1. A method for preparing hydrogen-rich synthesis gas by low-temperature degradation of polyolefin waste plastics is characterized by comprising the following steps:

(1) weighing 1 part by weight of polyolefin plastic and more than 3 parts by weight of hydrogen peroxide, wherein the hydrogen peroxide contains H₂O₂The concentration of (A) is 0.25% -6%;

(2) filling the weighed polyolefin plastic and hydrogen peroxide into a hydrothermal reactor for oxidation pretreatment reaction at the reaction temperature of 150 ℃ and 230 ℃ to obtain a liquid phase product and a gas phase product after the reaction is finished;

(3) and (3) filling a mesoporous carbon supported metal-based catalyst in the other hydrothermal reactor, and introducing the liquid-phase product obtained in the step (2) into the hydrothermal reactor for reforming reaction to obtain a hydrogen-rich synthesis gas product.

2. The method for preparing hydrogen-rich syngas by low-temperature degradation of polyolefin waste plastic as claimed in claim 1, wherein: h in hydrogen peroxide in the step (1)₂O₂The content of (B) is 0.5-2%.

3. The method for preparing hydrogen-rich syngas by low-temperature degradation of polyolefin waste plastic as claimed in claim 1, wherein: the hydrogen peroxide in the step (1) is 3-80 parts by weight.

4. The method for preparing hydrogen-rich syngas by low-temperature degradation of polyolefin waste plastic as claimed in claim 3, wherein: the hydrogen peroxide in the step (1) accounts for 5-10 parts by weight, the reaction pressure in the step (2) is 0.5-2MPa, and the reaction time is 30-90 min.

5. The method for preparing hydrogen-rich syngas by low-temperature degradation of polyolefin waste plastic according to claim 4, wherein: in the step (2), the reaction temperature is 190-.

6. The method for preparing hydrogen-rich syngas by low-temperature degradation of polyolefin waste plastic as claimed in claim 1, wherein: the main component of the liquid phase product obtained in the step (2) is acetic acid, and the gas phase product is oxygen and carbon dioxide.

7. The method for preparing hydrogen-rich syngas by low-temperature degradation of polyolefin waste plastic as claimed in claim 1, wherein: the reaction temperature of the reforming reaction in the step (3) is 200-.

8. The method for preparing hydrogen-rich syngas by low-temperature degradation of polyolefin waste plastic as claimed in claim 1, wherein: the mesoporous carbon-supported metal-based catalyst in the step (3) is one or more of mesoporous carbon-supported Ru monometal, mesoporous carbon-supported Ni monometal, mesoporous carbon-supported Pt monometal and mesoporous carbon-supported Ru-Ni bimetallic.

9. The method for preparing hydrogen-rich syngas by low-temperature degradation of polyolefin waste plastic according to claim 8, wherein: the mesoporous carbon-supported metal-based catalyst in the step (3) is a mesoporous carbon-supported Ru-Ni bimetallic catalyst, and the loading mass ratio of Ru to Ni is 4:1, 1:1 or 1: 4.

10. The method for preparing hydrogen-rich syngas by low-temperature degradation of polyolefin waste plastic as claimed in claim 1, wherein: the polyolefin plastic is selected from one or more of polypropylene, low density polyethylene and high density polyethylene.

[ background of the invention ]

Plastics, as one of the main synthetic materials, occupy an important position in the field of materials. China is the first plastic producing country in the world, a large amount of plastic garbage is produced every year, and a part of plastic which is difficult to decompose enters the natural environment on land and the sea, so that the ecological environment is greatly influenced. Some typical waste plastics include polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene plastics, and the like. The polyolefin plastics such as polyethylene, polypropylene and the like have the widest application range and account for the largest proportion in the total amount of waste plastics. In addition, as the main material of medical masks, the yields of polypropylene raw materials and wastes thereof are rapidly increased during the period of COVID-19, while the main methods for disposing domestic plastic wastes currently used are landfill, incineration and the like, and the two methods cause secondary pollution and waste of resources to a great extent. Therefore, efficient conversion of plastics into clean energy such as hydrogen energy has become a hot spot.

Liquid phase reforming is a low-temperature low-pressure hydrogen production technology, liquid oxygen-containing organic matters can be converted into hydrogen by utilizing the catalytic action of a catalyst under the hydrothermal condition of 200-260 ℃ and 1.5-4MPa, and waste polyolefin plastics are solid wastes and do not contain oxygen atoms, so that the hydrogen can not be directly produced by liquid phase reforming.

