Double-membrane recombination hydrogen production reactor and hydrogen production method

Abstract

The application provides a double-membrane recombination hydrogen production reactor and a hydrogen production method, and belongs to the field of fuel cells.The double-membrane recombination hydrogen production reactor comprises a reaction chamber, a deoxygenation fiber bundle, a dehydrogenation fiber bundle and a gasification unit, the reaction chamber provides a reaction space for hydrogen-containing compounds and water, the dehydrogenation fiber bundle and the deoxygenation fiber bundle are arranged in the reaction chamber, the deoxygenation fiber bundle is used for separating oxygen from air, and the gasification unit comprises a first heat exchanger, a second heat exchanger and a third heat exchanger which are sequentially connected, the hydrogen-containing compounds and water sequentially flow through the third heat exchanger, the second heat exchanger and the first heat exchanger and are heated and gasified, and the dehydrogenation fiber bundle is used for dehydrogenating the heated hydrogen-containing compounds and water.Compared with the prior art, the application solves the problems of the prior art, such as complex structure, high processing cost, low heat and mass transfer efficiency, slow response speed and impurities in generated hydrogen.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of fuel cells, and more particularly relates to a double-membrane reforming hydrogen production reactor and a hydrogen production method. BACKGROUND

[0002] Fuel cells are a new type of clean energy technology, which has the advantages of energy saving, high efficiency and environmental friendliness, and has broad application prospects in distributed power generation, mobile power supply, transportation and other fields. However, the high cost and low safety in the process of high-purity hydrogen production and high-pressure hydrogen transportation limit the commercial application of fuel cell technology.

[0003] At present, large-scale production of hydrogen mainly relies on the reforming conversion of hydrocarbons. Among them, steam reforming uses steam as a reforming medium, which has a high hydrogen production rate, but steam reforming is an endothermic reaction that requires external heating and has a slow start. The autothermal reforming method introduces oxygen into the steam reforming reaction to provide heat through the partial oxidation of hydrogen production raw materials, achieving self-heating and rapid response of the system. However, due to the use of air as the oxygen source in practical applications, a large amount of impurities such as nitrogen in the air that do not participate in the reaction need to be additionally provided with a separation device. SUMMARY

[0004] The purpose of the present application is to provide a double-membrane reforming hydrogen production reactor to solve the problems of complex structure, high processing cost, low heat and mass transfer efficiency, slow response speed and the presence of impurities in the generated hydrogen of the traditional reforming hydrogen production reactor.

[0005] To achieve the above purpose, the technical scheme adopted by the present application is to provide a double-membrane reforming hydrogen production reactor, comprising:

[0006] a reaction chamber, which provides a reaction space for hydrogen-containing compounds, water and oxygen;

[0007] a dehydrogenation fiber bundle and a deoxygenation fiber bundle arranged in the reaction chamber, the deoxygenation fiber bundle being used to separate oxygen from air;

[0008] a gasification unit comprising a first heat exchanger, a second heat exchanger and a third heat exchanger connected in sequence; wherein the hot fluid inlet of the first heat exchanger is connected to the tail gas outlet of the reaction chamber, the hot fluid inlet of the second heat exchanger is connected to the hydrogen outlet of the reaction chamber, and the hot fluid inlet of the third heat exchanger is connected to the deoxygenated air outlet of the reaction chamber; the hydrogen-containing compounds and water are heated and gasified by flowing through the first heat exchanger, the second heat exchanger and the third heat exchanger in sequence, and the heated hydrogen-containing compounds and water enter the reaction chamber and react with oxygen, and the dehydrogenation fiber bundle dehydrogenates the high-temperature hydrogen-containing compounds after the reforming.

[0009] In an implementable manner, the double-membrane recombination hydrogen production reactor further comprises a raw material supply unit configured to supply a raw material containing hydrocarbons and water.

[0010] In an implementable manner, the reaction chamber comprises an upper shell, a reactor shell, and a lower shell arranged in sequence along a reaction path; the upper shell is provided with an air inlet, the reactor shell is provided with a gasification material inlet and a reaction tail gas outlet, and the lower shell is provided with a pure nitrogen gas outlet and a hydrogen gas outlet; the deoxygenation fiber bundle is arranged between the upper shell and the reactor shell, the air inlet is communicated with the air inlet, and the permeation side of the deoxygenation fiber bundle is connected to the inner cavity of the reactor shell; the dehydrogenation fiber bundle is arranged in the inner cavity of the reactor shell, and the permeation side of the dehydrogenation fiber bundle is communicated with the hydrogen gas outlet.

