm.

4. The preparation method of the foamed copper low-temperature methanol steam reforming hydrogen production catalyst as described in claim 1, characterized in that: In step (5), the roasting temperature is 100-150℃ and the time is 2-4h. In step (6), a constant temperature magnetic stirrer is used for stirring, and the stirring temperature is 40-80℃.

5. The preparation method of the foamed copper low-temperature methanol steam reforming hydrogen production catalyst as described in claim 1, characterized in that: In step (7), the hydrothermal reaction temperature is 110-130℃, the reaction time is 8-12h, and the aging time is 2-4h.

6. The preparation method of the foamed copper low-temperature methanol steam reforming hydrogen production catalyst as described in claim 1, characterized in that: In step (8), the high-temperature treatment refers to raising the temperature of the tube furnace from room temperature to 300-400°C under nitrogen atmosphere protection, with a heating rate of 1-3°C / min, and maintaining it for 4-8 hours.

7. Using as claimed in claim 1 6. A foamed copper low-temperature methanol steam reforming hydrogen production catalyst prepared by any one of the preparation methods described in the present invention.