At present, the method for preparing hydrogen by waste plastics mainly takes high-temperature pyrolysis gasification (500-. In addition, research (Waste management 2020,102,520-7, Energy 2020, 191, 116527) has proposed to convert plastics into hydrogen by supercritical water gasification (T >374 ℃, P >22.1MPa), and because the operation of supercritical water gasification has high requirements on equipment, there is a certain limitation in industrial application, and at present, the yield of hydrogen (2-5mol/kg plastics) and the hydrogen concentration in synthesis gas obtained by converting polyethylene and polypropylene into hydrogen by supercritical water gasification are not high (10-40%).

[ summary of the invention ]

The invention aims to solve the problems in the prior art and provides a method for preparing hydrogen-rich synthesis gas by low-temperature degradation of polyolefin waste plastics, which adopts a two-step method combining oxidation pretreatment and reforming reaction, and dilute H is used in the first stage₂O₂The solution is used for carrying out oxidation pretreatment on polyolefin waste plastics such as polyethylene and polypropylene at the reaction temperature of lower than 250 ℃, and in the second stage, low-temperature reforming hydrogen production is carried out on the liquid phase obtained by pretreatment under the catalysis of a high-efficiency carbon-based catalyst, so that high-efficiency hydrogen production of the polyolefin plastics under mild conditions is realized.

In order to achieve the purpose, the invention provides a method for preparing hydrogen-rich synthesis gas by low-temperature degradation of polyolefin waste plastics, which adopts a two-step method combining oxidation pretreatment and reforming reaction and comprises the following steps:

(1) weighing 1 part by weight of polyolefin plastic and more than 3 parts by weight of hydrogen peroxide, wherein the hydrogen peroxide contains H₂O₂The concentration of (A) is 0.25% -6%;

(2) filling the weighed polyolefin plastic and hydrogen peroxide into a hydrothermal reactor for oxidation pretreatment reaction at the reaction temperature of 150 ℃ and 230 ℃ to obtain a liquid phase product and a gas phase product after the reaction is finished;

h in the reaction solution₂O₂Completely decomposing, and detecting that the product does not contain H₂O₂So there will be no residual H₂O₂A negative effect on the catalyst of the reforming reaction of the second stage;

(3) and (3) filling a mesoporous carbon supported metal-based catalyst in the other hydrothermal reactor, and introducing the liquid-phase product obtained in the step (2) into the hydrothermal reactor for reforming reaction to obtain a hydrogen-rich synthesis gas product. The step (1) and the step (2) are oxidation pretreatment stages, and the step (3) is a reforming reaction stage.

Preferably, the hydrogen in the hydrogen peroxide in the step (1)₂O₂The content of (A) is 0.5-2%;

as a strong oxidant, high concentrations of H₂O₂Harsh conditions liable to lead to oxidative cleavage of the C-C bond, H₂O₂Too low a concentration will lead to insufficient oxidation, so 0.25% -6% H₂O₂The hydrogen peroxide can effectively realize the preoxidation of polyolefin plastics under the condition of low temperature, and H₂O₂When the content of (b) is 0.5 to 2%, the yield and concentration of hydrogen obtained by the second-stage reforming reaction are optimum.

Preferably, the weight part of the hydrogen peroxide in the step (1) is 3-80;

preferably, the hydrogen peroxide in the step (1) is 5-10 parts by weight;

the residual hydrogen peroxide in the oxidation pretreatment has negative effects on the oxidation of a metal catalyst in the second-stage reforming reaction and the like, and the hydrogen peroxide has high H content₂O₂The reforming process generates more CO at the weight ratio of polyolefin plastics₂Resulting in H in the gaseous product₂The mole fraction of the hydrogen peroxide is reduced, and the optimal hydrogen peroxide is 5 to 10 weight parts.

Preferably, the reaction pressure in the step (2) is 0.5-2MPa, and the reaction time is 30-90 min.

Preferably, the reaction temperature in the step (2) is 190-.

Preferably, in the step (2), the reaction temperature is 200 ℃, and the reaction time is 60 min;

when the temperature is too low, the oxidation reaction of polyolefin plastics is weakened, and when the temperature is too high, organic matters can undergo decarboxylation reaction, namely, the thermal cracking of long-chain carboxylic acid, and the oxidation time is too long, so that the oxidation reaction and the reforming reaction of the polyolefin plastics are not favorable.

Preferably, the main component of the liquid phase product obtained in the step (2) is acetic acid, and the gas phase product is oxygen and carbon dioxide;

the liquid phase product is mainly acetic acid, and the contents of other short-chain small molecular acids such as formic acid, propionic acid and the like are very low, so that the activity of the catalyst for the reforming reaction is not adversely affected.

Preferably, the reaction temperature of the reforming reaction in the step (3) is 200-.