[0011] In an implementable manner, the dehydrogenation fiber bundle comprises at least one nickel alloy hollow fiber membrane or iron-based alloy hollow fiber membrane, and the dehydrogenation fiber bundle is fixed in the reaction chamber by high-temperature resistant metal solder; the deoxygenation fiber bundle comprises at least one perovskite-type hollow fiber oxygen permeation membrane, and the deoxygenation fiber bundle is fixed in the reaction chamber by high-temperature resistant ceramic sealant.

[0012] In an implementable manner, the reaction chamber is provided with a fixing member, the fixing member comprises a clamping seat and an array disc, the dehydrogenation fiber bundle and the deoxygenation fiber bundle are fixed on the array disc, and the dehydrogenation fiber bundle and the deoxygenation fiber bundle are sealingly connected with the array disc through the clamping seat.

[0013] In an implementable manner, the double-membrane recombination hydrogen production reactor further comprises a vacuum pump, a hydrogen gas detector, and a hydrogen gas storage tank arranged in sequence along a hydrogen gas discharge path.

[0014] Compared with the prior art, the double-membrane recombination hydrogen production reactor has the following advantages:

[0015] Firstly, the double-membrane reforming hydrogen production reactor in the application integrates the reaction chamber, the dehydrogenation / deoxidation fiber bundle and the gasification unit composed of three heat exchangers, uses the waste heat of the high-temperature tail gas, product hydrogen and deoxidized air discharged from the reaction chamber to preheat and gasify the liquid raw material in turn, and provides ideal gas-phase reactants for the subsequent dehydrogenation reaction. At the same time, the deoxidation fiber bundle directly separates oxygen from air to supply the reaction chamber, avoiding the introduction of impurities such as nitrogen into the reaction system, and directly using air as an oxygen source to produce heat by partial oxidation of raw materials without introducing other impurities such as nitrogen, without the need for an external heat source, and directly used for ultra-pure hydrogen for fuel cells and improving reaction conversion rate. In this way, the application solves the problems of complex structure, high processing cost, low heat and mass transfer efficiency, slow response speed of the traditional reforming hydrogen production reactor by integrating the double-membrane system and the heat exchange structure, without additional catalysts, fast hydrogen production speed per unit volume and high purity.

[0016] Secondly, the above structure sets a special raw material supply unit to cooperate with the reactor main body to stably and controllably transport the hydrocarbon-containing compound and water raw material into the system, ensuring the continuous supply and stable proportion of the reaction material in the reaction chamber, providing reliable raw material basis for the entire hydrogen production process, and solving the technical problems of reaction efficiency fluctuation or product quality unevenness caused by unstable feeding.

[0017] In addition, the reaction chamber is specifically designed as a combination of an upper shell, a reactor shell and a lower shell, and the installation positions and air flow paths of the deoxidation fiber bundle and the dehydrogenation fiber bundle in different shells are clearly defined. Air enters the upper shell, separates oxygen after the deoxidation fiber bundle, enters the reactor shell, the gasified raw material enters the reactor shell for reaction, the generated hydrogen-containing mixture is separated by the dehydrogenation fiber bundle in the reactor shell to the lower shell for discharge, and the remaining nitrogen after deoxidation is also discharged from the lower shell. This clear process cooperation optimizes the internal space layout of the reactor, clearly distinguishes the functional areas, and ensures the orderly flow of reactants and products.

[0018] Another object of the application is to provide a hydrogen production method using the double-membrane reforming hydrogen production reactor described above, which further comprises the following steps:

[0019] S1, air passes through the deoxidation fiber bundle, and oxygen selectively permeates into the reaction chamber, while obtaining pure nitrogen as a byproduct;

[0020] S2, the raw material containing hydrocarbon-containing compound and water is gasified in the gasification unit by using the waste heat generated in the reaction process to obtain gasified material;

[0021] S3, the gasified material and the permeated oxygen perform self-heating reforming reaction in the reaction chamber to generate a hydrogen-containing mixture;

[0022] S4, applying negative pressure on the permeation side of the hydrogen fiber bundle to separate hydrogen from the hydrogen-containing mixture to obtain hydrogen product.

