CN113457657A - Carbon-based methanol hydrogen production catalyst and preparation method and application thereof - Google Patents

Carbon-based methanol hydrogen production catalyst and preparation method and application thereof Download PDF

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CN113457657A
CN113457657A CN202110733267.1A CN202110733267A CN113457657A CN 113457657 A CN113457657 A CN 113457657A CN 202110733267 A CN202110733267 A CN 202110733267A CN 113457657 A CN113457657 A CN 113457657A
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methanol
biomass
catalyst
carbon
porous carbon
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潘立卫
李金晓
张晶
钟和香
韩新宇
易丹阳
赵艾琳
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Dalian University
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Dalian University
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Priority to PCT/CN2022/093471 priority patent/WO2023273670A1/en
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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Abstract

The invention provides a carbon-based methanol hydrogen production catalyst, and a preparation method and application thereof, and belongs to the field of catalytic materials. The method provided by the invention is beneficial to enabling all components to react uniformly and form a stable structure in the subsequent roasting process through aging, and synchronously reducing the metal oxide into the active component metal simple substance by utilizing the reducibility of the biomass-based porous carbon in the roasting process, so that the finally prepared catalyst can be directly used for preparing hydrogen from methanol, and the method omits the step of preparing the catalyst by agingUsing H in practice2The reduction step reduces the cost of the methanol hydrogen production, simplifies the methanol hydrogen production process, and simultaneously has the porous carbon material with high specific surface area as a carrier, thereby improving the loading capacity and dispersion degree of active component metals and further improving the activity of the catalyst. According to the method provided by the application, the catalyst prepared from the biomass waste can be directly used for preparing hydrogen from methanol, the link of hydrogen reduction is omitted, the conversion rate of methanol is 80%, and the selectivity of CO is 23%.

Description

Carbon-based methanol hydrogen production catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalytic materials, in particular to a carbon-based methanol hydrogen production catalyst, and a preparation method and application thereof.
Background
The hydrogen energy has the advantages of more heat released by combustion, no environmental pollution of combustion products, no limit on prepared raw materials, renewability and the like, can be directly combusted, and is incomparable with traditional energy sources such as coal, petroleum, natural gas and the like. The methanol has the characteristics of high H/C ratio, large energy density, high energy conversion efficiency, wide sources, easy transportation, supplement, storage and the like, and the technical problems of overhigh hydrogen storage and transportation cost, lack of infrastructure and the like can be solved by utilizing the methanol to produce hydrogen on site.
The methanol steam reforming process generally needs to use a catalyst to ensure that the reaction is carried out stably and efficiently. The active components of the currently used methanol hydrogen production catalyst are mainly metals, and active metal salt, an auxiliary agent and Al are required to be firstly prepared2O3、SiO2、MgO、CaO、TiO2And some composite metal oxides, etc. to convert the active metal salt into metal oxide through roasting, and before use, hydrogen is also introduced to reduce the metal oxide into metal. Therefore, in practical application, besides laying hydrogen production raw material pipelines, pipeline design of hydrogen reduction needs to be considered, the cost and process complexity of methanol hydrogen production are greatly increased, and how to simplify the preparation process of the methanol hydrogen production catalyst becomes a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a carbon-based methanol hydrogen production catalyst, a preparation method and application thereof, and the preparation method provided by the invention omits the step of hydrogen reduction in the actual application process, reduces the cost of methanol hydrogen production, and simplifies the methanol hydrogen production process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a carbon-based methanol hydrogen production catalyst, which comprises the following steps:
(1) mixing a metal precursor, an auxiliary agent, biomass-based porous carbon and deionized water, and then sequentially aging and drying to obtain an intermediate;
(2) and (2) roasting the intermediate obtained in the step (1) to obtain the carbon-based methanol hydrogen production catalyst.
Preferably, the ratio of the amounts of the metal precursor, the auxiliary agent and the biomass-based porous carbon is (0.01-0.4): (0-0.4): 1.
Preferably, the metal element in the metal precursor includes at least one of Pd, Pt, Cu, Ni, Co, Fe, and Se.
Preferably, the preparation method of the biomass-based porous carbon comprises the following steps:
1) pretreating the biomass material to obtain a pretreated biomass material;
2) sequentially carrying out carbonization, first acid washing, first water washing, activation, second acid washing, second water washing and drying on the pretreated biomass material obtained in the step 1) to obtain the biomass-based porous carbon material.