Preferably, the mesoporous carbon supported metal-based catalyst in the step (3) is one or more of a mesoporous carbon supported Ru monometal, a mesoporous carbon supported Ni monometal, a mesoporous carbon supported Pt monometal and a mesoporous carbon supported Ru-Ni bimetallic;

the specific surface area of the selected mesoporous carbon is 1400-1500m²More active sites are available per gram.

Preferably, the mesoporous carbon supported metal-based catalyst in the step (3) is a mesoporous carbon supported Ru-Ni bimetallic catalyst, and the loading mass ratio of Ru to Ni is 4:1, 1:1 or 1: 4;

mesoporous carbon supported Ru monometallic catalysts exhibit the highest H for oxidative pretreatment of polyolefins₂Selectivity, and the highest hydrogen yield and hydrogen concentration are obtained under the catalysis of the mesoporous carbon supported Ru single metal catalyst, but considering that Ru metal is expensive, and the single metal catalyst is not high in stability in a hydrothermal environment and is easy to inactivate, the cost of the catalyst can be effectively reduced by adding non-noble metal to replace part of active metal Ru under the condition of ensuring that the total amount of the supported metal is unchanged. The mesoporous carbon loaded Ru-Ni bimetallic catalyst provided by the invention realizes the multiple increase of hydrogen yield, and RuNi alloy is formed in the preparation process, so that the stability of the catalyst is greatly improved.

Preferably, the polyolefin plastic is selected from one or more of polypropylene, low density polyethylene and high density polyethylene.

Preferably, the mesoporous carbon supported metal baseThe preparation steps of the catalyst are as follows: sieving mesoporous carbon to 150 meshes; adding a certain amount of mesoporous carbon and soluble metal precursor into deionized water according to 5 wt% of total metal loading, uniformly stirring and soaking at room temperature for 12 hours, continuously stirring at 80 ℃ until the water is evaporated to dryness, and drying the obtained sample in a drying oven at 105 ℃ for 12 hours; finally at 550 ℃ 10% H₂Reduction in-90% Ar for 4 hours.

The invention adopts a two-step method combining oxidation pretreatment and reforming reaction to realize the degradation of polyolefin under the condition of low temperature and high-efficiency hydrogen production, and the two stages have synergistic effect, thereby producing the following beneficial effects:

(1) the invention adopts a two-step method to produce hydrogen, on one hand, the high-efficiency hydrogen production is realized by using the polyolefin waste plastic at the temperature lower than 250 ℃, the hydrogen yield is close to 11mol/kg of plastic, the energy consumption and the operation cost are reduced, on the other hand, the high-efficiency degradation of the polyolefin waste plastic is realized, and the method has higher utilization value in the aspect of treating the polyolefin plastic waste;

(2) in the oxidative pretreatment stage, H₂O₂As a strong oxidant, under the condition of higher concentration (6-8%), the raw material can be excessively oxidized, so that the C-C bond is subjected to oxidative cracking, the yield of the byproduct carbon dioxide is higher, and H is controlled₂O₂The concentration is 0.25% -6%, the yield of carbon dioxide is obviously reduced, and the peroxidation of carboxylic acid generated in the pre-oxidation stage can be effectively weakened, so that more carboxylic acid is ensured to participate in the reaction in the second stage of hydrogen production, and the hydrogen production is promoted;

(3) controlling the weight ratio of hydrogen peroxide to polyolefin to be 5: 1-10:1, so that the product generated in the oxidation pretreatment stage does not contain hydrogen peroxide, and the negative effects of oxidation and the like of the residual hydrogen peroxide on the metal catalyst in the second stage reforming reaction are avoided;

(4) the low-concentration hydrogen peroxide in the reaction liquid can perform selective oxidation fracture on carbon-carbon bonds in the polyolefin plastic in a low-temperature hydrothermal environment to form aldehyde and other micromolecular intermediate products, and then the aldehyde and other micromolecular intermediate products are quickly oxidized into acetic acid and other organic acids, so that the polyolefin plastic is degraded under the low-temperature condition;

(5) in the first-stage oxidation pretreatment reaction, the product mainly containing acetic acid is obtained, the content of other short-chain micromolecule acids such as formic acid, propionic acid and the like is very low, the yield of the acetic acid is 1.5-2mol/kg of plastic, the reaction activity of the acetic acid is lower than that of the formic acid, the activity of a carbon-based catalyst cannot be adversely affected, and the second-stage reforming reaction hydrogen production is facilitated;

(6) the mesoporous carbon loaded Ru-Ni bimetallic catalyst realizes the multiple increase of hydrogen yield, and RuNi alloy is formed in the preparation process, so that the stability of the catalyst is greatly improved;

