Methane catalytic reforming hydrogen production fuel cell system separated by hydrate method

Abstract

The invention relates to the technical field of fuel cells, and particularly provides a catalytic reforming hydrogen production fuel cell system for methane separation by a hydrate method. The cell system comprises a methane hydrate reaction module, a methane catalytic reforming module, a fuel cell module and a tail gas collection module. In the coal mining process, due to limitation of technical reasons, most low-concentration coal mine gas can be directly emptied, so that resource waste and environment damage are caused; in recent years, a hydrate technology is widely concerned to be used for separating and storing gas, and the method is relatively safe and can effectively reduce the risk of gas explosion. According to the invention, the low-concentration gas is separated and purified according to the temperature and pressure difference under the condition that different components in the low-concentration gas form hydrates, high-concentration CH4 is used as fuel and enters the fuel cell module, chemical energy is converted into electric energy, and the electric energy is provided for coal mine production and living places; the utilization scene of the low-concentration gas is expanded; and the utilization efficiency of the low-concentration gas is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of fuel cells, and in particular to a fuel cell system for hydrogen production by catalytic reforming of methane separated by the hydrate method. Background Art

[0002] Due to reasons such as the large total amount of low-concentration gas, low concentration, large concentration fluctuations, and relatively lagging relevant supporting policies and measures, the overall utilization rate is only about 40%, and the rest are directly discharged into the air, causing serious waste of resources.

[0003] In recent years, the hydrate technology for separating and storing gas has received extensive attention. The treatment process of this method is relatively safe and can effectively reduce the risk of gas explosion.

[0004] To solve the problem of direct evacuation of low-concentration coal mine gas and reduce the risk of gas explosion, the present invention is based on the separation and purification of low-concentration gas by the hydrate method. The separated high-concentration CH 4 enters the fuel cell for power generation, providing electrical energy for coal mine production and living places. This not only improves the utilization rate of low-concentration gas but also effectively improves the atmospheric environment. Summary of the Invention

[0005] The technical problem to be solved by the present invention is: to overcome the deficiencies in the prior art and provide a fuel cell system for hydrogen production by catalytic reforming of methane separated by the hydrate method. According to the temperature and pressure differences of the hydrate formation conditions of different components in low-concentration gas, the present invention separates and purifies low-concentration gas. The high-concentration CH 4 enters the fuel cell module as fuel, converts chemical energy into electrical energy, provides electrical energy for coal mine production and living places, expands the utilization scenario of low-concentration gas and improves its utilization efficiency.

[0006] The technical solution adopted by the present invention to solve its technical problems is:

[0007] A fuel cell system for hydrogen production by catalytic reforming of methane separated by the hydrate method, comprising a methane hydrate reaction module, a methane catalytic reforming module, a fuel cell module, and a tail gas collection module;

[0008] The low-concentration gas raw material module is used to provide low-concentration gas;

[0009] The methane hydrate reaction module includes a pressure control and detection unit, a temperature control and detection unit, a hydrate formation unit, and a hydrate decomposition unit;

[0010] The methane catalytic reforming module includes a catalytic reforming reaction unit, a gas flow control unit, and a temperature monitoring unit;

[0011] The fuel cell module includes a fuel cell reaction unit and a heat dissipation unit;

[0012] The tail gas collection module includes a gas separation unit and a gas storage unit.

[0013] Further, in the methane hydrate reaction module, the reaction pressure of the hydrate formation unit is 5 - 7 MPa, the reaction temperature is 1 - 5 °C, and hydrates are formed under stirring conditions. The formation process is accelerated by adding promoters; the promoters include thermodynamic promoters, kinetic promoters, and porous materials; the reaction temperature of the hydrate decomposition unit is 5 - 10 °C, and the reaction pressure is atmospheric pressure.

[0014] Further, the thermodynamic promoters are selected from one or more of tetrahydrofuran, tetrabutylammonium bromide, 1,3 - dioxolane, and cyclopentane; the kinetic promoters are selected from one or more of sodium dodecyl sulfate, leucine, sodium lignosulfonate, and rhamnolipid; the porous materials are selected from one or more of carbon nanotubes, activated carbon, porous foam metal, and aluminum nitride foam ceramics.

