Ethanol steam reforming hydrogen production catalyst and preparation method and application thereof

Abstract

The invention relates to the field of ethanol reforming catalysts, and discloses an ethanol steam reforming hydrogen production catalyst and a preparation method and application thereof. The catalyst comprises an active metal element Ni and a carrier CeO2, and based on the metal element, Ni accounts for 10-20wt% of the mass of the catalyst. The catalyst provided by the invention has the advantages of carbon deposition resistance, sintering resistance, high temperature resistance and good activity, selectivity and stability. The preparation method of the catalyst provided by the invention has the advantages of convenience in operation, low synthesis temperature, safety and economy.

Description

Technical Field

[0001] This invention relates to the field of ethanol reforming catalysts, specifically to an ethanol steam reforming hydrogen production catalyst, its preparation method, and its application. Background Technology

[0002] Bioethanol is one of the world's most widely used renewable energy sources, playing a vital role in ensuring food security, addressing energy crises, and protecting the environment. Bioethanol can also be used in ethanol steam reforming (ESR) to produce hydrogen, which not only releases hydrogen from hydrocarbon fuels but also activates hydrogen in water, obtaining hydrogen energy that can replace fossil fuels. This achieves both renewable and sustainable development goals and creates a closed CO2 loop (without generating new CO2), thus achieving environmentally friendly objectives.

[0003] Ethanol vapor reforming for hydrogen production (C2H5OH+3H2O→2CO2+6H2) is a very complex process involving many parallel reactions, such as water-gas shift reaction (CO+H2O→CO2+H2), dehydration reaction (C2H5OH→C2H4+H2O), decomposition reaction (C2H5OH→CH4+CO+H2), carbon formation reaction (2CO→C+CO2, CH4→C+2H2, C2H4→Coke), and carbon removal reaction (C+H2O→CO+H2). Therefore, developing highly selective ESR catalysts is crucial.

[0004] Researchers have extensively studied various catalytic systems, and many Pt, Ru, Co, or Ni-based catalysts have been developed for efficient ESR reactions. Compared to expensive noble metals, low-cost nickel-based catalysts exhibit higher C / C and CH bond breaking activity and are considered promising candidate catalysts. However, the main challenge facing nickel-based catalysts is the poor hydrogen selectivity and stability caused by severe carbon deposition and metal particle sintering. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of severe carbon deposition and metal particle sintering, as well as poor hydrogen selectivity and stability, in existing nickel-based catalysts for ethanol steam reforming to hydrogen production. This invention provides an ethanol steam reforming hydrogen production catalyst, its preparation method, and its applications. The catalyst exhibits advantages such as resistance to carbon deposition and sintering, high temperature resistance, and good activity, selectivity, and stability. The preparation method of the catalyst is convenient, has a low synthesis temperature, is safe, and is economical.

[0006] According to a first aspect of the present invention, the present invention provides a catalyst for hydrogen production by ethanol steam reforming, the catalyst comprising: an active metal element Ni and a support CeO2, wherein, based on the metal element, Ni accounts for 10-20 wt% of the catalyst by mass fraction.

[0007] According to a second aspect of the present invention, the present invention provides a method for preparing the catalyst of the present invention, the method comprising: (1) adding citric acid to an aqueous solution of nickel salt, cerium salt, or optionally lanthanum salt, and heating to obtain a sol; (2) drying, grinding, and calcining the sol to obtain the catalyst.

[0008] According to a third aspect of the present invention, the present invention provides a catalyst prepared by the preparation method described herein.

[0009] According to a fourth aspect of the present invention, the present invention provides the application of the catalyst described herein in the production of hydrogen from ethanol steam reforming.