(7) compared with the supercritical water gasification hydrogen production of polyolefin plastics, the method has the advantages that the reaction temperature and pressure are greatly reduced, the hydrogen production under the mild hydrothermal condition of polyolefin is realized, and the yield and the concentration of the obtained hydrogen are higher;

(8) mesoporous carbon supported Ru monometallic catalysts exhibit the highest H for oxidative pretreatment of polyolefins₂Selectivity, and the highest hydrogen yield and hydrogen concentration are obtained under the catalysis of the mesoporous carbon supported Ru single metal catalyst, but considering that Ru metal is expensive, and the single metal catalyst is not high in stability in a hydrothermal environment and is easy to inactivate, the cost of the catalyst can be effectively reduced by adding non-noble metal to replace part of active metal Ru under the condition of ensuring that the total amount of the supported metal is unchanged. The mesoporous carbon loaded Ru-Ni bimetallic catalyst provided by the invention realizes the multiple increase of hydrogen yield, and RuNi alloy is formed in the preparation process, so that the stability of the catalyst is greatly improved.

[ description of the drawings ]

FIG. 1 is the present invention H₂O₂A graph of the concentration of (d) against the yield of each product;

FIG. 2 is the present invention H₂O₂A graph of concentration of (a) versus gas composition in the syngas product;

FIG. 3 is the present invention H₂O₂A graph of concentration versus hydrogen selectivity;

FIG. 4 is a graph of hydrogen peroxide to polyolefin mass ratio versus syngas yield for the present invention;

FIG. 5 is the present inventionMing H₂O₂A graph of concentration versus carbon dioxide generated by pre-oxidation treatment;

FIG. 6 is a nitrogen adsorption-desorption isotherm of a fresh catalyst synthesized in accordance with the present invention;

FIG. 7 is a schematic of the pore size distribution of the fresh catalyst synthesized in accordance with the present invention;

FIG. 8 is a schematic XRD of a fresh catalyst synthesized in accordance with the present invention;

fig. 9 is a TEM image and a particle size distribution diagram of the mesoporous carbon supported catalyst of the present invention.

[ detailed description ] embodiments

Example 1:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 6% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2: and (3) introducing the liquid-phase product subjected to the first-stage oxidation pretreatment into a reactor filled with a mesoporous carbon-supported Ru single-metal catalyst. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

The preparation method of the mesoporous carbon supported Ru single metal catalyst comprises the following steps: sieving the mesoporous carbon to 150 meshes; adding a certain amount of mesoporous carbon and ruthenium chloride into deionized water according to 5 wt% of total metal loading, uniformly stirring and soaking for 12 hours at room temperature, continuously stirring at 80 ℃ until the water is evaporated to dryness, and drying the obtained sample in a drying oven at 105 ℃ for 12 hours; at 550 deg.C, 10% H₂Reduction in-90% Ar for 4 hours.

Example 2:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 4% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 3:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 2% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 4:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 1% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 5:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid phase product obtained by oxidation pretreatment is acetic acidThe gas phase products are carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 6:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.25% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 7:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio of 3: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 8:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 5: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 9:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 20: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 10:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 40: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 11:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 80: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 12:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide 80ml, 0.5 percentH₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 180 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 13:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 190 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 14:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 210 ℃, the reaction time is 60min, and the reaction pressure is 2 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 15:

step 1 is the same as step 1 of example 1.

Step 2: and introducing the liquid-phase product of the first-stage oxidation pretreatment into a reactor filled with a Ni single metal catalyst loaded by mesoporous carbon. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

The preparation method of the Ni single metal catalyst loaded by the mesoporous carbon comprises the following steps: sieving the mesoporous carbon to 150 meshes; adding a certain amount of mesoporous carbon and nickel chloride hexahydrate into deionized water according to the total metal loading amount of 5 wt%, uniformly stirring and soaking at room temperature for 12 hours, continuously stirring at 80 ℃ until the water is evaporated to dryness, and drying the obtained sample in a drying oven at 105 ℃ for 12 hours; at 550 deg.C, 10% H₂Reduction in-90% Ar for 4 hours.

Example 16:

step 1 is the same as step 1 of example 1.

Step 2: and (3) introducing the liquid-phase product of the first-stage oxidation pretreatment into a reactor filled with a mesoporous carbon-supported Pt single metal catalyst. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

The preparation method of the mesoporous carbon supported Pt single metal catalyst comprises the following steps: sieving the mesoporous carbon to 150 meshes; adding a certain amount of mesoporous carbon and chloroplatinic acid into deionized water according to 5 wt% of total metal loading, uniformly stirring and soaking at room temperature for 12 hours, continuously stirring at 80 ℃ until the water is evaporated to dryness, and drying the obtained sample in an oven at 105 ℃ for 12 hours; at 550 deg.C, 10% H₂Reduction in-90% Ar for 4 hours.