[0023] In an implementation, the raw material is a mixture of water and any one or more of methanol, ethanol, ethylene glycol, formic acid, acetic acid, acetone, glucose, glycerol, bio-oil or bio-diesel, and the mass ratio of water to hydrocarbon or biomass derivative is 1:1 to 1:5.

[0024] In an implementation, the autothermal reforming reaction temperature is 600 to 1000℃.

[0025] In an implementation, when separating hydrogen, the vacuum degree applied on the permeation side of the hydrogen fiber bundle is 0.01 to 0.1 MPa; and the generated nitrogen, the generated reaction tail gas and the generated outlet hydrogen all enter the gasification unit to exchange heat with the raw material as heat source.

[0026] Compared with the prior art, the hydrogen production method in the application has all the advantages of the double-membrane recombination hydrogen production reactor described above, and the continuous process of in-situ oxygen permeation using air as oxygen source, gasification using reaction waste heat, autothermal reforming reaction and membrane separation of hydrogen can be continuously carried out through the sequential execution of steps S1 to S4 and the cooperation of the reactor structure, thereby simplifying the hydrogen production process, reducing energy consumption, improving hydrogen selectivity and reaction conversion rate, directly producing high-purity hydrogen, and solving the technical problems of traditional hydrogen production methods, such as complex process, high energy consumption, reaction equilibrium limiting conversion rate, and hydrogen purity depending on subsequent purification unit.

[0027] Moreover, the raw material is limited to a mixture of water and a specific hydrocarbon or biomass derivative and the ratio range thereof, and the reactor and the hydrogen production method are cooperated to optimize the reaction conditions for different raw material characteristics, ensure that the water-carbon ratio is in an appropriate range, promote the reforming reaction to proceed fully and inhibit carbon deposition. The cooperation of the above-mentioned raw material selection widens the adaptability of the raw material, improves the reaction efficiency and stability, thereby solving the technical problems of catalyst deactivation, reactor coking and hydrogen production rate reduction caused by unsuitable raw material or improper ratio.

[0028] Finally, the vacuum degree range when separating hydrogen is limited, and the generated nitrogen, reaction tail gas and outlet hydrogen are used as heat source of the gasification unit to exchange heat, which realizes the efficient driving of hydrogen separation while maximizing the recycling of all process waste heat. The cooperation of this operating parameter and energy integration strategy reduces external energy consumption, improves the energy efficiency of the whole process, reduces impurities in the hydrogen separation and generation process, thereby solving the technical problems of low hydrogen separation efficiency, low system thermal efficiency, increased operation cost and insufficient purity of generated hydrogen. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or prior art description will be briefly introduced as follows. Obviously, the drawings in the following description only constitute some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort based on these drawings. In the drawings:

[0030] Fig. 1 The overall structure schematic diagram of the double-membrane recombination hydrogen production reactor provided by the present application is shown in the figure.

[0031] Fig. 2 The partial structure schematic diagram of the double-membrane recombination hydrogen production reactor provided by the present application is shown in the figure.

[0032] Fig. 3 The step schematic diagram of the hydrogen production method of the present application is shown in the figure.

[0033] In the figure:

[0034] 1, reaction chamber; 11, upper shell; 12, reactor shell; 13, lower shell;

[0035] 21, dehydrogenated fiber bundle; 22, deoxygenated fiber bundle;

[0036] 3, gasification unit; 31, first heat exchanger; 32, second heat exchanger; 33, third heat exchanger;

[0037] 4, raw material supply unit;

[0038] 5, vacuum pump;

[0039] 6, hydrogen detector. DETAILED DESCRIPTION

[0040] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict.

[0041] In the description of the present application, it should be noted that if terms indicating orientation or position relationship such as "upper", "lower", "inner", "back" and the like appear, they are based on the orientation or position relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and therefore cannot be understood as limiting the present application in that the devices or elements indicated must have a specific orientation, be constructed and operated in a specific orientation.

