CN108722327A - A kind of biomass membrane type micro-wave reactor and its experimental provision and method applied to methane reforming - Google Patents

Abstract

The invention discloses a kind of biomass membrane type micro-wave reactors, the internal quartz ampoule for filling biomass-based charcoal film catalyst is fixed on microwave heating equipment central area with flange and screw rod, the new-type biomass membrane type micro-wave reactor is made, wherein, using biomass carbon membrane made from sawdust as carrier, using the active component of nickel and cobalt as catalyst, the load biomass-based charcoal film catalyst of Ni-Co active components is made；The biomass membrane type micro-wave reactor is assembled and is applied in the experimental provision of methane reforming, and carries out methane reforming experiment.The invention has the advantages that new-type biomass membrane type micro-wave reactor substitutes conventional heating device, methane reforming is carried out using the methane reforming experimental provision, strengthens reaction collaboration and carries out, the H of synthesis gas₂With CO ratios 1.10, CH are increased to by 0.83₄And CO₂High conversion rate is up to 95%, and experimental method of the invention is at low cost, reaction-ure conversion-age is high.

Description

A biomass membrane microwave reactor and its experimental device for methane reforming and method

technical field

The invention relates to the technical field of methane reforming, in particular to a biomass membrane microwave reactor and its experimental device and method for methane reforming.

Background technique

CH ₄ and CO ₂ are small molecular substances with stable structures, and the reforming of CH ₄ -CO ₂ should be carried out under catalytic conditions. Catalysts mainly include noble metal catalysts, transition metal catalysts and carbon-based catalysts. Precious metal catalysts have high activity, but the main bottleneck is high price and difficult promotion; transition metal catalysts have better performance, mainly due to problems such as carbon deposition inactivation and active material sintering; carbon-based catalysts have obvious advantages in raw material sources and prices, and carbon deposition Can be directly used as a carrier.

Carbon film is a film material formed by pyrolysis of carbonaceous substances at high temperature. It has the characteristics of high temperature resistance, corrosion resistance, acid and alkali resistance, good chemical stability and high mechanical strength. Oxidative modification and loading of active substances on the carbon membrane can improve the surface chemical properties and catalytic performance of the carbon membrane. Microwave heating has the characteristics of immediacy, integrity, high efficiency and controllability, etc. The rise of carbon-based catalysts has promoted the application of microwave technology in the reforming reaction of CH ₄ -CO ₂ .

Patent CN102416328A discloses a catalyst for reforming methane and carbon dioxide to produce synthesis gas and its preparation method. The catalyst is composed of nickel, iron, cerium oxide, and Alcoa spinel; the preparation method is to first prepare mesoporous MgAl ₂ O ₄ spinel Stone carrier, then prepare nickel-based catalyst suspension, and finally filter, wash, dry and roast.

Patent CN101637726A discloses a method for preparing a catalyst for methane carbon dioxide reforming to synthesis gas, in which a modified component is obtained by immersing the carrier in a mixed solution of cerous nitrate and lanthanum nitrate. Then the modified component is immersed in the soluble solution of nickel salt, dried and calcined to obtain the catalyst precursor.

Patent CN102464299A discloses a method for producing hydrogen by steam reforming of fluidized bed methane, which includes decomposing and regenerating the adsorption catalyst with low bulk density in the regenerator, and regenerating the adsorption catalyst at the bottom of the reactor and the high bulk density of the external circulation. reforming catalyst mix. Among them, the regeneration of the catalyst is realized, but the CO ₂ generated by the regeneration of the catalyst is directly discharged into the atmosphere, and the process is complicated and consumes a lot of energy.

At present, conventional microwave technology is applied to CH ₄ -CO ₂ reforming experiments, but there are problems of low reaction efficiency, low conversion rate, high cost and high energy consumption.

Contents of the invention

Aiming at the above-mentioned deficiencies, the present invention proposes a biomass membrane microwave reactor and its experimental device and method for methane reforming.

To achieve the above object, the present invention adopts the following technical solutions:

A biomass membrane microwave reactor, including a microwave heating device, a biomass-based carbon membrane catalyst and a quartz tube, the quartz tube containing the biomass-based carbon membrane catalyst is fixed to the microwave with a flange and a screw made of polytetrafluoroethylene. In the central area of the heating device, a porous quartz plate is set at a distance of 28-32mm from the bottom of the quartz tube, and the biomass-based carbon membrane catalyst and the quartz plate are separated by quartz wool.