Preferably, the carbonization in the step 2) is carried out in an inert gas atmosphere, the carbonization temperature is 300-800 ℃, and the carbonization time is 60-180 min.
Preferably, the activating in step 2) comprises: the first water-washed product is impregnated with an activating agent and then heated.
Preferably, the aging time in the step (1) is 6-18 h.
Preferably, the roasting in the step (2) is carried out in an inert gas atmosphere, the roasting temperature is 650-900 ℃, and the roasting time is 1-6 h.
The invention also provides the carbon-based methanol hydrogen production catalyst prepared by the preparation method in the technical scheme, which comprises porous carbon and active component metal loaded on the surface of the porous carbon.
The invention also provides the application of the carbon-based methanol hydrogen production catalyst in the technical scheme in methanol hydrogen production.
The invention provides a preparation method of a carbon-based methanol hydrogen production catalyst, which takes a metal precursor, an auxiliary agent and biomass-based porous carbon as raw materials, is favorable for enabling all components to react uniformly and form a stable structure in the subsequent roasting process through aging, and synchronously reduces metal oxides into active component metal simple substances by utilizing the reducibility of the biomass-based porous carbon in the roasting process, so that the finally prepared catalyst can be directly used for methanol hydrogen production, and the use of H in the practical application process is omitted2The reduction link reduces the cost of the methanol hydrogen production, simplifies the methanol hydrogen production process, and simultaneously has a high specific surface area porous carbon material as a carrier, so that the loading capacity and the dispersity of active component metals are improved, the activity of the catalyst is improved, the activity, the selectivity and the stability of active metals of the main catalyst are improved by the aid of the auxiliary agent, and finally the high-activity carbon-based methanol hydrogen production catalyst which can be directly used for the methanol hydrogen production is obtained. The results of the embodiments show that the method provided by the application, which utilizes biomass waste to prepare the carbon-based methanol hydrogen production catalyst, effectively realizes the recycling of biomass resources, reduces the preparation cost, and the obtained carbon-based methanol hydrogen production catalyst can be directly used for methanol hydrogen production, omits the link of hydrogen reduction, reduces the cost of methanol hydrogen production, and simplifies the methanol hydrogen production process, and the methanol conversion rate can reach 80%, and the selectivity of CO is 23%.
The preparation method of the carbon-based methanol hydrogen production catalyst provided by the invention is simple to operate, mild in reaction conditions and suitable for large-scale production.
Drawings
FIG. 1 is a FTIR plot of a biomass-based porous carbon support prepared in example 1 of the present invention;
fig. 2 is an XRD chart of the carbon-based catalyst for methanol hydrogen production prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a carbon-based methanol hydrogen production catalyst, which comprises the following steps:
(1) mixing a metal precursor, an auxiliary agent, biomass-based porous carbon and deionized water, and then sequentially aging and drying to obtain an intermediate;
(2) and (2) roasting the intermediate obtained in the step (1) to obtain the carbon-based methanol hydrogen production catalyst.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
In the present invention, the operation is carried out at room temperature unless otherwise specified.
The method comprises the steps of mixing a metal precursor, an auxiliary agent, biomass-based porous carbon and water, and then aging and drying the mixture in sequence to obtain the precursor.
In the invention, the ratio of the amounts of the metal precursor, the auxiliary agent and the biomass-based porous carbon is preferably (0.01-0.4): 0-0.4): 1. According to the invention, the ratio of the amounts of the metal precursor, the auxiliary agent and the biomass-based porous carbon is controlled within the above range, so that the metal precursor is completely reduced to active component metal elements by the biomass-based porous carbon in the subsequent roasting process, and higher loading capacity and dispersity of the active component metal are maintained.
In the present invention, the metal element in the metal precursor preferably includes at least one of Pd, Pt, Cu, Ni, Co, Fe, and Se. In the present invention, the metal precursor is preferably at least one of a nitrate, a carbonate, a sulfate, and a hydrochloride of the active metal element. In the present invention, when the active metal element is Pt, the metal precursor is preferably H14Cl6O6And (3) Pt. In an embodiment of the present invention, the metal precursor may be specifically Cu (NO)3)2And Co (NO)3)2、Ni(NO3)2Or H14Cl6O6Pt。
In the invention, the auxiliary agent is preferably ZnO or CeO2、ZrO2、Ga2O3、MoC、La2O3、MnO2、MgAl2O4、SiO2Zeolite, In2O3、MgO、Ta2O3、HfO2At least one of (1). In the present invention, the CeO2Preferably Ce (NO)3)2The form of the porous carbon is firstly loaded on carrier biomass-based porous carbon and is formed in the subsequent roasting process. In the invention, the auxiliary agent can effectively improve the activity, selectivity and stability of the active component metal of the main catalyst.