[0042] Furthermore, in the description of the present application, unless otherwise specifically defined, the terms "mounting", "connection", "connecting", "connected", "connection piece" should be interpreted broadly. For example, the connection can be fixed connection, or detachable connection, or integral connection; can be mechanical connection, or electrical connection; can be direct connection, or indirect connection through intermediate medium, or internal connection of two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood in combination with specific circumstances.

[0043] In order to make the technical problems to be solved by the present application, technical solutions and beneficial effects more clearly, the present application will be further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not used to limit the present application.

[0044] Please refer to Figs. 1 to 3 , now the double membrane recombination hydrogen production reactor provided by the present application will be described. The double membrane recombination hydrogen production reactor comprises a reaction chamber 1, dehydrogenation fiber bundle 21 and deoxygenation fiber bundle 22 arranged in the reaction chamber 1, and a gasification unit 3, wherein the reaction chamber 1 provides a reaction space for hydrogen-containing compounds, water and oxygen; the deoxygenation fiber bundle 22 is used for separating oxygen from air; the gasification unit 3 comprises a first heat exchanger 31, a second heat exchanger 32 and a third heat exchanger 33 connected in sequence; wherein the hot fluid inlet of the first heat exchanger 31 is connected to the tail gas outlet of the reaction chamber 1, the hot fluid inlet of the second heat exchanger 32 is connected to the hydrogen gas outlet of the reaction chamber 1, and the hot fluid inlet of the third heat exchanger 33 is connected to the deoxygenation air outlet of the reaction chamber 1; the hydrogen-containing compounds and water are heated and gasified by flowing through the first heat exchanger 31, the second heat exchanger 32 and the third heat exchanger 33 in sequence, and after being heated, the hydrogen-containing compounds and water enter the reaction chamber 1 and react with oxygen to recombine, and the dehydrogenation fiber bundle 21 dehydrogenates the high-temperature hydrogen-containing compounds after recombination.

[0045] Compared with the prior art, the double-membrane recombination hydrogen production reactor provided by the application has the advantages that in the specific implementation process, the double-membrane recombination hydrogen production reactor integrates the reaction chamber 1, the dehydrogenation / deoxidation fiber bundle, and the gasification unit 3 composed of three heat exchangers, utilizes the waste heat of the high-temperature tail gas, product hydrogen, and deoxidized air discharged from the reaction chamber 1 to sequentially preheat and gasify the liquid raw material, and provides ideal gas-phase reactants for the subsequent dehydrogenation reaction. The deoxidation fiber bundle 22 directly separates oxygen from air to supply the reaction chamber 1, avoids the introduction of impurities such as nitrogen into the reaction system, can directly utilize air as an oxygen source to produce heat through partial oxidation of raw materials without introducing other impurities such as nitrogen, does not need an external heat source, can be directly used for ultra-pure hydrogen for fuel cells, and improves the reaction conversion rate. The above arrangement solves the problems of complex structure, high processing cost, low heat and mass transfer efficiency, and slow response speed of the traditional reforming hydrogen production reactor through heat exchange and a double-membrane system, does not need an additional catalyst, has a high hydrogen production speed per unit volume, and has high purity.

[0046] In a feasible implementation manner, the double-membrane recombination hydrogen production reactor further includes a raw material supply unit 4, and the raw material supply unit 4 is configured to supply raw materials containing hydrocarbons and water. The above structure provides a special raw material supply unit 4 to cooperate with the reactor main body, stably and controllably convey the hydrocarbon-containing and water raw materials entering the system, ensure the continuous supply and proportion stability of the reactant materials in the reaction chamber 1, and provide a reliable raw material basis for the entire hydrogen production process, so as to solve the technical problems of reaction efficiency fluctuation or product quality unevenness caused by unstable feeding.

[0047] In a feasible implementation manner, the reaction chamber 1 includes an upper shell 11, a reactor shell 12, and a lower shell 13 arranged along a reaction path in sequence; the upper shell 11 is provided with an air inlet, the reactor shell 12 is provided with a gasification material inlet and a reaction tail gas outlet, and the lower shell 13 is provided with a pure nitrogen gas outlet and a hydrogen gas outlet; the deoxidation fiber bundle 22 is arranged between the upper shell 11 and the reactor shell 12, the air inlet is in communication with the gas inlet side of the deoxidation fiber bundle 22, and the permeation side of the deoxidation fiber bundle 22 leads to the inner cavity of the reactor shell 12; the dehydrogenation fiber bundle 21 is arranged in the inner cavity of the reactor shell 12, and the permeation side of the dehydrogenation fiber bundle 21 is in communication with the hydrogen gas outlet.