With the biochar membrane as the carrier and Ni and Co as the active components of the catalyst, the biomass-based carbon membrane catalyst loaded with Ni-Co active components was prepared by the co-impregnation method.

The preparation steps of the biochar membrane are as follows:

(1) Mud mixing: mix wood chips and reagents in a certain proportion, and knead them evenly in a kneader;

(2) Extrusion molding: Put the mud material into the hopper of the molding machine, and the mud material is squeezed into the mold under the action of the pressing rod, and the product can be obtained at the other end. The shape of the product depends on the internal shape of the extrusion nozzle of the mold. The original film obtained in this experiment has strong mass production capacity. By adjusting the extrusion pressure and other process parameters, a defect-free original film with smooth surface and regular shape is obtained.

(3) Drying: Constant temperature drying method is adopted. The drying process is to remove the solvent in the original film, let the original film solidify into a skeleton, and improve the strength of the original film for easy handling and carbonization. During the drying process, with the volatilization of the solvent , the original film will shrink, so the drying procedure must be strictly controlled to avoid defects during drying.

(4) Carbonization: put the dried original film into a carbonization furnace, raise the temperature to 940-960°C under the protection of nitrogen, and after constant temperature, naturally cool to room temperature to obtain a biomass carbon film. Put the dried original film into the carbonization furnace. In order to keep the original film shrinking naturally under the condition of thermal decomposition to obtain a flat carbon film, the pretreated original film was placed between two stone flakes, placed in a self-made fixture and used The powder tableting machine applies a positive pressure of 5MPa to evenly compress it and then tightens it with bolts, then puts it into the reactor, fixes the reactor in the middle of the constant temperature zone of the tubular furnace, and raises the temperature for carbonization under the protection of _N2 gas; the pyrolysis gas is At high temperature, the carrier gas is exported from the reactor into 20% H ₂ SO ₄ , cuproammonia solution and 10% ferrous sulfate solution to eliminate harmful gases such as NH ₃ , CO and HCN in the tail gas, and finally into the fume hood middle discharge.

The technical scheme of the present invention also includes that the reagent in step (1) is a mixture of a binder, a pore-forming agent, a wetting agent and a plasticizer, wherein the binder is carboxymethyl cellulose, and the pore-forming agent It is polyvinyl butyral, the plasticizer is dibutyl phthalate, and the wetting agent is dodecylbenzenesulfonic acid.

The technical solution of the present invention also includes that the ratio of the sawdust to the binder, pore-forming agent, wetting agent and plasticizer in step (1) is 8-10:1:1:1:1.

The technical solution of the present invention also includes that the carbonization process in step (4) is as follows: the flow rate of N ₂ gas is controlled to be 320-350mL·min ^-1 , the heating rate is 2.5-3.5°C·min ^-1 , and the temperature is first raised to 280-300°C , keep the temperature for 55-65 minutes, then raise the temperature to 550°C, and keep the temperature for 110-130 minutes, continue to heat up to different carbonization final temperatures of 940-950°C, and keep the temperature for 120-150 minutes, and finally cool naturally to room temperature under the protection of _N2 .

The preparation steps of the biomass-based carbon membrane catalyst loaded with Ni-Co active components are as follows:

(1) Immersion precipitation: The prepared biochar membrane was immersed in the mixed solution of Ni(NO ₃ ) ₂ 6H ₂ O and Co(NO ₃ ) ₂ 6H ₂ O for 1.5-2.5 hours, and then CO(NH ₂ ) Stir at room temperature for 0.4 to 0.6 hours, put the mixed system in a constant temperature water bath at 92 to 96° C., react at normal pressure for 0.4 to 0.6 hours, then precipitate begins to appear, and continue the constant temperature treatment for 3 to 5 hours to obtain a gel precipitate;

(2) Drying: filter the gel precipitate, and wash it successively with deionized water and absolute ethanol to remove unreacted reactants, and then place it in a drying oven at 110-130°C for 10-12 hours to remove free water and partially bound water to prepare catalyst precursor;

(3) Calcination: the catalyst precursor is placed in a _N2 atmosphere in a muffle furnace, and calcined at 500-550°C for 4-6 hours to obtain a biochar membrane loaded with Ni-Co active components;

(4) Reduction: Under a hydrogen atmosphere, the biomass-based carbon membrane obtained in step (3) is activated and reduced to obtain a biomass-based carbon membrane catalyst loaded with Ni-Co active components.