Example 17:

step 1 is the same as step 1 of example 1.

Step 2: and (3) introducing the liquid-phase product subjected to the first-stage oxidation pretreatment into a reactor filled with a mesoporous carbon loaded Ru-Ni bimetallic catalyst, wherein the loading mass ratio of Ru to Ni in the mesoporous carbon loaded Ru-Ni bimetallic catalyst is 4: 1. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

The preparation method of the mesoporous carbon loaded Ru-Ni bimetallic catalyst comprises the following steps: sieving the mesoporous carbon to 150 meshes; adding a certain amount of mesoporous carbon, nickel chloride hexahydrate and ruthenium chloride into deionized water according to the total metal loading amount of 5 wt% in proportion, uniformly stirring and soaking for 12 hours at room temperature, continuously stirring at 80 ℃ until the water is evaporated to dryness, and drying the obtained sample in a drying oven at 105 ℃ for 12 hours;at 550 deg.C, 10% H₂Reduction in-90% Ar for 4 hours.

Example 18:

step 1 is the same as step 1 of example 1.

Step 2: and (3) introducing the liquid-phase product subjected to the first-stage oxidation pretreatment into a reactor filled with a mesoporous carbon loaded Ru-Ni bimetallic catalyst, wherein the loading mass ratio of Ru to Ni in the mesoporous carbon loaded Ru-Ni bimetallic catalyst is 1: 1. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

The preparation method of the mesoporous carbon loaded Ru-Ni bimetallic catalyst comprises the following steps: sieving the mesoporous carbon to 150 meshes; adding a certain amount of mesoporous carbon, nickel chloride hexahydrate and ruthenium chloride into deionized water according to the total metal loading amount of 5 wt% in proportion, uniformly stirring and soaking for 12 hours at room temperature, continuously stirring at 80 ℃ until the water is evaporated to dryness, and drying the obtained sample in a drying oven at 105 ℃ for 12 hours; at 550 deg.C, 10% H₂Reduction in-90% Ar for 4 hours.

Example 19:

step 1 is the same as step 1 of example 1.

Step 2: and (3) introducing the liquid-phase product subjected to the first-stage oxidation pretreatment into a reactor filled with a mesoporous carbon loaded Ru-Ni bimetallic catalyst, wherein the loading mass ratio of Ru to Ni in the mesoporous carbon loaded Ru-Ni bimetallic catalyst is 1: 4. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

The preparation method of the mesoporous carbon loaded Ru-Ni bimetallic catalyst comprises the following steps: sieving the mesoporous carbon to 150 meshes; adding a certain amount of mesoporous carbon, nickel chloride hexahydrate and ruthenium chloride into deionized water according to the total metal loading amount of 5 wt% in proportion, uniformly stirring and soaking for 12 hours at room temperature, continuously stirring at 80 ℃ until the water is evaporated to dryness, and drying the obtained sample in a drying oven at 105 ℃ for 12 hours; at 550 deg.C, 10% H₂Reduction in-90% Ar for 4 hours.

Example 20:

step 1 is the same as step 1 of example 1.

Step 2: the liquid phase product of the first stage of oxidation pretreatment was passed into a reactor filled with a mesoporous carbon supported Ru-Ni bimetallic catalyst, which was recovered after use in example 17. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

Example 21:

step 1 is the same as step 1 of example 1.

Step 2: the liquid phase product of the first stage of oxidation pretreatment was passed into a reactor filled with a mesoporous carbon supported Ru-Ni bimetallic catalyst, which was recovered after use in example 20. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

Example 22:

step 1 is the same as step 1 of example 1.

Step 2: the liquid phase product of the first stage of oxidation pretreatment was passed into a reactor filled with a mesoporous carbon supported Ru-Ni bimetallic catalyst, which was recovered after use in example 21. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

Example 23:

step 1 is the same as step 1 of example 1.

Step 2: and (3) introducing the liquid-phase product subjected to the first-stage oxidation pretreatment into a reactor filled with a mesoporous carbon-supported Ru monometallic catalyst, wherein the Ru monometallic catalyst is the Ru monometallic catalyst recovered in example 5. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

Example 24:

step 1 is the same as step 1 of example 1.

Step 2: the liquid phase product of the first stage of oxidation pretreatment was passed into a reactor filled with a mesoporous carbon supported Ru-Ni bimetallic catalyst, which was recovered after use in example 23. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

Example 25:

step 1 is the same as step 1 of example 1.