[0048] In this embodiment, the reaction chamber 1 is specifically designed as a combination of an upper shell 11, a reactor shell 12, and a lower shell 13. The installation positions and airflow paths of the deoxygenation fiber bundle 22 and the dehydrogenation fiber bundle 21 within the different shells are clearly defined. Specifically, air enters from the upper shell 11, is separated from oxygen by the deoxygenation fiber bundle 22, and then enters the reactor shell 12. The gasified feedstock enters from the reactor shell 12 to react. The generated hydrogen-containing mixture is separated into hydrogen by the dehydrogenation fiber bundle 21 within the reactor shell 12 and discharged to the lower shell 13. Simultaneously, the remaining nitrogen from deoxygenation is also discharged from the lower shell 13. This clear process, combined with optimized internal space layout of the reactor, clear differentiation of functional areas, and ensures the orderly flow of reactants and products, ensures efficient operation of the reactor.

[0049] Based on the above embodiments, in one feasible implementation, the dehydrogenation fiber bundle 21 includes at least one bundle of nickel alloy hollow fiber membrane or iron-based alloy hollow fiber membrane, and the dehydrogenation fiber bundle 21 is sealed and fixed in the reaction chamber 1 by high-temperature resistant metal solder; the deoxygenation fiber bundle 22 includes at least one bundle of perovskite-type hollow fiber oxygen-permeable membrane, and the deoxygenation fiber bundle 22 is fixed in the reaction chamber 1 by high-temperature resistant ceramic sealant. This combination achieves high selectivity, high permeability, and mechanical stability of the dehydrogenation membrane under high-temperature reforming reaction conditions, as well as high oxygen permeability of the deoxygenation membrane under high oxygen partial pressure differentials and good thermal compatibility with the reactor materials. This combination of materials and process achieves the technical effect of ensuring long-term stable operation of the two membranes under harsh reaction conditions and maintaining high separation efficiency, thereby helping to solve the technical problems of membrane material failure and poor sealing leading to decreased product purity or reduced reaction efficiency.

[0050] For perovskite hollow fiber oxygen-permeable membranes, considering that the carbon dioxide generated during the raw material oxidative reforming process may react with metal ions in some configurations of the perovskite type, thereby depositing carbonate compounds on the oxygen-permeable membrane, preferably, the perovskite type ( In this design, component A is limited to Sr, Zr, or lanthanides, while component B can be Cr, Mn, Fe, Ni, Cu, etc., with the number of A ions in a single crystal ranging from 1 to 0.5. This utilizes the high stability and oxygen permeability of the material to maintain its functional stability in hydrogen-rich environments. Furthermore, research on the carbon dioxide resistance of perovskite-type oxygen-permeable membranes with the above configuration has been fully disclosed in existing technologies and will not be elaborated upon here.

[0051] In an available embodiment, the reaction chamber 1 is provided with a fixing member including a clamping seat and an array disc, and the dehydrogenation fiber bundle 21 and the deoxygenation fiber bundle 22 are both fixed to the array disc and are in sealed connection with the array disc through the clamping seat. The above structure realizes the orderly and stable installation of the double-membrane fiber bundle in the reaction chamber 1 by arranging the fixing member including the clamping seat and the array disc, fixing the dehydrogenation fiber bundle 21 and the deoxygenation fiber bundle 22 to the array disc, and realizing the sealed connection through the clamping seat. The effective packaging of each fiber membrane and the smooth passage of the airflow are ensured. The cooperation of mechanical fixation and sealing improves the assembly precision and reliability of the membrane assembly, facilitates the maintenance and replacement of the membrane assembly, and optimizes the fluid distribution in the reactor, thereby solving the technical problems of vibration damage caused by unstable fixation of the membrane bundle, easy leakage caused by too many sealing points, and the influence of the reaction and separation efficiency caused by uneven fluid distribution.