An experimental device for applying biomass membrane microwave reactors to methane reforming, including sequentially connected reactors, biomass membrane microwave reactors, three stub tuners, directional couplers, circulators, magnetic Control and power supply and control devices, the top of the reactor is connected to the methane tank and the carbon dioxide tank through the pipeline, the nitrogen tank is connected to the reactor through the pipeline, and the outlet pipeline at the bottom of the reactor is also connected to the steam generator, so The biomass membrane microwave reactor is also connected with a gas chromatograph.

An experimental method for methane reforming, using the above-mentioned biomass membrane microwave reactor applied to the experimental device for methane reforming, CH ₄ : CO ₂ : N ₂ : H ₂ O at a ratio of 1:1:3:3～ The ratio of 1.5:1.5:3:3 enters the reactor, and the gas after the reaction enters the assembled biomass membrane microwave reactor. After staying for 5s, the synthesis gas _H2 and CO can be obtained.

The beneficial effect of the present invention is that in the traditional methane reforming experiment, the heating is a conventional heating device, while the present invention uses a new type of biomass membrane microwave reactor, with a biomass charcoal film made of wood chips as a carrier, nickel Using cobalt as the active component as the catalyst, a biomass-based carbon membrane catalyst loaded with Ni-Co active components was prepared. This new catalyst overcomes the defects of weak mechanical properties and poor stability of conventional catalysts, and the new catalyst has good wave-absorbing performance; Put the prepared new catalyst in a quartz tube, assemble a new type of biomass membrane microwave reactor, assemble the microwave reactor in the methane reforming experimental device, and the methane reforming experimental device is used in the methane reforming experiment method, the reaction efficiency of this experiment is 20% higher than that of the conventional reaction device, there is no obvious carbon deposition, the synergistic reaction is strengthened, the ratio of _H2 to CO is increased from 0.83 to 1.10, the energy saving is 27%, the cost is reduced by 10%, and the conversion of _CH4 and _CO2 The efficiency can reach 95%, which significantly improves the conversion rate of methane and carbon dioxide, and is energy-saving and environmentally friendly.

Description of drawings

Fig. 1 is the schematic diagram of the carbonization process of biomass charcoal film among the present invention;

Figure 2 is a diagram of the methane reforming experimental device;

Among them, 1—methane tank; 2—carbon dioxide tank; 3—nitrogen tank; 4—steam generator; 5—mass flow controller; 6—reactor; 7—biomass membrane microwave reactor; 8—three short cuts Line tuner; 9—directional coupler; 10—circulator; 11—magnetron; 12—power supply and control device; 13—microwave power meter; 14—gas chromatograph; 15—MS, FID, TCD detector; 16—Computer.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

A biomass membrane microwave reactor, including a microwave heating device, a biomass-based carbon membrane catalyst and a quartz tube, the quartz tube containing the biomass-based carbon membrane catalyst is fixed to the microwave with a flange and a screw made of polytetrafluoroethylene. In the central area of the heating device, a porous quartz plate is set at a distance of 28-32mm from the bottom of the quartz tube, and the biomass-based carbon membrane catalyst and the quartz plate are separated by quartz wool.

With the biochar membrane as the carrier and Ni and Co as the active components of the catalyst, the biomass-based carbon membrane catalyst loaded with Ni-Co active components was prepared by the co-impregnation method.

As shown in Figure 2, the preparation steps of the biochar membrane are as follows:

(1) Mud mixing: Mix wood chips and reagents in a certain proportion, and knead them evenly in a kneader. The reagents are a mixture of binders, pore-forming agents, wetting agents and plasticizers. It is carboxymethyl cellulose, the pore-forming agent is polyvinyl butyral, the plasticizer is dibutyl phthalate, the wetting agent is dodecylbenzenesulfonic acid, and the wood chips and binder, making The ratio of pore agent, wetting agent and plasticizer is 8-10:1:1:1:1.

(2) Extrusion molding: Put the mud material into the hopper of the molding machine, and the mud material is squeezed into the mold under the action of the pressing rod, and the product can be obtained at the other end. The shape of the product depends on the internal shape of the extrusion nozzle of the mold. The original film obtained in this experiment has strong mass production capacity. By adjusting the extrusion pressure and other process parameters, a defect-free original film with smooth surface and regular shape is obtained.

(3) Drying: Constant temperature drying method is adopted. The drying process is to remove the solvent in the original film, let the original film solidify into a skeleton, and improve the strength of the original film for easy handling and carbonization. During the drying process, with the volatilization of the solvent , the original film will shrink, so the drying procedure must be strictly controlled to avoid defects during drying.