Step 2: the liquid phase product of the first stage of oxidation pretreatment was passed into a reactor filled with a mesoporous carbon supported Ru-Ni bimetallic catalyst, which was recovered after use in example 24. The reaction conditions are as follows: the reaction temperature is 240 ℃, the reaction time is 120min, and the reaction pressure is 4 MPa.

Example 26:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of high density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 the same as example 17, step 2; the catalyst was prepared in the same manner as in example 17.

Example 27:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 2% H₂O₂Hydrogen peroxide, 0.16g of polypropylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 28:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 1% H₂O₂Hydrogen peroxide, 0.16g of polypropylene andthe prepared dilute hydrogen peroxide is loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 60min, and the reaction pressure is 0.5 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 29:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of high density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 30min, and the reaction pressure is 1 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2: and (3) introducing the liquid-phase product subjected to the first-stage oxidation pretreatment into a reactor filled with a mesoporous carbon loaded Ru-Ni bimetallic catalyst, wherein the loading mass ratio of Ru to Ni in the mesoporous carbon loaded Ru-Ni bimetallic catalyst is 4: 1. The reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 180min, and the reaction pressure is 2 MPa.

The catalyst was prepared in the same manner as in example 16.

Example 30:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of high density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction time is 90min, and the reaction pressure is 1 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 the same as step 2 of example 29; the catalyst was prepared in the same manner as in example 17.

Example 31:

step 1: commercial 30 dilution with deionized Water％H₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 150 ℃, the reaction time is 60min, and the reaction pressure is 2 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 32:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 220 ℃, the reaction time is 60min, and the reaction pressure is 2 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

Example 33:

step 1: commercial 30% H dilution with deionized water₂O₂Hydrogen peroxide, 80ml of 0.5% H₂O₂Hydrogen peroxide, 0.16g of low density polyethylene and the prepared dilute hydrogen peroxide are loaded into a hydrothermal reactor to ensure that H is generated₂O₂-plastic ratio 10: 1; the reaction conditions are as follows: the reaction temperature is 230 ℃, the reaction time is 60min, and the reaction pressure is 2 MPa; the main liquid-phase product obtained by the oxidation pretreatment is acetic acid, and the gas-phase product is carbon dioxide and oxygen;

step 2 is the same as step 2 of example 1; the catalyst preparation method was the same as in example 1.

The gas products obtained from examples 1-33 after catalytic reforming were tested by gas chromatography and calculated to obtain the relevant indices, with the experimental data shown in table 1:

TABLE 1

Note: MEC is mesoporous carbon; Ru/MEC is a Ru single metal catalyst loaded by mesoporous carbon; Ni/MEC is Ni single metal catalyst loaded by mesoporous carbon; the Pt/MEC is a Pt single metal catalyst loaded by mesoporous carbon; 4Ru-1Ni/MEC is a Ru-Ni bimetallic catalyst loaded by mesoporous carbon, and the loading mass ratio of Ru to Ni is 4: 1; 1Ru-1Ni/MEC is a Ru-Ni bimetallic catalyst loaded by mesoporous carbon, and the loading mass ratio of Ru to Ni is 1: 1; 1Ru-4Ni/MEC is a Ru-Ni bimetallic catalyst loaded by mesoporous carbon, and the loading mass ratio of Ru to Ni is 1: 4; h₂O₂The plastic ratio, namely the mass ratio of hydrogen peroxide to polyolefin.

From examples 1 to 6, H in hydrogen peroxide in the first stage₂O₂When the concentration of (A) is 0.25-1%, the yield and concentration of hydrogen obtained in the second stage process are good, and H is₂O₂When the concentration of (A) is 0.5%, the hydrogen production effect is optimal;

study H according to examples 1-6₂O₂The results are shown in FIG. 1, in which the abscissa represents H₂O₂In wt% and the ordinate represents the yield of the respective product in mol/kg, C in the figure₁-C₃Is represented by C₁-C₃Alkalkene, CO stands for carbon monoxide, CO₂Denotes carbon dioxide, H₂Represents hydrogen; from FIG. 1, following H₂O₂The concentration is from 8% (H)₂The yield was reduced to 3.05mol/kg) to 0.5% (H)₂Yield 10.83mol/kg), H₂The yield showed a clear increasing trend. But when H₂O₂When the concentration is further reduced to 0.25%, H₂The yield decreased from 10.83mol/kg to 10.34mol/kg by 4.5%, due to H₂O₂Lower concentrations result from insufficient oxidation. When H is present₂O₂At a concentration of0.25% by weight, CO₂The yield was 3.65 mol/kg. This is because CO is present during the oxidative pretreatment₂Not only from the peroxidation of carboxylic acids, but also directly during the oxidative cleavage of the C-C bond. The high concentration of carbon dioxide produced by the oxidative pretreatment process is likely to be used for further carbon capture, utilization and storage.