[0052] In addition to the above available embodiment, more preferably, the double-membrane reforming hydrogen production reactor further includes a vacuum pump 5, a hydrogen detector 6 and a hydrogen storage tank arranged in sequence along the hydrogen discharge path. In this embodiment, by arranging the above structure, the negative pressure can be continuously applied to the permeation side to drive the hydrogen separation, the purity of the produced hydrogen can be monitored in real time, and the qualified hydrogen can be safely stored, thereby ensuring the hydrogen separation efficiency, monitoring the product quality and ensuring the safe operation of the system, and preventing the problems of insufficient driving force for hydrogen separation and safety hazards in hydrogen storage.

[0053] Based on the above double-membrane reforming hydrogen production reactor, another object of the present application is to provide a hydrogen production method, which uses the above double-membrane reforming hydrogen production reactor for hydrogen production, and further includes the following steps:

[0054] S1, making air pass through the deoxygenation fiber bundle 22, and selectively permeating oxygen into the reaction chamber 1 to obtain pure nitrogen as a byproduct;

[0055] S2, gasifying the raw material containing hydrocarbons and water in the gasification unit 3 by using the waste heat generated in the reaction process to obtain a gasified material;

[0056] S3, performing a self-thermal reforming reaction on the gasified material and the permeated oxygen in the reaction chamber 1 to generate a hydrogen-containing mixture;

[0057] S4, applying a negative pressure to the permeation side of the hydrogen fiber bundle to separate hydrogen from the hydrogen-containing mixture to obtain a hydrogen product.

[0058] In the specific implementation process of this embodiment, the hydrogen all enters the gasification unit 3 as a heat source to exchange heat with the raw material.

[0059] Compared with the prior art, the hydrogen production method in the application has all the advantages of the double-membrane hydrogen production reactor described above, which will not be repeated here. The continuous process of in-situ oxygen permeation using air as the oxygen source, gasification using reaction waste heat, autothermal reforming reaction, and membrane separation of hydrogen can be continuously carried out through the sequential execution of steps S1 to S4 and the coordination of the reactor structure. Thus, the hydrogen production process is simplified, energy consumption is reduced, hydrogen selectivity and reaction conversion rate are improved, and high-purity hydrogen is directly produced, which helps to solve the technical problems of traditional hydrogen production methods, such as complex process, high energy consumption, reaction equilibrium limiting conversion rate, and hydrogen purity dependent on subsequent purification units.

[0060] Based on the above method, further, in a feasible embodiment, the raw material is a mixture of water and any one or more of methanol, ethanol, ethylene glycol, formic acid, acetic acid, acetone, glucose, glycerol, bio-oil or biodiesel, and the mass ratio of water to hydrocarbon or biomass derivative is 1:1 to 1:5. The raw material is limited to a mixture of water and a specific hydrocarbon or biomass derivative and its ratio range, and by coordinating the reactor and the hydrogen production method, the reaction conditions are optimized for different raw material characteristics, ensuring that the water-carbon ratio is in the appropriate range, promoting the full progress of the reforming reaction and inhibiting carbon deposition. The above-mentioned cooperation of raw material selection widens the adaptability of raw materials, improves the reaction efficiency and stability, and can solve the technical problems of catalyst deactivation, reactor coking, and hydrogen production rate reduction caused by unsuitable raw materials or improper ratio.

[0061] Preferably, in a feasible implementation, the autothermal reforming reaction temperature is 600-1000℃. The autothermal reforming reaction temperature is controlled in the range of 600-1000℃. In this temperature range, the reforming reaction has a faster kinetic rate and a higher equilibrium conversion rate, while ensuring that the dehydrogenation membrane has sufficient hydrogen permeability and stable material performance. Further optimizing the reaction kinetics and thermodynamics, ensuring the efficiency and life of the membrane separation, solving the technical problems of insufficient conversion rate caused by too low reaction temperature or increased energy consumption and material degradation caused by too high reaction temperature.