(4) Carbonization: Put the dried original film into a carbonization furnace, raise the temperature to 940-960°C under the protection of nitrogen, and after constant temperature, cool it down to room temperature naturally to obtain a biomass carbon film, as shown in Figure 1. Put the dried original film into the carbonization furnace. In order to keep the original film shrinking naturally under the condition of thermal decomposition to obtain a flat carbon film, the pretreated original film was placed between two stone flakes, placed in a self-made fixture and used Apply a positive pressure of 5MPa to the powder tablet press and tighten it with bolts evenly, then put it into the reactor 6, fix the reactor 6 in the middle of the constant temperature zone of the tubular furnace, heat up and carbonize under the protection of _N2 gas; thermal decomposition The gas is exported from the reactor 6 with the carrier gas at high temperature and successively enters 20% H ₂ SO ₄ , cuproammonia solution and 10% ferrous sulfate solution to eliminate harmful gases such as NH ₃ , CO and HCN that may be produced in the tail gas. Drain into a fume hood.

Among them, the carbonization process of step (4) is: the carbonization process of step (4) is: the flow rate of N ₂ gas is controlled at 320-350mL·min ^-1 , the heating rate is 2.5-3.5°C·min ^-1 , and the temperature is first raised to 280 ~300°C, keep the temperature constant for 55-65 minutes, then raise the temperature to 550°C, and keep the temperature constant for 110-130 minutes, continue to heat up to different carbonization final temperatures of 940-950°C, and keep the temperature constant for 120-150 minutes, and finally cool naturally to room temperature under the protection of _N2 .

The preparation steps of the biomass-based carbon membrane catalyst loaded with Ni-Co active components are as follows:

(1) Immersion precipitation: The prepared biochar membrane was immersed in the mixed solution of Ni(NO ₃ ) ₂ 6H ₂ O and Co(NO ₃ ) ₂ 6H ₂ O for 2 hours, then CO(NH ₂ ) was added at room temperature Stir for 0.5h, put the mixed system into a constant temperature water bath at 95°C, react at normal pressure for 0.5h, and then precipitate begins to appear, continue constant temperature treatment for 4h, and obtain a gel precipitate;

(2) Drying: filter the gel precipitate and wash it successively with deionized water and absolute ethanol to remove unreacted reactants, then place it in a drying oven at 120°C for 10 hours to remove free water and some Combined with water, the catalyst precursor is prepared;

(3) Calcination: the catalyst precursor is placed in a _N2 atmosphere in a muffle furnace, and calcined at 500 ° C for 5 hours to obtain a biochar film loaded with Ni-Co active components;

(4) Reduction: Under a hydrogen atmosphere, activate and reduce the biomass-based carbon membrane obtained in step (3) for 1 h to obtain a biomass-based carbon membrane catalyst loaded with Ni-Co active components.

An experimental device that applies a biomass membrane microwave reactor to methane reforming, as shown in Figure 2, includes a reactor 6, a biomass membrane microwave reactor 7, and a three-stub tuner 8 that are sequentially connected , directional coupler 9, circulator 10, magnetron 11 and power supply and control device 12, the top of reactor 6 connects methane tank 1 and carbon dioxide tank 2 through pipeline, nitrogen tank 3 is connected in reactor 6 through pipeline, reaction The outlet pipeline at the bottom of the device 6 is also connected with the steam generator 4, and the biomass membrane microwave reactor 7 is also connected with the gas chromatograph 14 equipped with MS, FID, TCD detector 15, and the gas chromatograph 14 is connected with a computer 16 Connection, the microwave power meter 13 is connected to the directional coupler 9, the methane tank 1, the carbon dioxide tank 2, the nitrogen tank 3 and the reactor 6 are all provided with a mass flow controller 5 on the connecting pipeline.

An experimental method for methane reforming. _The above _- mentioned _biomass membrane microwave reactor ₇ is applied to the experimental device for methane reforming. The ratio enters the reactor 6, and the gas after the reaction enters the assembled biomass membrane microwave reactor 7. After staying for 5s, the synthesis gas _H2 and CO can be obtained.