[0015] Further, in the methane catalytic reforming module, the catalyst of the catalytic reforming reaction unit is one or two of bimetallic alloy catalysts and trimetallic alloy catalysts.

[0016] Further, the bimetallic alloy catalyst is selected from one of Ni - Fe alloy catalysts, Ni - Pd alloy catalysts, and Ni - Cu alloy catalysts, and the trimetallic catalyst is Fe - Ni - Al alloy catalyst.

[0017] Further, in the fuel cell module, the anode electrode material of the fuel cell reaction unit is nickel - zirconia cermet or a mixture of nickel and yttria - zirconia, with the nickel content being 30% - 35%; the catalyst material is one of Pt - based catalyst layers, non - noble metal catalysts, and non - metal catalysts, and the catalyst material is used to optimize the electrical conductivity and thermal expansion matching of electrons and oxides, resist CO poisoning and carbon deposition;

[0018] The cathode support tube of the fuel cell reaction unit is yttria - zirconia, and the cathode material of the fuel cell reaction unit is a composite material made of strontium - doped lanthanum manganate and nickel oxide / yttria - stabilized zirconia;

[0019] The electrolyte of the fuel cell reaction unit is yttria - doped zirconia, samarium - doped ceria, or gadolinium - doped ceria.

[0020] Further, the Pt - based catalyst layer is selected from one of Pt / C, PtCo / C, and PtCoMn / C; the non - noble metal catalyst is Fe - N - C or Co - N - C; the non - metal catalyst is P - doped C or N - doped C.

[0021] Furthermore, in the fuel cell module, the heat dissipation unit is a heat dissipation pipe and a fan.

[0022] Furthermore, in the tail gas collection module, the gas separation unit separates the tail gas by the hydrate method; for the nitrogen separated from the low-concentration gas, the gas storage unit stores it by compression; the tail gas collection module preferably uses the hydrate method to capture and store carbon dioxide.

[0023] Furthermore, this methane catalytic reforming hydrogen production fuel cell system using the hydrate method for separation also includes an electrolytic hydrogen production module. A part of the water produced by the methane hydrate reaction module enters the electrolytic hydrogen production module as a raw material, and the hydrogen produced by the electrolytic hydrogen production module enters the fuel cell module to participate in the negative electrode reaction.

[0024] The beneficial effects of the present invention are as follows: The present invention is reasonably designed and has the following advantages:

[0025] (1) By injecting low-concentration gas into the hydrate reactor and separating and purifying it in the form of hydrate, the concentrated high-concentration methane gas hydrate decomposes to produce methane and water. The methane and water enter the methane reforming reactor to react and produce hydrogen, and this part of hydrogen enters the negative electrode of the fuel cell to participate in the reaction; a part of the water produced by the decomposition of the hydrate enters the electrolytic hydrogen production system, and the generated H 2 enters the negative electrode of the hydrogen fuel cell to participate in the reaction; the N 2 +O 2 mixed gas enters the positive electrode of the fuel cell to participate in the reaction;

[0026] (2) The hydrate method can reduce the risk of explosion of low-concentration gas, and the gas release rate of CH 4 hydrate decomposition in the porous material is relatively gentle, with less impact on the container, which belongs to a relatively safe and economical gas hydrate storage and transportation technology;

[0027] (3) By separating and purifying low-concentration gas by the hydrate method, supplemented by the H 2 produced by catalytic reforming and entering the fuel cell to convert chemical energy into electrical energy; at the same time, the remaining water is used to produce H 2 through the water electrolysis device and enters the hydrogen fuel cell, realizing the synergistic and efficient utilization of CH 4 and water in methane hydrate in hydrogen fuel cell power generation, providing electrical energy supply for coal mine production and surrounding living places; the present invention not only solves the problem of waste of resources caused by direct discharge of low-concentration coal mine gas, but also improves the atmospheric environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0029] Figure 1 is the structural schematic diagram of the present invention;

[0030] Figure 2 is the structural schematic diagram of the hydrate reactor;

[0031] Figure 3 is Figure 2 the cross-sectional view taken along the A-A direction in

[0032] Figure 4 is the temperature and pressure curve graph of the gas released by the decomposition of methane hydrate in the different pore density copper foam carriers in Example 1.