[0062] In one possible embodiment, when separating hydrogen, the vacuum degree applied to the permeation side of the hydrogen fiber bundle is 0.01 MPa to 0.1 MPa; and the generated pure nitrogen, the generated reaction tail gas, and the generated outlet hydrogen all enter the gasification unit 3 to exchange heat with the raw material as a heat source. This embodiment limits the vacuum degree range when separating hydrogen, and utilizes the generated pure nitrogen, reaction tail gas, and outlet hydrogen as a heat source for the gasification unit 3 to exchange heat, thereby achieving efficient driving of hydrogen separation while maximizing the recovery and utilization of all process waste heat. The combination of this operating parameter and energy integration strategy reduces external energy consumption, improves the overall process energy efficiency, and reduces impurities in the hydrogen separation and generation process, thereby solving the technical problems of low hydrogen separation efficiency, low system thermal efficiency, increased operating cost, and insufficient purity of generated hydrogen.

[0063] In summary, the present application integrates and coordinates the reaction chamber 1, the dehydrogenation and deoxidation double membrane fiber bundle, and the high-efficiency gasification unit 3 composed of the first, second, and third heat exchangers in series, thereby achieving a high degree of coordination of the work process. First, air enters the upper end of the reaction chamber 1 and selectively permeates oxygen through the deoxidation fiber bundle 22 (such as a perovskite hollow fiber membrane), thereby directly participating in the reaction in the form of pure oxygen and effectively excluding nitrogen from the main reaction system, and byproduct pure nitrogen is generated. The raw material containing hydrogen compounds (such as methanol) and water enters the gasification unit 3 and flows through the first heat exchanger 31 (heated by the high-temperature tail gas after reaction), the second heat exchanger 32 (heated by the high-temperature hydrogen product), and the third heat exchanger 33 (heated by the high-temperature air after deoxidation) in sequence, thereby utilizing multiple waste heat generated by the process to preheat and completely gasify in a stepwise manner from low temperature to high temperature, and forming uniform gasification material entering the reaction chamber 1.

[0064] In the reaction chamber 1, the gasification material and the permeated oxygen undergo an efficient self-thermal reforming reaction (the exothermic partial oxidation reaction provides energy for the subsequent endothermic reforming reaction), generating a hydrogen-rich gas mixture; then, the dehydrogenation fiber bundle 21 (such as a nickel alloy hollow fiber membrane or an iron-based alloy hollow fiber membrane) selectively separates and exports the hydrogen generated by the reaction from the reaction mixture in situ and in real time on the permeation side under the driving of the moderate negative pressure applied by the vacuum pump 5, and the reaction tail gas is discharged and returned to the gasification unit 3 as the primary heat source. This series of precise structures and processes cooperate to achieve three core advantages: using air as a direct oxygen source without the need for an air separation device, using the self-produced waste heat from the reaction process to realize gasification and preheating of the raw material without the need for an external heat source, and through the synergistic action of the double membranes, hydrogen is separated and purified in situ during the reaction. The triple core advantages achieve the comprehensive technical effects of significantly simplifying the system structure, greatly improving the energy utilization efficiency, breaking through the chemical reaction balance limitation to improve the raw material conversion rate, and directly producing high-purity hydrogen suitable for fuel cells. It is beneficial to solve a series of interrelated technical problems existing in traditional reforming hydrogen reactors, such as complex and large structure, high processing and operating cost, dependence on external heating leading to high energy consumption, low heat and mass transfer efficiency restricting reaction rate and conversion rate, slow response speed, and the need for complex subsequent purification of hydrogen products.