Example

(1) Preparation of biochar membrane

① Grind the wood chips to 80 mesh, and knead them evenly in the kneader with the binder, pore-forming agent, wetting agent and plasticizer in the ratio of 10:1:1:1:1, among which, the binder It is carboxymethyl cellulose, the pore-forming agent is polyvinyl butyral, the plasticizer is dibutyl phthalate, and the wetting agent is dodecylbenzenesulfonic acid;

②Put the mud material into the hopper of the 10T molding machine, and the mud material is squeezed into the mold under the action of the pressure rod 5MPa, and the original film with smooth surface and regular shape is obtained at the other end;

③The original film was dried at a constant temperature at 120°C, and the obtained honeycomb original film was dried for 4 days. During the drying process, the drying procedure must be strictly controlled to avoid defects in the original film;

④ In order to keep the natural shrinkage of the original film under thermal decomposition conditions to obtain a flat carbon film, place the pretreated original film flat between two stone flakes, place it in a self-made fixture, and apply a positive pressure of 5 MPa with a powder tablet press to compress it evenly Fasten it with bolts, then put it into a quartz container, fix the quartz container in the middle of the constant temperature zone of the tubular furnace, raise the temperature to 950°C at a rate of 3°C/min under the protection of _N2 , and cool it naturally after constant temperature pyrolysis to room temperature. The biochar membrane can be obtained.

(2) Catalysts for preparation of biomass-based carbon membranes loaded with Ni-Co active components

① Dissolve Ni(NO ₃ ) ₂ 6H ₂ O and Co(NO ₃ ) ₂ 6H ₂ O in deionized water at a molar ratio of 1:3 to prepare a mixed solution, and soak the obtained biomass-based membrane in this solution, Immerse at room temperature for 2 hours, stir at room temperature for 0.5 hours, put the mixed system in a constant temperature water bath at 95°C, and react at normal pressure for 0.5 hours. After 0.5 hours, precipitation begins to appear. Continue constant temperature treatment for 4 hours to obtain gel precipitation;

②Filtrate the precipitate, wash it with deionized water and absolute ethanol successively to remove unreacted reactants, and then place it in a drying oven at 110°C for 12 hours to remove free water and part of bound water to obtain a catalyst precursor body;

③The catalyst precursor is placed in a muffle furnace, and roasted for 5 hours under the condition of a roasting temperature of 500 ° C in an _N2 atmosphere;

④ After the calcined catalyst was reduced for 1 h under a hydrogen atmosphere, a Ni-Co-loaded biomass-based carbon membrane catalyst could be obtained.

(3) Assembly of biomass membrane microwave reactor

The microwave source of the microwave heating device used has 10 adjustable powers (0 ~ 1000W). The microwave used in this experiment is 1000W. The flange and screw made of polytetrafluoroethylene will hold the biomass-based carbon membrane catalyst with an inner diameter of 40mm and a height of 200mm. The quartz tube is fixed in the central area of the microwave heating device to complete the assembly of the biomass mode reactor.

(4) Methane reforming experiment

The biomass membrane microwave reactor 7 assembled in the above steps was installed in the methane reforming experiment shown in FIG. 2 .

(5) Experimental process

Feed CH ₄ /CO ₂ /N ₂ /H ₂ O into the reactor at a ratio of 1:1:3:3, and the reacted gas enters the assembled new biomass membrane microwave reactor 7, and the biomass membrane microwave reaction The temperature of the device 7 is controlled at 950°C, and the gas stays in the biomass membrane microwave reactor 7 for 5s to obtain the synthesis gas _H2 and CO.

(6) Test results

The synthetic gas composition H ₂ /CO=1.10 obtained after the experiment was measured, and its H ₂ and CO yields were increased by 32% compared with conventional devices; its reaction speed was also increased by 25% compared with conventional devices; the conversion rate of CH ₄ and CO ₂ was about 95% %; the energy utilization efficiency of composite reforming reaction is 97%; and there is no obvious carbon deposition in the process of preparing synthesis gas.

Of course, the above descriptions are not intended to limit the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or replacements made by those skilled in the art within the scope of the present invention shall also belong to the present invention. protection scope of the invention.

Claims (9)