Study H according to examples 1-6₂O₂The results are shown in FIG. 2, in which the abscissa represents the mole fraction of each gas component and the ordinate represents H₂O₂In wt% of H in the product synthesis gas for the reforming reaction₂Is greater than 40% in all H₂O₂At a concentration of H₂O₂The concentration reached a maximum (51.52%) at 0.5%.

H₂O₂As a strong oxidant, under the condition of higher concentration (6-8%), the raw material can be excessively oxidized, so that C-C bond is subjected to oxidative cracking, the yield of the byproduct carbon dioxide is higher, and H is reduced₂O₂The concentration and the yield of carbon dioxide are obviously reduced, and the peroxidation of the carboxylic acid generated in the pre-oxidation stage can be effectively weakened, so that more carboxylic acid is ensured to participate in the reaction in the second stage hydrogen production process, and the hydrogen production is promoted.

Study H according to examples 1-6₂O₂The results are shown in FIG. 3, in which the abscissa represents H₂O₂In wt% and the ordinate represents the mole fraction of carbon dioxide in the synthesis gas and the hydrogen selectivity; as can be seen from FIG. 3, during the reforming reaction, H is accompanied₂O₂Reduction of concentration, carbon to CO₂The transformation of (a) is increased.

The effect of the hydrogen peroxide-polyolefin ratio on the syngas yield was investigated according to example 5 and examples 7-11, and the results are shown in fig. 4, where the abscissa represents the hydrogen peroxide-polyolefin mass ratio and the ordinate represents the syngas yield and the mole fraction of hydrogen and carbon dioxide in the syngas. From fig. 4, it can be seen that when the mass ratio of hydrogen peroxide to polyolefin is 10:1, the hydrogen concentration and the synthesis gas yield in the synthesis gas obtained in the second stage process are optimal.

Study H according to examples 1-6₂O₂The effect of concentration on carbon dioxide generated by the pre-oxidation treatment is shown in FIG. 5, in which the left abscissa represents H₂O₂The concentration of (b) is in wt%, the abscissa on the right represents the mass ratio of hydrogen peroxide to polyolefin, and the ordinate represents the yield of carbon dioxide in mol/kg. As can be seen from FIG. 5, the CO produced during the oxidative pretreatment₂The amount increases as the amount of plastic decreases. This is probably due to the fact that during the cleavage of the C-C bond more H is present₂O₂Promote CO₂Rather than over-oxidation. However, at higher hydrogen peroxide-polyolefin mass ratios, the reforming reaction process produces more CO₂Resulting in H in the gaseous product₂The mole fraction of (a) decreases.

In conclusion, it can be concluded that H in hydrogen peroxide in the first stage reaction₂O₂When the concentration of (A) is 0.25-1%, the yield and concentration of hydrogen obtained in the second stage process are good, and H is₂O₂When the concentration of (A) is 0.5%, the hydrogen production effect is optimal.

It follows from example 5 and examples 12 to 14 that the yield and concentration of hydrogen in the synthesis gas obtained in the second stage is highest at a pretreatment temperature of 200 ℃ in the first stage;

according to example 5 and examples 15-19, the mesoporous carbon supported Ru, Ni, Pt monometallic catalysts and Ru-Ni bimetallic catalysts have the order of Ru/MEC >4Ru-1Ni/MEC >1Ru-1Ni/MEC > Pt/MEC >1Ru-4Ni/MEC > Ni/MEC for the second stage catalytic performance of the present invention, and the pore structures of the fresh catalysts of example 5 and examples 14-17 were characterized, and the results are shown in Table 2:

TABLE 2

The nitrogen adsorption-desorption isotherms of the fresh catalysts synthesized in example 5 and examples 15 to 19 are shown in FIG. 6, in which the abscissa of FIG. 6 represents the relative pressure P/P⁰,P⁰Represents the saturated vapor pressure of the gas at the adsorption temperature, P represents the pressure of the gas phase at the adsorption equilibrium, and the ordinate represents the adsorption amount (unit: cm) measured in the standard state³(iv)/g); the pore size distribution of the fresh catalyst is shown in FIG. 7, in which FIG. 7 the abscissa represents the pore diameter (unit: nm) and the ordinate represents the pore volume (cm)³In terms of/g). As can be seen from FIGS. 6 and 7, all the catalysts have IV-type isotherms with narrow pore size distribution and center at about 5nm, because they have developed mesoporous structures and have a structure of 1000-1400m²Specific surface area/g, the specific surface area and pore volume of all mesoporous carbon supported metal based catalysts are lower compared to mesoporous carbon due to the introduction of metal particles in the pores of the mesoporous carbon, resulting in a reduction of specific surface area and void volume; the specific surface area and pore volume of 4Ru-1Ni/MEC are higher compared to Ru/MEC, while the specific surface area and pore volume of 1Ru-1Ni/MEC and 1Ru-4Ni/MEC are lower. These results indicate that the addition of a small amount of the second metal improves the texture properties of the single metal catalyst.