[0010] The catalyst provided by this invention has the advantages of being resistant to carbon deposition, sintering, and high temperature, as well as exhibiting good activity, selectivity, and stability. The catalyst preparation method provided by this invention has the advantages of being convenient to operate, having a low synthesis temperature, being safe, and being economical. Attached Figure Description

[0011] Figure 1 This refers to the generation rate of the gaseous products in Examples 1-3;

[0012] Figure 2 The ethanol conversion rate and the rate of gaseous product generation are those of Examples 1, 4-7. Detailed Implementation

[0013] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the invention. The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0014] This invention provides a catalyst for hydrogen production via ethanol steam reforming. The catalyst comprises: an active metal element Ni and a support CeO2, wherein Ni accounts for 10-20 wt% of the catalyst by mass fraction (based on metal element content). The formula for calculating the mass fraction of Ni in the catalyst is: (mass of Ni / total mass of metal elements in the catalyst) × 100%, where the mass of each element is based on the amount fed into the catalyst. The catalyst possessing the aforementioned technical characteristics exhibits resistance to carbon deposition, sintering, and high temperature resistance, and demonstrates good activity, selectivity, and stability.

[0015] According to a preferred embodiment of the present invention, the catalyst further includes the metal auxiliary element La.

[0016] In this invention, the content of La in the catalyst can be selected from a wide range, as illustrated below, but this does not limit the scope of the invention. According to a preferred embodiment of the invention, the molar percentage of La, n... La / n (La+Ce) It is 0.1-0.3.

[0017] In this invention, the form in which the metal promoter element La is provided in the catalyst is not particularly limited; any suitable form can be selected as long as it achieves the purpose of this invention. According to a preferred embodiment of this invention, the metal promoter element La is provided in the catalyst in the form of La₂O₃.

[0018] Catalysts with the aforementioned technical features exhibit better activity and selectivity.

[0019] This invention provides a method for preparing the catalyst described herein, comprising: (1) adding citric acid to an aqueous solution of nickel salt, cerium salt, or optionally lanthanum salt, and heating to obtain a sol; (2) drying, grinding, and calcining the sol to obtain the catalyst. The catalyst preparation method with the aforementioned technical features has the advantages of convenient operation, low synthesis temperature, safety, and economy.

[0020] In the preparation method provided by this invention, the type of nickel salt is not particularly limited; any suitable type can be selected as long as it can achieve the purpose of this invention. According to a preferred embodiment of this invention, the nickel salt is selected from one or more of nitrates, hydrated nitrates, chlorides, and hydrated chlorides, preferably from nitrates and / or hydrated nitrates.

[0021] In the preparation method provided by this invention, there is no particular limitation on the type of cerium salt; any suitable type can be selected as long as it achieves the purpose of this invention. According to a preferred embodiment of this invention, the cerium salt is selected from nitrates and / or hydrated nitrates.

[0022] In the preparation method provided by this invention, the type of lanthanum salt is not particularly limited; any suitable type can be selected as long as it achieves the purpose of this invention. According to a preferred embodiment of this invention, the lanthanum salt is selected from one or more of nitrates, hydrated nitrates, chlorides, and hydrated chlorides, preferably from nitrates and / or hydrated nitrates.

[0023] In the preparation method provided by this invention, the amount of citric acid added in step (1) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the ratio of the molar amount of citric acid to the sum of the molar amounts of nickel, cerium, and lanthanum is 1.5-2.5:1, for example, it can be 1.7:1, 1.9:1, 2.1:1, or 2.3:1.

[0024] In the preparation method provided by the present invention, the heating temperature in step (1) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the heating temperature is 50-70°C, for example, it can be 53°C, 56°C, 59°C, 62°C, 65°C, or 68°C.

[0025] In the preparation method provided by this invention, the heating time in step (1) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the heating time is 8-16 hours, for example, 10 hours, 12 hours, or 14 hours.

[0026] According to a preferred embodiment of the present invention, in the preparation method provided by the present invention, in step (1), heating is performed dynamically in order to ensure uniform mixing and heating of the materials.

[0027] According to a preferred embodiment of the present invention, in the preparation method provided by the present invention, step (1) is carried out in the presence of ethanolamine.