In the present invention, the method for preparing the biomass-based porous carbon preferably comprises the steps of:
1) pretreating the biomass material to obtain a pretreated biomass material;
2) sequentially carrying out carbonization, first acid washing, first water washing, activation, second acid washing, second water washing and drying on the pretreated biomass material obtained in the step 1) to obtain the biomass-based porous carbon material.
The invention preferably pretreats the biomass material to obtain a pretreated biomass material. In the present invention, the biomass material is preferably wood chips, fruit shells or seaweeds. In an embodiment of the invention, the biomass material may be specifically gulfweed or xanthoceras sorbifolia shells.
In the present invention, the pretreatment preferably comprises washing, drying and pulverizing the biomass material in sequence to obtain a pretreated biomass material. The invention has no special limitation on the washing mode, and the biomass material can be washed clean. The present invention is not particularly limited in the manner of drying, and may remove moisture. The present invention is not particularly limited in the manner of pulverization, and the biomass material may be pulverized into a powder.
After the pretreated biomass material is obtained, the invention preferably sequentially carries out carbonization, first acid washing, first water washing, first drying, activation, second acid washing, second water washing and second drying on the pretreated biomass material to obtain the biomass-based porous carbon material.
In the present invention, the carbonization is preferably performed in an inert gas atmosphere; the carbonization temperature is preferably 300-800 ℃, and more preferably 400-600 ℃; the carbonization time is preferably 60-180 min, and more preferably 90-120 min. In the present invention, the device for carbonizing is preferably a tube furnace. In the invention, in the carbonization process, moisture and volatile matters in the pretreated biomass material are promoted to be gasified and separated out, so that fixed carbon with certain initial pores is obtained, and a framework with certain structural strength is formed, which is beneficial to activating and pore-forming on the framework in the subsequent activation process, thereby obtaining the porous carbon material with high specific surface area.
In the present invention, the acid used for the first acid washing and the second acid washing is independently preferably at least one of an aqueous solution of sulfuric acid, hydrochloric acid, nitric acid, or hydrofluoric acid; the concentration of the acid is preferably 1 to 60 wt%, and more preferably 8 to 40 wt%. In the present invention, the time for the first acid washing and the second acid washing is preferably 5 to 50min, and more preferably 10 to 30 min. In the present invention, the temperature of the first acid washing and the second acid washing is preferably 20 to 99 ℃ independently, and more preferably 70 to 90 ℃. In the invention, the first acid washing can wash away ash in the carbonized sample, so that initial pores formed in the carbonization process can be exposed, the activator can penetrate into pore canals to perform pore-forming in the subsequent activation process, and the second acid washing can remove impurities generated in the activation process.
In the invention, the temperature of the first water washing and the second water washing is preferably 20-99 ℃ independently, and more preferably 70-90 ℃. The first washing and the second washing are not particularly limited, and the washing is carried out until the washing liquid is neutral.
In the present invention, the activation preferably includes: the first water-washed product is impregnated with an activating agent and then heated. In the present invention, the mass ratio of the product of the first washing to the activator is preferably 1 (1E to E)5) More preferably 1 (2-4). In the invention, the activating agent is preferably KOH, NaOH or K2CO3、H3PO4、ZnCl2、FeCl3、Fe(NO)3And K2FeO4One or more of (a). In an embodiment of the invention, the activator may be in particular KOH or K2FeO4. In the present invention, the activation is preferably performed in an inert gas atmosphere. In the invention, the activation temperature is preferably 700-900 ℃, and more preferably 750-850 ℃; the activation time is preferably 60-140 min, and more preferably 90-120 min. In the activation process, the activating agent reacts with the first washing product to carry out etching pore-forming.
In the present invention, the first drying and the second drying are preferably performed in a forced air drying oven; the temperature of the first drying and the second drying is preferably 90-120 ℃. The drying time is not particularly limited, and the moisture can be removed.
The biomass-based porous carbon material prepared by the method provided by the invention adopts biomass waste as a raw material, so that the recycling of biomass resources is effectively realized, the preparation cost is reduced, and the specific surface area of the biomass-based porous carbon material prepared by the BET method is 500-3500 m2The method can provide more active sites, and the pore size distribution and the porosity can be adjusted within a certain range by controlling the temperature and time of carbonization, the time of acid washing and the temperature and time of activity.