[0033] In the figure: 1. low-concentration gas injection tank, 2. hydrate reactor, 3. methane reforming catalytic reactor, 4. hydrogen fuel cell, 5. air compressor, 6. tail gas capture and separation device, 7. hydrogen production electrolytic cell;

[0034] 21. reactor housing, 22. cooling circulation pipeline, 23. double stirring paddles, 24. motor, 25. pressure transmitter, 26. temperature sensor, 27. inlet gas pipeline, 28. exhaust gas pipeline, 29. drain pipeline, 30. porous foam metal layer, 31. gas hydrate. Specific Embodiments

[0035] It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present application belongs.

[0036] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form also includes the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0037] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative work shall fall within the protection scope of the present invention.

[0038] A fuel cell system for hydrogen production by catalytic reforming of methane separated by the hydrate method includes a methane hydrate reaction module, a methane catalytic reforming module, a fuel cell module, and a tail gas collection module; a low-concentration gas raw material module is used to provide low-concentration gas; the methane hydrate reaction module includes a pressure control and detection unit, a temperature control and detection unit, a hydrate formation unit, and a hydrate decomposition unit; the methane catalytic reforming module includes a catalytic reforming reaction unit, a gas flow control unit, and a temperature monitoring unit; the fuel cell module includes a fuel cell reaction unit and a heat dissipation unit; the tail gas collection module includes a gas separation unit and a gas storage unit.

[0039] As Figure 1 shown, this fuel cell system for hydrogen production by catalytic reforming of methane separated by the hydrate method includes a low-concentration gas injection tank 1. The low-concentration gas injection tank 1 is connected to a hydrate reactor 2 through a pipeline. The top of the hydrate reactor 2 has two gas pipelines. One of the gas pipelines is connected to a methane reforming catalytic reactor 3, and the other gas pipeline is connected to a hydrogen fuel cell 4; the bottom of the hydrate reactor 2 has two liquid pipelines. One of the liquid pipelines is connected to the methane reforming catalytic reactor 3, and the other liquid pipeline is connected to a hydrogen production electrolytic cell 7; the tail gas of the methane reforming catalytic reactor 3 and the hydrogen fuel cell 4 is collected and processed by a tail gas capture and separation device 6. The hydrogen fuel cell 4 is also connected to an air compressor 5 for supplementing oxygen.

[0040] The working process of the above fuel cell system for hydrogen production by catalytic reforming of methane separated by the hydrate method is as follows: After the low-concentration gas is extracted, it is injected into the low-concentration gas injection tank 1, enters the hydrate reactor 2 through the gas pipeline, the temperature and pressure are set, a promoter is added to the hydrate reactor 2, and cyclic refrigeration is carried out using the circulation system. Under the condition of stirring, CH 4 hydrate is generated. The high-concentration N 2 separated by the hydrate method and O 2 as well as the O 2 compressed by the air compressor 5 enter the positive electrode reaction of the fuel cell 4. Then, the methane hydrate is heated up, and the CH 4 hydrate decomposes to produce CH 4 and water. CH 4 and water vapor generate H 2, enter the negative electrode of the fuel cell 4 through the gas pipeline for reaction. The hydrogen fuel cell directly converts chemical energy into electrical energy through an electrochemical reaction, providing electrical energy supply for coal mine production and living places.