1. A biomass membrane type microwave reactor, is characterized in that, comprises microwave heating device, biomass-based carbon membrane catalyst and quartz tube, with the flange and screw rod of polytetrafluoroethylene material, will be filled with biomass-based carbon membrane catalyst inside The quartz tube is fixed in the central area of the microwave heating device, and a porous quartz plate is set at a distance of 28-32mm from the bottom of the quartz tube. The biomass-based carbon membrane catalyst and the quartz plate are separated by quartz wool. 2. A kind of biomass membrane type microwave reactor as claimed in claim 1, is characterized in that, with biomass charcoal membrane as carrier, Ni and Co are the catalyst of active component, make loaded Ni-Co by co-impregnation method Biomass-based carbon membrane catalysts with active components. 3. A kind of biomass membrane type microwave reactor as claimed in claim 2, is characterized in that, the preparation step of described biomass charcoal membrane is as follows: (1) Mud mixing: mix wood chips and reagents in a certain proportion, and knead them evenly in a kneader; (2) Extrusion molding: Put the mud material into the hopper of the molding machine, adjust the process parameters, and obtain a defect-free original film with a smooth surface and regular shape; (3) Drying: Dry at a constant temperature at a certain temperature, strictly control the drying procedure, and avoid shrinkage defects of the original film during drying; (4) Carbonization: put the dried original film into a carbonization furnace, raise the temperature to 940-960°C under the protection of nitrogen, and after constant temperature, naturally cool to room temperature to obtain a biomass carbon film. 4. a kind of biomass membrane microwave reactor as claimed in claim 3, is characterized in that, the reagent in step (1) is the mixing agent of binding agent, pore forming agent, wetting agent and plasticizer, Wherein, the binder is carboxymethyl cellulose, the pore-forming agent is polyvinyl butyral, the plasticizer is dibutyl phthalate, and the wetting agent is dodecylbenzenesulfonic acid. 5. a kind of biomass membrane type microwave reactor as claimed in claim 3 is characterized in that, the proportioning of sawdust in step (1) and binding agent, pore-forming agent, wetting agent and plasticizer is 8～10:1:1:1:1. 6. A biomass membrane microwave reactor as claimed in claim 1, characterized in that, the carbonization process in step (4) is as follows: the flow rate of N ₂ gas is controlled to be 320-350mL·min ^-1 , the heating rate is 2.5-3.5°C·min ^-1 , first raise the temperature to 280-300°C, keep the temperature constant for 55-65 minutes, then raise the temperature to 550°C, and keep the temperature constant for 110-130 minutes, continue to heat up to different final carbonization temperatures of 940-950°C, and keep the temperature at 120 ~150min, and finally cooled naturally to room temperature under the protection of _N2 . 7. A kind of biomass membrane microwave reactor as claimed in claim 1, is characterized in that, the preparation step of the biomass-based carbon membrane catalyst of loading Ni-Co active component is as follows: (1) Immersion precipitation: The prepared biochar membrane was immersed in the mixed solution of Ni(NO ₃ ) ₂ 6H ₂ O and Co(NO ₃ ) ₂ 6H ₂ O for 1.5-2.5 hours, and then CO(NH ₂ ) Stir at room temperature for 0.4 to 0.6 hours, put the mixed system in a constant temperature water bath at 92 to 96° C., react at normal pressure for 0.4 to 0.6 hours, then precipitate begins to appear, and continue the constant temperature treatment for 3 to 5 hours to obtain a gel precipitate; (2) Drying: filter the gel precipitate, and wash it successively with deionized water and absolute ethanol to remove unreacted reactants, and then place it in a drying oven at 110-130°C for 10-12 hours to remove free water and partially bound water to prepare catalyst precursor; (3) Calcination: the catalyst precursor is placed in a _N2 atmosphere in a muffle furnace, and calcined at 500-550°C for 4-6 hours to obtain a biochar membrane loaded with Ni-Co active components; (4) Reduction: Under a hydrogen atmosphere, the biomass-based carbon membrane obtained in step (3) is activated and reduced to obtain a biomass-based carbon membrane catalyst loaded with Ni-Co active components. 8. An experimental device applying the biomass membrane microwave reactor described in any one of claims 1 to 7 to methane reforming, characterized in that it comprises sequentially connected reactors, biomass membrane microwave reactors tuner, three stub tuner, directional coupler, circulator, magnetron, power supply and control device, the top of the reactor is connected to the methane tank and the carbon dioxide tank through the pipeline, and the nitrogen tank is connected to the reactor through the pipeline In the above, the outlet pipeline at the bottom of the reactor is also connected to a steam generating device, and the biomass membrane microwave reactor is also connected to a gas chromatograph. 9. An experimental method for methane reforming, using the methane reforming experimental device described in claim 8, characterized in that CH ₄ : CO ₂ : N ₂ : H ₂ O is mixed at a ratio of 1:1:3:3 ～The ratio of 1.5:1.5:3:3 enters the reactor. After the reaction, the gas enters the assembled biomass membrane microwave reactor. The temperature of the biomass membrane microwave reactor is controlled at 950 ° C. The gas reacts in the biomass membrane microwave The device stays for 5s, and the synthesis gas _H2 and CO can be obtained.