After the biomass-based porous carbon material is obtained, the metal precursor, the auxiliary agent, the biomass-based porous carbon and deionized water are mixed, and then are aged and dried in sequence to obtain an intermediate.
The operation of mixing the metal precursor, the auxiliary agent, the biomass-based porous carbon and the deionized water is not particularly limited, and the components can be fully mixed.
The invention has no special limit on the dosage of the deionized water, and can fully immerse all the components.
According to the invention, the metal precursor, the auxiliary agent, the biomass-based porous carbon and the deionized water are preferably mixed and then subjected to ultrasonic treatment. In the invention, the time of the ultrasonic treatment is preferably 5-30 min, and more preferably 10-15 min.
In the invention, the aging time is preferably 6-18 h, and more preferably 10-14 h. In the invention, the aging is beneficial to enabling all components to react uniformly and form a stable structure in the subsequent roasting process. In the invention, the drying mode is preferably drying in a forced air drying oven; the drying temperature is preferably 90-120 ℃, and more preferably 100-110 ℃. The drying time is not particularly limited, and the moisture can be removed.
After the intermediate is obtained, the intermediate is roasted to obtain the carbon-based methanol hydrogen production catalyst
In the present invention, the calcination is preferably performed in an inert gas atmosphere. In the invention, the roasting temperature is preferably 650-900 ℃, and more preferably 700-850 ℃; the roasting time is preferably 1-6 hours, and more preferably 2-4 hours. According to the invention, the roasting temperature and time are controlled within the above ranges, so that the components can uniformly react and form a stable structure, the biomass-based porous carbon is further carbonized to form more microcrystals containing a large amount of unsaturated bonds, the activity of the finally prepared catalyst is improved, and the biomass-based porous carbon with reducibility is promoted to directly reduce the metal precursor into the active component metal simple substance under the condition of high-temperature inert atmosphere.
The invention preferably cools the calcined product naturally to room temperature.
The preparation method of the carbon-based methanol hydrogen production catalyst provided by the invention is simple to operate, mild in reaction conditions and suitable for large-scale production.
The invention also provides a carbon-based methanol hydrogen production catalyst prepared by the preparation method in the technical scheme, which comprises porous carbon and active component metal loaded on the surface of the porous carbon. The carbon-based methanol hydrogen production catalyst prepared by the method can be directly used for methanol hydrogen production, and the use of H in the practical application process is omitted2The reduction step reduces the cost of the methanol hydrogen production, simplifies the methanol hydrogen production process, and simultaneously has the porous carbon material with high specific surface area as a carrier, thereby improving the loading capacity and dispersion degree of active component metals and further improving the activity of the catalyst.
The invention also provides the application of the carbon-based methanol hydrogen production catalyst in the technical scheme in methanol hydrogen production.
In the present invention, the application of the catalyst in the production of hydrogen from methanol preferably comprises the following steps:
under the condition that the catalyst prepared by the preparation method in the technical scheme exists, methanol water solution is added and then heated, and hydrogen is obtained through reduction reaction.
In the invention, the molar ratio of methanol to water in the methanol aqueous solution is preferably 1 (0.5-5), and more preferably 1: 3.
In the invention, the heating temperature is preferably 250-300 ℃, and more preferably 270-290 ℃.
The apparatus for the reduction reaction is not particularly limited in the present invention, and a reactor known to those skilled in the art may be used.
In the invention, the liquid inlet space velocity of the methanol aqueous solution is preferably 2000-4000 h-More preferably 2500 to 3500h-. The present invention preferably employs a gas chromatograph to analyze the composition of the hydrogen product.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1. The preparation method of the biomass-based porous carbon comprises the following steps:
1) 17.2596g of shinyleaf yellowhorn shells are sequentially washed, dried and dried for 24h at 105 ℃ and crushed to obtain 15.2453g of pretreated shinyleaf yellowhorn shells;
2) placing 15.2453g of pretreated xanthoceras sorbifolia shells obtained in the step 1) in a tubular furnace in a nitrogen atmosphere for carbonization at 600 ℃ for 2h to obtain 4.6902g of carbonized products, then adding 10 wt% of hydrochloric acid, placing the carbonized products in a water bath kettle at 80 ℃ for magnetic stirring for carrying out first acid washing for 30min, then carrying out first water washing with deionized water until the carbonized products are neutral, then carrying out first drying in a forced air drying oven at 105 ℃, mixing 4.6083g of solids obtained after drying with 18.4302g of activating agent KOH in a mass ratio of 1:4, placing the mixture in an atmosphere muffle furnace in a nitrogen atmosphere for activation at 800 ℃ for 120min, then adding 10ml of hydrochloric acid with a mass concentration of 36% -38% in a water bath kettle at 80 ℃ for carrying out second acid washing for 30min, then carrying out second water washing with deionized water until the activated solids are neutral, drying to obtain 2.8146g of biomass-based porous carbon materials, analyzing the specific surface area of the materials by using a BET method, and analyzing the pore volume and pore diameter of the materials by using a BJH method, the specific surface area of the prepared biomass-based porous carbon material is measured to be 2456m2·g-1The pore volume is 1.358cm3·g-1The average pore diameter was 2.213 nm.