[0041] The formation of methane hydrate is essentially a gas-liquid-solid phase change process, accompanied by the generation of a large amount of hydrate heat (such as CH 4 The heat of hydrate is 438.54 ± 13.78 kJ·kg-1). An efficient hydration process includes sufficient gas-liquid contact (mass transfer), rapid nucleation and growth (reaction), and timely removal of hydrate heat (heat transfer). The hydrate method can enrich and purify CH in low-concentration gas. The whole process is carried out in a low-temperature aqueous phase, reducing the risk of explosion of low-concentration gas. After separating and purifying the low-concentration gas, catalytic reforming is carried out to produce hydrogen, and then power generation is carried out through a fuel cell, which can achieve multiple purposes such as saving resources, reducing environmental pollution, and adjusting the energy structure. 4

[0042] In the methane hydrate reaction module, the reaction pressure of the hydrate formation unit is 5 - 7 MPa, and the reaction temperature is 1 - 5 °C. Hydrate is formed under stirring conditions, and the formation process is accelerated by adding promoters; the promoters include thermodynamic promoters, kinetic promoters, and porous materials; the reaction temperature of the hydrate decomposition unit is 5 - 10 °C, and the reaction pressure is atmospheric pressure.

[0043] The thermodynamic promoter is selected from one or more of tetrahydrofuran (5.56 mol%), 1,3-dioxolane (5.56 mol%), and cyclopentane (5.6 mol%); the kinetic promoter is selected from one or more of sodium dodecyl sulfate SDS (0.035 - 0.15 wt%), leucine Leucine (0.1 - 1.0 wt%), sodium lignosulfonate SL (0.0015 mol / L), and rhamnolipid Rha (100 - 800 mg / L); the porous material (a porous columnar material with the inner diameter of the hydrate reaction kettle as the diameter) is selected from one or more of carbon nanotubes, activated carbon, porous foam metal, and aluminum nitride foam ceramics.

[0044] Figure 2 As shown, the hydrate reaction kettle 2 includes a reaction kettle housing 21. The outer wall of the reaction kettle housing 21 is provided with a cooling circulation pipeline 22, the inner wall of the reaction kettle housing 21 is provided with a porous foam metal layer 30, and the inner cavity of the reaction kettle housing 21 is filled with gas hydrate 31. The top of the reaction kettle housing 21 is provided with an air inlet pipeline 27 and an exhaust pipeline 28. A pressure transmitter 25 is installed on the air inlet pipeline 27, and a temperature sensor 26 is installed on the reaction kettle housing 21. A double stirrer 23 is installed in the inner cavity of the reaction kettle housing 21. The double stirrer 23 is driven by a motor 24, and the motor 24 is installed outside the reaction kettle housing 21.

[0045] In the hydrate reactor 2, the stirring method is double stirring paddles 23; the thermodynamic promoter can reduce the phase equilibrium conditions of gas hydrates (shift towards room temperature and low pressure, with milder formation conditions); the kinetic promoter improves gas consumption by increasing the solubility of gas in a large amount of water and by increasing the permeation rate in the hydrate layer formed during hydrate formation; the porous material (porous foam metal layer 30) accelerates hydrate formation by increasing the gas-liquid contact area and enhancing the heat and mass transfer processes of hydrates.

[0046] Using a porous material as the carrier for the formation and storage of gas hydrates, when the gas hydrates are decomposed by heating to release gas, compared with the hydrates without a porous carrier, the gas release rate is milder and the high-pressure impact on the container is smaller, providing a safe and economical technology for the formation and decomposition of gas hydrates.

[0047] Methane hydrates decompose by heating in the hydrate reactor 2, and the decomposed CH 4 and water generate H 2 through the methane reforming catalytic reactor 3. The hydrogen fuel cell 4 uses the H 2 produced by the methane reforming catalytic reactor 3 and the O 2 separated by the hydrate method, as well as the O 2 produced by the air compressor 5 to participate in the reaction of the hydrogen fuel cell 4 to generate electric energy and provide power supply.

[0048] In the catalytic reforming reaction unit, the gas flow rate of the methane reforming catalytic reactor 3 is controllable, the outlet steam is adjustable, the steam generation is stable and continuous, and the outlet pipeline is heated and temperature-controlled to prevent condensation; the steam generation measures the liquid water flow rate through a precision constant flow pump.