[0028] In the preparation method provided by this invention, the type of ethanolamine is not particularly limited; any suitable type can be selected as long as it achieves the purpose of this invention. According to a preferred embodiment of this invention, the ethanolamine is selected from one or more of monoethanolamine, diethanolamine, and triethanolamine.

[0029] In the preparation method provided by this invention, the amount of ethanolamine added in step (1) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the molar ratio of the hydroxyl group in ethanolamine to citric acid is 0.3-0.7:1.

[0030] In the preparation method provided by this invention, the drying temperature in step (2) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the drying temperature is 80-120°C.

[0031] In the preparation method provided by the present invention, the heating rate of calcination in step (2) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the heating rate of calcination is 3-7℃ / min, for example, it can be 4℃ / min, 5℃ / min, or 6℃ / min.

[0032] In the preparation method provided by the present invention, the calcination temperature in step (2) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the calcination temperature is 500-700℃, for example, it can be 530℃, 560℃, 590℃, 620℃, 650℃, or 680℃.

[0033] In the preparation method provided by this invention, the calcination time in step (2) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the calcination time is 3-5 hours.

[0034] This invention provides a catalyst prepared by the method described herein.

[0035] This invention provides the application of the catalyst described herein in hydrogen production from ethanol steam reforming.

[0036] In the applications provided by this invention, there is no particular limitation on the type of reactor for ethanol vapor reforming to produce hydrogen; any suitable type can be selected as long as it achieves the purpose of this invention. According to a preferred embodiment of this invention, the reactor for ethanol vapor reforming to produce hydrogen is a fixed-bed reactor.

[0037] In the applications provided by this invention, the inner diameter of the quartz reaction tube in the fixed-bed reactor can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of the invention, the inner diameter of the quartz reaction tube in the fixed-bed reactor is 5-7 mm.

[0038] In the applications provided by this invention, the gas hourly space velocity (GHSV) for hydrogen production via ethanol vapor reforming has a wide selectable range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of the invention, the GHSV is 15000-17000 mL·g. -1 ·h -1 .

[0039] In the applications provided by this invention, the molar ratio of water to ethanol for hydrogen production via ethanol vapor reforming can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of the invention, the molar ratio of water to ethanol is 3-5:1.

[0040] In the applications provided by this invention, the temperature range for hydrogen production via ethanol vapor reforming is relatively wide. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the temperature for hydrogen production via ethanol vapor reforming is 550-700°C, for example, 580°C, 610°C, 640°C, or 670°C.

[0041] In the applications provided by this invention, a wide range of pressures can be selected for ethanol vapor reforming to produce hydrogen. The following examples illustrate this, but do not limit the scope of the invention. According to a preferred embodiment of the invention, the pressure for ethanol vapor reforming to produce hydrogen is atmospheric pressure.

[0042] According to a preferred embodiment of the present invention, before hydrogen production by ethanol vapor reforming, the reactor loaded with the catalyst is subjected to a reduction treatment.

[0043] According to a preferred embodiment of the present invention, hydrogen gas is introduced into the reactor during the reduction process.

[0044] In the application provided by the present invention, the flow rate of hydrogen gas introduced into the reactor during the reduction process can be selected from a wide range. The following is an illustrative example, but it does not limit the scope of the present invention. For example, the flow rate of hydrogen gas introduced into the reactor is 40-60 mL / min.

[0045] In the applications provided by this invention, the temperature range for the reduction treatment is relatively wide. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the temperature for the reduction treatment is 550-700°C, for example, 530°C, 560°C, 590°C, 620°C, 650°C, or 680°C.

[0046] In the applications provided by this invention, the reduction process time has a wide selectable range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the reduction process time is 0.5-3 hours.