Fig. 1 is an FTIR chart of the biomass porous carbon prepared in example 1, and it can be seen from fig. 1 that the surface of the biomass-based porous carbon support prepared in example 1 has abundant functional groups.
2. Preparation of carbon-based catalyst for preparing hydrogen from methanol
(1) 0.2489gCu (NO)3)2·3H2O and 0.2813gCo (NO)3)2·6H2O, 0.6035g of biomass-based porous carbon prepared by the preparation method is mixed with 150ml of deionized water, ultrasonic treatment is carried out for 15min, then the mixture is aged for 12h at room temperature, and drying is carried out in a forced air drying oven at 105 ℃ to obtain 0.9086g of precursor; wherein the metal precursor comprises Cu (NO)3)2And Co (NO)3)2) And the amount of biomass-based porous carbon in a molar ratio of 0.1:0.1: 1;
(2) and (2) roasting the precursor obtained in the step (1) for 3h at 800 ℃ in a nitrogen atmosphere, and naturally cooling to room temperature to obtain 0.8476g of the carbon-based methanol hydrogen production catalyst.
Fig. 2 is an XRD chart of the carbon-based catalyst for methanol hydrogen production prepared in example 1 of the present invention, from fig. 2, distinct Cu and Co peaks can be seen, which illustrates that the active components Cu and Co in the catalyst prepared in example 1 are successfully supported on the porous carbon support.
Application example 1
The catalyst prepared from example 1 was applied to the production of methanol:
0.2g of the catalyst prepared in example 1 is placed in the middle of a reaction tube, the temperature is raised to 280 ℃, a methanol aqueous solution with the molar ratio of 1:3 is pumped into a raw material sample inlet by a feed pump, the feed liquid flow rate is 0.037ml/min, and the feed liquid space velocity is controlled to 3000h-1After stable sample introduction, a gas sample is collected at a reaction gas outlet, the composition of a product is analyzed by adopting a gas chromatograph, after reaction for 30-300 min, the methanol conversion rate of the carbon-based methanol hydrogen production catalyst can reach 80%, the selectivity of CO is 60%, and specific results are shown in Table 1.
Example 2
According to the method of the embodiment 1, the biomass-based porous carbon material and the carbon-based methanol hydrogen production catalyst are prepared, and the prepared carbon-based methanol hydrogen production catalyst is applied to the methanol hydrogen production by adopting the same method.
Wherein, in the process of preparing the biomass-based porous carbon material, 20.4986g of gulfweed is adopted as the biomass material, the carbonization temperature is 500 ℃, the acid used in the first acid washing and the second acid washing is hydrochloric acid with the mass concentration of 36-38%, and the activating agent is 19.9761gH3PO4The mass ratio of 13.3259g of solid obtained after the first drying to 19.9761g of activating agent is 1: 1.5; and the specific surface area of the prepared biomass-based porous carbon material was 460m measured by the same method as in example 12·g-1Pore volume of 0.421cm3·g-1The average pore diameter is 3.663 nm;
0.1539gNi (NO) is adopted in the process of preparing the carbon-based catalyst for preparing hydrogen from methanol3)2·6H2O、0.2317gCe(NO3)2·6H20.4233g of biomass-based porous carbon prepared by the preparation method and 150ml of deionized water, wherein the mass ratio of the metal precursor, the auxiliary agent and the biomass-based porous carbon is 0.125:0.125: 1; the roasting temperature is 700 ℃.