[0049] In the methane catalytic reforming module, the catalyst of the catalytic reforming reaction unit is one or two of bimetallic and trimetallic alloy catalysts. The bimetallic and trimetallic alloy catalysts optimize the electronic and structural modification of bimetallic and trimetallic catalysts through alloy formation to obtain higher stability. Specifically, bimetallic catalysts such as Ni-Fe, Ni-Pd, Ni-Cu alloy catalysts, and trimetallic catalysts such as Fe-Ni-Al alloy catalysts can be used.

[0050] In the catalytic reforming reaction unit, CH 4 reacts with water vapor under high temperature and high pressure to generate CO and H 2 . The main way to produce hydrogen-rich syngas industrially is through natural gas steam reforming. In recent years, using CH 4 steam reforming to produce hydrogen for fuel cells has also become a research hotspot. The CH 4 steam reforming reaction equation is: CH 4 +H 2 O → 3H 2+CO.

[0051] A part of the water generated by the hydrate reactor 2 enters the hydrogen production electrolyzer 7, and the generated H 2 enters the hydrogen fuel cell 4 to participate in the negative electrode reaction, realizing CH 4 and the synergistic utilization of water in hydrogen fuel cell power generation.

[0052] In the fuel cell module, the anode electrode material of the fuel cell reaction unit is nickel-zirconia cermet, or a mixture of nickel and yttria-stabilized zirconia, where the nickel content is 30% - 35%; the catalyst material is one of a Pt-based catalyst layer, a non-precious metal catalyst, and a non-metal catalyst. The catalyst material is used to optimize the electrical conductivity and thermal expansion matching of electrons and oxides, and resist CO poisoning and carbon deposition. The Pt-based catalyst layer is selected from one of Pt / C, PtCo / C, and PtCoMn / C; the non-precious metal catalyst is Fe-N-C, or Co-N-C; the non-metal catalyst is P-doped C, or N-doped C.

[0053] The cathode support tube of the fuel cell reaction unit is yttria-stabilized zirconia, and the cathode material of the fuel cell reaction unit is a composite material made of strontium-doped lanthanum manganite and nickel oxide / yttria-stabilized zirconia; the electrolyte of the fuel cell reaction unit is yttria-doped zirconia, samarium-doped ceria (SDC), or gadolinium-doped ceria (GDC).

[0054] In the hydrogen fuel cell 4, the oxygen supply system separates O from the low-concentration coal mine gas through hydrates 2 and the O generated by the air compressor 5 2 maintains the progress of the positive electrode reaction of the fuel cell. When the oxygen separated by the hydrate method is insufficient, the air compressor 5 is started for oxygen supply.

[0055] Reaction principle of the hydrogen fuel cell 4: O 2 diffuses to the cathode surface and is reduced to oxygen ions (O 2- ) at the cathode. The reaction is O 2 + 4e- → 2O 2- . Driven by the oxygen concentration difference, O 2- reaches the anode through the dense electrolyte and reacts with H 2 to generate water and release electrons. The reaction is 2H 2 + 2O 2- → 2H 2 O + 4e-. The electrons flow through the external circuit to the cathode to form a loop, and then an electric current is generated.

[0056] The power generation efficiency of the hydrogen fuel cell 4 can reach more than 50%, which is determined by the conversion properties of the fuel cell. It directly converts chemical energy into electrical energy without going through the intermediate conversion of thermal energy and mechanical energy.

[0057] In the fuel cell module of the present invention, the heat dissipation unit mainly relies on the fuel cell radiator to work. When the temperature of the fuel cell reaches the set threshold, the radiator starts to work, absorbs the heat emitted from the fuel cell through the heat dissipation pipe, and is also equipped with a fan. By rotating the fan blades, the heat dissipation pipe and the fuel cell are cooled.

[0058] The gas mainly collected by the tail gas collection module is N separated from low-concentration gas 2 and CH 4 CO generated by catalytic reforming 2 and CO. The present invention preferentially uses the hydrate method to separate and apply these several gases.