XRD spectra of Ni/MEC, Ru/MEC and bimetallic catalyst in different molar ratios are shown in FIG. 8. For Ni/MEC, there are larger peaks at 44.5 ° and 51.5 ° corresponding to Ni (111) face and (200) face, respectively. The XRD spectra of Ru/MEC and Ru-based bimetallic catalysts have two weak peaks at 38.5 degrees and 42.3 degrees respectively, which represent the 100 and 002 crystal planes of Ru species respectively. The weak diffraction peaks of metallic Ru in Ru/MEC and Ru-Ni bimetallic catalysts indicate that Ru nanoparticles are small in size and highly dispersed on the MEC surface [38,45,49,50], which is consistent with the scanning result of an electron microscope, and small nanoparticles can provide more surface atoms, so that the catalytic activity of the Ru/MEC and Ru-Ni bimetallic catalysts is improved.

According to example 5, example 17 and examples 20 to 25 it is concluded that mesoporous carbon supported Ru — Ni bimetallic catalysts show higher stability than Ru monometallics under the operating conditions of the present invention.

TEM images and metal particle size distributions of the single-metal and bimetallic carbon supported catalysts are shown in FIG. 9, where a is TEM and particle size distribution image of Ni/MEC, b is TEM and particle size distribution image of Ru/MEC, c is TEM and particle size distribution image of 4Ru-1Ni/MEC, and the average particle size of Ru-Ni is 14.1nm and larger than that of single-metal Ru/MEC (average particle size is 7.2nm) in FIG. 9. This phenomenon is probably due to the synergistic effect of Ru and Ni. It was observed that the Ru and Ni atoms were almost in the same position, and each atom was not separated throughout the imaged region, indicating that a uniform Ru — Ni alloy structure was formed.

The results of further studies on the effect of operating parameters of the oxidative pretreatment reactions on the performance of the first stage oxidative pretreatment and the second stage reforming reactions are shown in Table 3:

TABLE 3

From table 3, the oxidation reaction of polyolefin is weakened at a lower hydrothermal temperature, and in a hydrothermal environment of 220 ℃ or higher, organic matters may undergo decarboxylation reaction, i.e., thermal cracking of long-chain carboxylic acids, and the reforming reaction is adversely affected by an excessively long pre-oxidation reaction time. When the time of the oxidation pretreatment is 60min and the temperature is 200 ℃, the yield of the acetic acid is the highest, and the subsequent reforming reaction is most favorably carried out.

The hydrogen production catalytic activities of the fresh bimetallic 4Ru-1Ni/MEC catalyst and the monometallic Ru catalyst were most similar, so the 4Ru-1Ni/MEC and Ru/MEC catalysts were selected for stability testing and comparison. After each use, the catalyst was recovered and dried overnight in an oven at 105 ℃. H of the second run compared to the first run₂Yield and H₂The mole fraction dropped significantly and the third and fourth runs varied smoothly. The decline in catalyst performance is due to catalyst deactivation caused by carbon deposits and sintering of the active metal.

The results of examples 20-25 show that the specific surface area is reduced after use for both 4Ru-1Ni/MEC and Ru/MEC catalysts, and that the pore size of the catalysts is reduced although the average pore size of both catalysts is reduced after useThe distribution is still narrow, with a central position around 5 nm. In addition, no NiO peak was observed in the XRD spectrum of the mesoporous carbon supported Ru — Ni bimetallic catalyst, probably due to the inhibitory effect of metallic Ru on the oxidation of Ni. The hydrogen production amounts in the third and fourth runs did not change much compared to the second run, but H₂The mole fraction tends to decrease. H of reforming reaction process of mesoporous carbon loaded Ru-Ni bimetallic catalyst₂Yield and H₂The mole fractions are all higher than that of the mesoporous carbon supported Ru single metal catalyst. This indicates that the Ru — Ni bimetallic catalyst has higher stability than the monometallic Ru catalyst due to the interaction between the two metals.

The above embodiments are illustrative of the present invention, and are not intended to limit the present invention, and any simple modifications of the present invention are within the scope of the present invention.