Application example 2
According to the method of application example 1, the catalyst prepared in example 2 is applied to the hydrogen production from methanol, a gas chromatograph is adopted to analyze the composition of the product, the methanol conversion rate and the CO selectivity of the carbon-based catalyst for hydrogen production from methanol are calculated after the reaction is carried out for 30-300 min, and the specific results are shown in Table 1.
Example 3
According to the method of the embodiment 1, the biomass-based porous carbon material and the carbon-based methanol hydrogen production catalyst are prepared, and the prepared carbon-based methanol hydrogen production catalyst is applied to the methanol hydrogen production by adopting the same method.
Wherein, in the process of preparing the biomass-based porous carbon material, 20.0596g of gulfweed is adopted as the biomass material, the carbonization temperature is 550 ℃, the acid used in the first acid washing and the second acid washing is hydrochloric acid with the mass concentration of 36-38%, and the activating agent is 75.3684gK2FeO4The mass ratio of the solid obtained after the first drying to the activating agent is 1: 5; and the specific surface area of the prepared biomass-based porous carbon material was 531m measured by the same method as in example 12·g-1Pore volume of 0.593cm3·g-1The average pore diameter is 4.470 nm;
0.1021gH is adopted in the process of preparing the catalyst for preparing the hydrogen from the carbon-based methanol14Cl6O6Pt, 0.5062g of biomass-based porous carbon prepared by the preparation method and 100ml of deionized water, wherein the mass ratio of the metal precursor to the biomass-based porous carbon is 0.2: 1; the temperature of the calcination is 650 ℃.
Application example 3
The catalyst prepared in the example 3 is applied to the hydrogen production from methanol according to the method of the application example 1, the composition of the product is analyzed by using a gas chromatograph, the methanol conversion rate and the CO selectivity of the carbon-based catalyst for hydrogen production from methanol are calculated after the reaction is carried out for 30-300 min, and the specific results are shown in Table 1.
TABLE 1 Performance of catalysts prepared in examples 1-3
Application example Methanol conversion (%) Selectivity for CO (%)
1 80 60
2 66 40
3 77 23
As can be seen from the examples and table 1, the method provided by the present invention omits the step of hydrogen reduction in the actual application process, reduces the cost of methanol hydrogen production, simplifies the methanol hydrogen production process, and uses the porous carbon material with high specific surface area as the carrier, improves the loading amount and dispersion degree of the active component metals, has high catalytic activity, and when the prepared carbon-based methanol hydrogen production catalyst is applied to methanol hydrogen production, the methanol conversion rate can still reach 80%, and the selectivity of CO is 23%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a carbon-based methanol hydrogen production catalyst comprises the following steps:
(1) mixing a metal precursor, an auxiliary agent, biomass-based porous carbon and deionized water, and then sequentially aging and drying to obtain an intermediate;
(2) and (2) roasting the intermediate obtained in the step (1) to obtain the carbon-based methanol hydrogen production catalyst.
2. The preparation method according to claim 1, wherein the ratio of the amounts of the metal precursor, the auxiliary agent and the biomass-based porous carbon in the step (1) is (0.01-0.4): (0-0.4): 1.
3. The production method according to claim 1, wherein the metal element in the metal precursor in the step (1) includes at least one of Pd, Pt, Cu, Ni, Co, Fe, and Se.
4. The preparation method according to claim 1, wherein the preparation method of the biomass-based porous carbon in the step (1) comprises the following steps:
1) pretreating the biomass material to obtain a pretreated biomass material;
2) sequentially carrying out carbonization, first acid washing, first water washing, activation, second acid washing, second water washing and drying on the pretreated biomass material obtained in the step 1) to obtain the biomass-based porous carbon material.
5. The preparation method according to claim 4, wherein the carbonization in the step 2) is performed in an inert gas atmosphere, the carbonization temperature is 300-800 ℃, and the carbonization time is 60-180 min.
6. The method according to claim 4, wherein the activating in step 2) includes: the first water-washed product is impregnated with an activating agent and then heated.
7. The preparation method according to claim 1, wherein the aging time in the step (1) is 6-18 h.
8. The preparation method according to claim 1, wherein the roasting in the step (2) is carried out in an inert gas atmosphere, the roasting temperature is 650-900 ℃, and the roasting time is 1-6 h.
9. The catalyst for preparing hydrogen from carbon-based methanol, which is prepared by the preparation method of any one of claims 1 to 8, comprises porous carbon and active component metal loaded on the surface of the porous carbon.
10. Use of the carbon-based methanol to hydrogen catalyst of claim 9 in the production of hydrogen from methanol.
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