[0059] Example 1

[0060] After the low-concentration gas is extracted, it is injected into the hydrate reactor 2. Under the condition of stirring (600 r / min), by adding tetrahydrofuran (5.56 mol%), rhamnolipid (500 mg / L), and porous copper foam, the formation of CH hydrate is accelerated. 4 After the hydrate is formed, the gas (high-concentration N 2 and O 2 ) in the hydrate reactor 2 and the air generated by the air compressor 5 are sent to the positive electrode of the hydrogen fuel cell 4; CH 4 The hydrate is decomposed by heating treatment, and the CH and part of the water generated are sent to the methane reforming catalytic reactor 3 for catalytic reforming to produce H 4 , and the generated H 2 is sent to the negative electrode of the hydrogen fuel cell 4; part of the water generated by the decomposition of the hydrate enters the hydrogen production electrolytic cell 7, and the generated H 2 enters the negative electrode of the hydrogen fuel cell 4; the tail gas enters the tail gas capture and separation device 6. The temperature and pressure changes of the gas released by the decomposition of methane hydrate in different pore density copper foam carriers are as 2 shown. Figure 4 shown.

[0061] The pressure transmitter 25 and the temperature sensor 26 provide the main data basis for the formation and decomposition of CH hydrate; the pressure transmitter 25 is used to control the pressure of the reactor (6 MPa) in real time, and the temperature monitoring unit is used to control the temperature of the reactor (6 °C) in real time. 4 The pressure transmitter 25 and the temperature sensor 26 provide the main data basis for the formation and decomposition of CH hydrate; the pressure transmitter 25 is used to control the pressure of the reactor (6 MPa) in real time, and the temperature monitoring unit is used to control the temperature of the reactor (6 °C) in real time.

[0062] The hydrogen fuel cell 4 is supplied with H generated by the methane reforming catalytic reactor 3 2 , H electrolytically produced by the decomposition of the hydrate 2 and O separated by the hydrate method 2 and O generated by the air compressor 5 2An electrochemical reaction is carried out to directly convert the chemical energy of the fuel into electrical energy for use in coal mine production and living areas. At the same time, the reaction of the hydrogen fuel cell 4 is an exothermic reaction. When the reaction proceeds, the heat dissipation system starts to operate, and the heat generated by the battery reaction is removed in a timely manner through the heat dissipation pipes and the heat dissipation fan.

[0063] The tail gas capture and separation device 6 includes a gas capture and separation unit and a gas storage unit. The hydrate method is preferably used for gas separation of the tail gas, and high-concentration N 2 It is stored and utilized by compression method, CO 2 The hydrate method is preferably used for capture and storage.

[0064] Example 2

[0065] The combustible ice (natural gas hydrate) in the deep sea area and the permafrost area is mined and utilized. The combustible ice is heated and decomposed in the hydrate reactor 2, and the required O 2 is supplied by an air compressor, and other conditions are the same as those in Example 1

[0066] In summary, the design of the present invention is reasonable and has the following advantages:

[0067] (1). The low-concentration gas is injected into the hydrate reactor and separated and purified in the form of hydrate. The concentrated high-concentration methane gas hydrate decomposes to produce methane and water. The methane and water enter the methane reforming reactor to react to produce hydrogen, and this part of hydrogen enters the negative electrode of the fuel cell to participate in the reaction; part of the water produced by the decomposition of the hydrate enters the electrolytic hydrogen production system, and the produced H 2 enters the negative electrode of the hydrogen fuel cell to participate in the reaction; the N 2 +O 2 mixed gas enters the positive electrode of the fuel cell to participate in the reaction;

[0068] (2). The hydrate method can reduce the risk of explosion of low-concentration gas, and the gas release rate of CH 4 in the porous material during the decomposition of the hydrate is relatively gentle, and the impact on the container is small. It belongs to a relatively safe and economical storage and transportation technology for gas hydrate;

[0069] (3). By separating and purifying the low-concentration gas by the hydrate method and supplementing the H 2 produced by catalytic reforming to enter the fuel cell to convert chemical energy into electrical energy; at the same time, the residual water is passed through the water electrolysis device to produce H 2 to enter the hydrogen fuel cell, realizing the synergistic and efficient utilization of CH 4 and water in the methane hydrate in hydrogen fuel cell power generation, providing electrical energy supply for coal mine production and surrounding living areas; the present invention not only solves the problem of resource waste caused by the direct discharge of low-concentration coal mine gas, but also can improve the atmospheric environment.