[0065] The above is only a preferred embodiment of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A dual-membrane reforming hydrogen production reactor, characterized in that, include: The reaction chamber (1) provides a reaction space for hydrocarbons, water and oxygen; A dehydrogenated fiber bundle (21) and a deoxygenated fiber bundle (22) are disposed in the reaction chamber (1), the deoxygenated fiber bundle (22) being used to separate oxygen from the air; The gasification unit (3) includes a first heat exchanger (31), a second heat exchanger (32), and a third heat exchanger (33) connected in sequence; wherein, the hot fluid inlet of the first heat exchanger (31) is connected to the tail gas outlet of the reaction chamber (1), the hot fluid inlet of the second heat exchanger (32) is connected to the hydrogen outlet of the reaction chamber (1), and the hot fluid inlet of the third heat exchanger (33) is connected to the deoxygenated air outlet of the reaction chamber (1); Hydrocarbons and water flow sequentially through the first heat exchanger (31), the second heat exchanger (32) and the third heat exchanger (33) and are heated and vaporized. After being heated, the hydrocarbons and water enter the reaction chamber (1) and react with oxygen to recombine. The dehydrogenation fiber bundle (21) dehydrogenates the recombined high-temperature hydrocarbons. The dual-membrane recombinant hydrogen production reactor also includes a raw material supply unit (4), which is used to provide hydrocarbons and water as raw materials; The reaction chamber (1) includes an upper shell (11), a reactor shell (12), and a lower shell (13) arranged sequentially along the reaction path; the upper shell (11) is provided with an air inlet, the reactor shell (12) is provided with a gasified material inlet and a reaction tail gas outlet, and the lower shell (13) is provided with a pure nitrogen outlet and a hydrogen outlet; The deoxygenated fiber bundle (22) is disposed between the upper shell (11) and the reactor shell (12). The air inlet side of the deoxygenated fiber bundle (22) is connected to the air inlet, and its permeation side is connected to the inner cavity of the reactor shell (12). The air inlet side of the dehydrogenated fiber bundle (21) is placed in the inner cavity of the reactor shell (12), and the permeation side of the dehydrogenated fiber bundle (21) is connected to the hydrogen outlet.

2. The dual-membrane reforming hydrogen production reactor as described in claim 1, characterized in that, The dehydrogenation fiber bundle (21) includes at least one bundle of nickel alloy hollow fiber membrane or iron-based alloy hollow fiber membrane, and the dehydrogenation fiber bundle (21) is sealed and fixed in the reaction chamber (1) by high-temperature resistant metal solder; the deoxygenation fiber bundle (22) includes at least one bundle of perovskite type hollow fiber oxygen-permeable membrane, and the deoxygenation fiber bundle (22) is fixed in the reaction chamber (1) by high-temperature resistant ceramic sealant.

3. The dual-membrane reforming hydrogen production reactor as described in claim 2, characterized in that, The reaction chamber (1) is equipped with a fixing component, which includes a snap-fit ​​seat and an array disk. The dehydrogenated fiber bundle (21) and the deoxygenated fiber bundle (22) are both fixed on the array disk. The dehydrogenated fiber bundle (21) and the deoxygenated fiber bundle (22) are both sealed to the array disk through the snap-fit ​​seat.

4. The dual-membrane reforming hydrogen production reactor as described in claim 3, characterized in that, The dual-membrane recombinant hydrogen production reactor also includes a vacuum pump (5), a hydrogen detector (6), and a hydrogen storage tank arranged sequentially along the hydrogen emission path.

5. A method for producing hydrogen, wherein the method uses the dual-membrane recombination hydrogen production reactor according to any one of claims 1-4, characterized in that, The hydrogen production method further includes the following steps: S1. Air is separated by the deoxygenated fiber bundle (22), allowing oxygen to selectively permeate into the reaction chamber (1), while pure nitrogen is obtained as a byproduct. S2. The raw materials of hydrocarbons and water are gasified in the gasification unit (3) using the waste heat generated during the reaction process to obtain gasified feedstock; S3. The gasified material and the permeated oxygen undergo an autothermal reforming reaction in the reaction chamber (1) to generate a hydrogen-containing mixture; S4. Apply negative pressure to the permeation side of the hydrogen fiber bundle to separate hydrogen from the hydrogen-containing mixture to obtain hydrogen products.

6. The hydrogen production method as described in claim 5, characterized in that, The raw material is water and any one or more of methanol, ethanol, ethylene glycol, formic acid, acetic acid, acetone, glucose, and glycerol, and the mass ratio of water to hydrocarbon is 1:1 to 1:

5.

7. The hydrogen production method as described in claim 6, characterized in that, The autothermal reforming reaction temperature is 600℃ to 1000℃.

8. The hydrogen production method as described in claim 5, characterized in that, When separating hydrogen, the vacuum applied to the permeation side of the hydrogen fiber bundle is 0.01 MPa to 0.1 MPa; and the generated pure nitrogen, the generated reaction tail gas and the generated outlet hydrogen all enter the gasification unit (3) to exchange heat with the raw materials as a heat source.

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