[0047] The present invention will be described in detail below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0048] For any experimental steps or conditions not specified in the examples and comparative examples, the procedures or conditions described in the literature in this field can be followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0049] In the examples and comparative examples,

[0050] The composition of the gaseous products was analyzed using Agilent chromatography.

[0051] The remaining reaction liquid was analyzed and detected using Shimadzu chromatography.

[0052] The anti-carbon deposition performance was analyzed and tested using a thermogravimetric analyzer: The catalyst used for hydrogen production from ethanol steam reforming was taken as the test sample, and the time for the catalyst to be used for hydrogen production from ethanol steam reforming was recorded as the reaction time t. In the anti-carbon deposition performance tests of the examples and comparative examples, t was 5 h. Under the condition of flowing nitrogen gas, the test sample was heated to 105 °C at a rate of 5 °C / min and held at this temperature until the moisture was removed. The mass of the catalyst after moisture removal was recorded as the initial mass m0. Then, the temperature was increased from 105 °C to 1000 °C at a rate of 5 °C / min and held at this temperature until the catalyst mass stabilized. The mass of the stabilized catalyst was recorded as the calcined mass m1. The carbon deposition rate is calculated as (m1-m0) / (t×m0). The smaller the carbon deposition rate, the better the anti-carbon deposition performance.

[0053] In the examples and comparative examples, Table 1 shows the reaction temperature, ethanol conversion rate, and gas phase product yield of ethanol vapor reforming for hydrogen production in the examples.

[0054] Example 1

[0055] Catalyst preparation:

[0056] (1) Dissolve 0.9909g Ni(NO3)2·6H2O and 5.5782g Ce(NO3)3·6H2O evenly in 20mL of water, then add 6.2455g citric acid. After the citric acid is completely dissolved, stir at 60℃ for 12h on a magnetic stirrer heater and heat to evaporate to obtain a sol.

[0057] (2) The sol was dried in an oven at 100°C to obtain a sponge-like solid. This solid was then ground into powder and calcined in a muffle furnace at 600°C for 4 hours at a heating rate of 5°C / min to obtain the catalyst. In the obtained catalyst, Ni accounted for 10 wt% of the catalyst by metal element.

[0058] Ethanol vapor reforming for hydrogen production:

[0059] 0.1 g of catalyst was loaded into a fixed-bed reactor at atmospheric pressure. The quartz reaction tube in the reactor had an inner diameter of 6 mm. The reactor was subjected to reduction treatment for 1 h at a hydrogen flow rate of 50 mL / min and a temperature of 600 °C. Afterwards, an ethanol vapor reforming reaction to produce hydrogen was carried out under the following conditions: GHSV of 16000 mL·g -1 ·h -1 The molar ratio of water to ethanol was 4:1, and the temperature was 600℃. After cooling in a cold trap, the reaction products yielded gaseous products (H2, CO2, CH4, CO, C2H4) and the remaining liquid (CH3CH2OH, H2O). The formation rate of the gaseous products was as follows: Figure 1 As shown, the ethanol conversion rate and the rate of gaseous product generation are as follows: Figure 2As shown in Table 1, the ethanol conversion rate and H2 yield are as follows. After 5 hours of reaction, the carbon deposition rate of the catalyst was tested, and the carbon deposition rate was 4.02 mg C / gcat·h.

[0060] Example 2

[0061] The method of Example 1 was followed, except that the amount of Ni(NO3)2·6H2O added was 1.4864 g, the amount of Ce(NO3)3·6H2O added was 5.2683 g, and the amount of citric acid added was 6.6260 g. In the obtained catalyst, Ni accounted for 15 wt% of the catalyst by metal element, and the generation rate of gaseous products was as follows... Figure 1 As shown in Table 1, the ethanol conversion rate and H2 yield are as follows. After 5 hours of reaction, the carbon deposition rate of the catalyst was tested, and the carbon deposition rate was 3.78 mg C / g cat·h.