[0070] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation, characterized in that: It includes a methane hydrate reaction module, a methane catalytic reforming module, a fuel cell module and an exhaust gas collection module; The methane hydrate reaction module includes a pressure control detection unit, a temperature control detection unit, a hydrate generation unit and a hydrate decomposition unit; The methane catalytic reforming module includes a catalytic reforming reaction unit, a gas flow control unit and a temperature monitoring unit; The fuel cell module includes a fuel cell reaction unit and a heat dissipation unit; The tail gas collection module includes a gas separation unit and a gas storage unit.

2. A fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation according to claim 1, characterized in that: In the methane hydrate reaction module, the reaction pressure of the hydrate formation unit is 5-7 MPa, the reaction temperature is 1-5°C, and hydrates are formed under stirring conditions, and the formation process is accelerated by adding a promoter; the promoter includes a thermodynamic promoter, a kinetic promoter and a porous material; The reaction temperature of the hydrate decomposition unit is 5-10° C., and the reaction pressure is atmospheric pressure.

3. A fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation according to claim 2, characterized in that: The thermodynamic promoter is selected from one or more of tetrahydrofuran, tetrabutylammonium bromide, 1,3-dioxolane and cyclopentane; the kinetic promoter is selected from one or more of sodium dodecyl sulfate, leucine, sodium lignin sulfonate and rhamnolipid; the porous material is selected from one or more of carbon nanotubes, activated carbon, porous foam metal and aluminum nitride foam ceramic.

4. A fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation according to claim 1, characterized in that: In the methane catalytic reforming module, the catalyst of the catalytic reforming reaction unit is one or both of a bimetallic alloy catalyst and a trimetallic alloy catalyst.

5. A fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation according to claim 4, characterized in that: The bimetallic alloy catalyst is selected from one of a Ni-Fe alloy catalyst, a Ni-Pd alloy catalyst and a Ni-Cu alloy catalyst, and the trimetallic catalyst is a Fe-Ni-Al alloy catalyst.

6. A fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation according to claim 1, characterized in that: In the fuel cell module, the anode electrode material of the fuel cell reaction unit is nickel-zirconia metal ceramic, or a mixture of nickel and yttria-zirconia, wherein the nickel content is 30% to 35%; the catalyst material is one of a Pt-based catalyst layer, a non-precious metal catalyst and a non-metal catalyst, and the catalyst material is used to optimize the conductivity and thermal expansion matching of electrons and oxides, and resist CO poisoning and carbon deposition; The cathode support tube of the fuel cell reaction unit is yttria-zirconia, and the cathode material of the fuel cell reaction unit is a composite material made of strontium-doped lanthanum manganate and nickel oxide / yttria-stabilized zirconia; The electrolyte of the fuel cell reaction unit is yttria-doped zirconium oxide, samarium-doped ceria or gadolinium-doped ceria.

7. A fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation according to claim 6, characterized in that: The Pt-based catalyst layer is selected from one of Pt / C, PtCo / C, and PtCoMn / C; the non-precious metal catalyst is Fe-NC or Co-NC; the non-metal catalyst is P-doped C or N-doped C.

8. The fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation according to claim 1, characterized in that: In the fuel cell module, the heat dissipation unit is a heat dissipation pipe and a fan.

9. A fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation according to claim 1, characterized in that: In the tail gas collection module, the gas separation unit separates the tail gas using a hydrate method; The gas storage unit uses compression to store nitrogen separated from low-concentration gas; the tail gas collection module preferably uses the hydrate method to capture and store carbon dioxide.

10. A fuel cell system for producing hydrogen by catalytic reforming of methane through hydrate separation according to claim 1, characterized in that: It also includes an electrolytic hydrogen production module. Part of the water produced by the methane hydrate reaction module enters the electrolytic hydrogen production module as a raw material, and the hydrogen produced by the electrolytic hydrogen production module enters the fuel cell module to participate in the negative electrode reaction.

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