[0062] Example 3

[0063] The method of Example 1 was followed, except that the amount of Ni(NO3)2·6H2O added was 1.9818 g, the amount of Ce(NO3)3·6H2O added was 4.9584 g, and the amount of citric acid added was 7.0065 g. In the obtained catalyst, Ni accounted for 20 wt% of the catalyst by metal element, and the generation rate of gaseous products was as follows... Figure 1 As shown in Table 1, the ethanol conversion rate and H2 yield are as follows. After 5 hours of reaction, the carbon deposition rate of the catalyst was tested, and the carbon deposition rate was 3.94 mg C / g cat·h.

[0064] Example 4

[0065] The method is the same as in Example 1, except that the reaction temperature for hydrogen production by ethanol vapor reforming is 500°C, and the ethanol conversion rate and the rate of gaseous product generation are as follows: Figure 2 As shown in Table 1, the ethanol conversion rate and H2 yield are as follows.

[0066] Example 5

[0067] The method is the same as in Example 1, except that the reaction temperature for hydrogen production by ethanol vapor reforming is 550°C, and the ethanol conversion rate and the rate of gaseous product generation are as follows: Figure 2 As shown in Table 1, the ethanol conversion rate and H2 yield are as follows.

[0068] Example 6

[0069] The method is the same as in Example 1, except that the reaction temperature for ethanol vapor reforming to produce hydrogen is 650°C, and the ethanol conversion rate and the rate of gaseous product generation are as follows: Figure 2 As shown in Table 1, the ethanol conversion rate and H2 yield are as follows.

[0070] Example 7

[0071] The method is the same as in Example 1, except that the reaction temperature for hydrogen production by ethanol vapor reforming is 700°C, and the ethanol conversion rate and the rate of gaseous product generation are as follows: Figure 2 As shown in Table 1, the ethanol conversion rate and H2 yield are as follows.

[0072] Example 8

[0073] Following the method of Example 1, except that the amount of Ce(NO3)3·6H2O added was 4.4703 g, the amount of La(NO3)3·6H2O added was 1.1145 g, and the amount of citric acid added was 6.2541 g. In the obtained catalyst, based on metal elements, Ni accounted for 10 wt% of the catalyst mass, and La accounted for 0.2 mol% of the support molar fraction. The ethanol conversion rate and H2 yield are shown in Table 1. After 5 h of reaction, the carbon deposition rate of the catalyst was tested, and the carbon deposition rate was 3.88 mg C / g cat·h.

[0074] Example 9

[0075] The method was followed in Example 1, except that 9.3948 g of citric acid was added. The ethanol conversion and H2 yield are shown in Table 1. After 5 hours of reaction, the carbon deposition rate of the catalyst was tested, and it was 5.34 mg C / g cat·h.

[0076] Example 10

[0077] The method was followed as in Example 8, except that in step (1), 0.5974 g of monoethanolamine was added after citric acid. The ethanol conversion rate and H2 yield are shown in Table 1. After 5 h of reaction, the carbon deposition rate of the catalyst was tested, and the carbon deposition rate was 3.81 mgC / g cat·h.

[0078] Example 11

[0079] The method was followed as in Example 8, except that in step (1), after adding citric acid, 0.5974 g of monoethanolamine and 0.3427 g of diethanolamine were added. The ethanol conversion rate and H2 yield are shown in Table 1. After reacting for 5 h, the carbon deposition rate of the catalyst was tested, and the carbon deposition rate was 3.84 mg C / g cat·h.

[0080] Example 12

[0081] The method was the same as in Example 1, except that the reduction temperature in the ethanol vapor reforming for hydrogen production was 800°C. The ethanol conversion rate and H2 yield are shown in Table 1.

[0082] Comparative Example 1

[0083] A catalyst with the same composition as in Example 1 was prepared using an equal-volume impregnation and loading method. Ethanol steam reforming for hydrogen production was performed according to the method in Example 1. The ethanol conversion and H2 yield are shown in Table 1. After 5 h of reaction, the coking rate of the catalyst was tested, and the coking rate was 123.66 mg C / g cat·h.

[0084] Comparative Example 2

[0085] A catalyst with the same composition as in Example 1 was prepared using an equal-volume impregnation and loading method. Ethanol steam reforming for hydrogen production was carried out according to the method in Example 1, except that the reaction temperature was 650°C. The ethanol conversion and H2 yield are shown in Table 1.

[0086] Comparative Example 3

[0087] A catalyst with the same composition as in Example 1 was prepared using an equal-volume impregnation and loading method. Ethanol steam reforming for hydrogen production was carried out according to the method in Example 1, except that the reaction temperature was 700°C. The ethanol conversion and H2 yield are shown in Table 1.

[0088] Table 1. Reaction temperature, ethanol conversion rate, and H2 yield of ethanol steam reforming for hydrogen production in the examples and comparative examples.

[0089]

[0090]

[0091] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various specific technical features in any suitable manner. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. However, these simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A catalyst for hydrogen production via ethanol vapor reforming, characterized in that, The catalyst comprises: active metal element Ni and support CeO2, wherein, based on metal elements, Ni accounts for 10-20 wt% of the catalyst by mass.

2. The catalyst according to claim 1, wherein, The catalyst also includes the metallic auxiliary element La, with the molar percentage of La being n. La / n (La+Ce) It is 0.1-0.

3.

3. A method for preparing the catalyst according to claim 1 or 2, characterized in that, The method includes: (1) Add citric acid to an aqueous solution of nickel salt, cerium salt, or optionally lanthanum salt, and heat to obtain a sol; (2) The sol is dried, ground and calcined to obtain the catalyst.

4. The preparation method according to claim 3, wherein, Nickel salts are selected from one or more of nitrates, hydrated nitrates, chlorides, and hydrated chlorides, preferably from nitrates and / or hydrated nitrates; and / or Cerium salts are selected from nitrates and / or hydrated nitrates; and / or The lanthanum salt is selected from one or more of nitrates, hydrated nitrates, chlorides, and hydrated chlorides, preferably from nitrates and / or hydrated nitrates.

5. The preparation method according to claim 3 or 4, wherein, In step (1), The ratio of the molar mass of citric acid to the sum of the molar masses of nickel, cerium, and lanthanum is 1.5-2.5:1; and / or The heating conditions include: The temperature is 50-70℃; and / or The time is 8-16 hours; and / or It is carried out under dynamic conditions.

6. The preparation method according to any one of claims 3-5, wherein, Step (1) is carried out in the presence of ethanolamine, wherein, Ethanolamine is selected from one or more of monoethanolamine, diethanolamine, and triethanolamine; and / or The molar ratio of the hydroxyl group in ethanolamine to citric acid is 0.3-0.7:

1.

7. The preparation method according to any one of claims 3-6, wherein, In step (2), Drying conditions include: The drying temperature is 80-120℃; and / or Dry the sol until it becomes a spongy solid; and / or The conditions for roasting include: The heating rate is 3-7℃ / min; and / or Temperature of 500-700℃; and / or The time is 3-5 hours.

8. The catalyst prepared by the method according to any one of claims 3-7.

9. The use of the catalyst according to any one of claims 1-2 and 8 in ethanol steam reforming for hydrogen production. Preferably, the conditions for hydrogen production by ethanol vapor reforming include: The gas hourly space velocity (GHSV) is 15000-17000 mL·g -1 ·h -1 ; and / or The molar ratio of water to ethanol is 3-5:1; and / or Temperatures of 550-700℃; and / or The pressure is normal pressure.

10. The application according to claim 9, wherein, Before hydrogen production via ethanol vapor reforming, the reactor loaded with the catalyst undergoes a reduction treatment. The reduction treatment conditions include: Introduce hydrogen gas; and / or Temperatures of 550-700℃; and / or The time is 0.5-3 hours.

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