WO2024046397A1 - Desalination-free in-situ direct electrolytic hydrogen production device for non-pure-water solution, and use method - Google Patents

Desalination-free in-situ direct electrolytic hydrogen production device for non-pure-water solution, and use method Download PDF

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Publication number
WO2024046397A1
WO2024046397A1 PCT/CN2023/115956 CN2023115956W WO2024046397A1 WO 2024046397 A1 WO2024046397 A1 WO 2024046397A1 CN 2023115956 W CN2023115956 W CN 2023115956W WO 2024046397 A1 WO2024046397 A1 WO 2024046397A1
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chamber
solution
electrolyte
aqueous solution
electrolysis
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PCT/CN2023/115956
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French (fr)
Chinese (zh)
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谢和平
赵治宇
刘涛
吴一凡
朱亮宇
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四川大学
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention belongs to the technical field of electrolytic hydrogen production, and is specifically a device and a method of using in-situ direct electrolysis hydrogen production from non-pure aqueous solution without desalination.
  • Hydrogen energy has the advantages of wide source, storability, multiple uses, zero carbon and zero pollution, and high energy density. It is a key component of the future energy field.
  • composition is complex, and the composition changes with factors such as season, climate, temperature, region, and human activities. Therefore, non-pure water direct hydrogen production electrolysis devices in different regions are not directly compatible;
  • the second is to desalinize/purify the non-pure water solution and prepare pure water for electrolysis to produce hydrogen.
  • a seawater desalination process is required.
  • This method requires the establishment of a seawater desalination plant on the coast, which greatly increases the cost in terms of construction, operation, manpower, maintenance, etc.; and it is difficult to use offshore wind power coupling on a large scale to form an in-situ integrated green plant. Hydrogen production system to achieve stable storage of renewable energy.
  • the purpose of the present invention is to address the shortcomings of the existing technology and solve the problems of the existing direct hydrogen production technology from non-pure aqueous solutions, which are limited by time and space and cannot produce hydrogen in situ, low electrolysis efficiency, high energy consumption, substantial increase in cost, catalyst corrosion and membrane clogging. and other problems; provide an in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solutions and a method of use.
  • the present invention directly uses non-pure aqueous solutions to produce hydrogen without desalination/purification.
  • the water vapor passes through the energy-free water vapor mass transfer layer and is liquefied by the phase change induced by the self-driven electrolyte to form an electrolyte solution.
  • the hydrophobic effect of the energy-free water vapor mass transfer layer removes the water vapor in the non-pure aqueous solution. Impurities are effectively blocked.
  • the electrolyte solution is synchronously electrolyzed to produce hydrogen.
  • the water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous, efficient and stable hydrogen production.
  • An in-situ direct electrolysis hydrogen production device without desalination from non-pure aqueous solutions has two modes: static hydrogen production from electrolyte and dynamic hydrogen production from electrolyte.
  • An in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution, used for static hydrogen production from electrolyte includes:
  • Energy supply module used to provide electrical energy for the hydrogen production reaction
  • An electrolysis unit connected to the energy supply module includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber.
  • the anode plate and the cathode plate are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber; multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack, for Hydrogen production reaction produces hydrogen gas.
  • the anode plates in the electrolysis unit are connected in series or in parallel to the positive electrode of the energy supply module, and the cathode plates in the electrolysis unit are connected in series or in parallel to the negative electrode of the energy supply module.
  • Bracket used to fix the electrolysis stack
  • Porous mesh trough used to place the bracket.
  • the inner wall of the porous mesh trough is close to the water vapor mass transfer layer.
  • the water vapor mass transfer layer forms a concave space to form an electrolyte solution chamber for storing self-driven electrolyte solution;
  • the collection device is connected to the electrolysis unit to collect hydrogen and oxygen produced by electrolysis.
  • the device includes: an energy supply module: used to provide electrical energy for the hydrogen production reaction;
  • An electrolysis unit connected to the energy supply module includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber.
  • the anode plate and the cathode plate are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber;
  • multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack, for Hydrogen production reaction produces hydrogen gas;
  • Bracket used to fix the electrolysis stack
  • Tank body with frame used to place the bracket, forming an electrolyte solution chamber in the gap between the bracket and the tank body, used to store self-driven electrolyte solution;
  • the collection device is connected to the electrolysis unit to collect the hydrogen produced by electrolysis.
  • the electrolysis unit further includes an anode catalytic layer disposed in the anode solution chamber and a cathode catalytic layer disposed in the cathode solution chamber; the anode plate, the anode catalytic layer and the flow channel gap of the insulating slot form an anode.
  • the anode solution chamber is filled with a self-driven electrolyte solution; the flow channel gap between the cathode plate and the cathode catalytic layer forms a cathode solution chamber, and the cathode solution chamber is filled with a self-driven electrolyte solution; the electrolyte solution is immersed in the electrolysis stack.
  • the collection device includes a hydrogen collection pipe and an oxygen collection pipe; a hydrogen scrubber, a hydrogen dryer and a hydrogen storage are connected in sequence behind the hydrogen collection pipe; an oxygen scrubber, an oxygen storage tank are connected in sequence behind the oxygen collection pipe. Dryer and oxygen storage.
  • the hydrogen collection pipe transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle, and the hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen.
  • Hydrogen scrubbers are used to remove particulate matter or gaseous contaminants, thereby further improving the purity of the collected hydrogen.
  • an upper end cover is provided on the porous mesh trough, and an interface is provided on the upper end cover for the hydrogen collection pipe, the oxygen collection pipe and the conductive wire of the energy supply module to pass through, and the interfaces are sealed and connected; electrolysis
  • part of the porous mesh tank is immersed in the impure water solution, which generates a vapor pressure difference at the interface of the water vapor mass transfer layer, inducing the gasification phase change of the impure aqueous solution.
  • the porous mesh trough body and the water vapor mass transfer layer attached to the inner wall are sealed and connected with the upper end cover to form a sealed space, which is isolated from the outside air.
  • the upper end cover when used for dynamic hydrogen production, there is an upper end cover at the upper end of the tank body.
  • the upper end cover is provided with interfaces for the hydrogen collection pipe, the oxygen collection pipe and the conductive wires of the energy supply module to pass through, and the interfaces are sealed and connected.
  • an electrolyte energy-free circulation regeneration module is also provided on one side of the tank body.
  • the electrolyte energy-free circulation regeneration module is connected to the tank body through an electrolyte solution circulation pipeline with an electrolyte solution circulation pump; the electrolyte energy-free circulation regeneration module is based on Membrane module types are divided into two types: hollow fiber membrane electrolyte energy-free recycling regeneration module and flat membrane electrolyte energy-free recycling regeneration module.
  • the hollow fiber membrane type electrolyte energy-free recycling regeneration module includes a hollow fiber membrane mass transfer chamber, a hollow fiber membrane, a hollow fiber membrane inner cavity, a hollow fiber membrane outer chamber, a non-pure aqueous solution tank, and a non-pure aqueous solution chamber.
  • non-pure aqueous solution circulation pipeline and non-pure aqueous solution circulation pump a plurality of parallel hollow fiber membranes are densely arranged in the hollow fiber membrane mass transfer chamber, and the flowable solution space inside the hollow fiber membrane membrane layer is the hollow fiber membrane inner cavity, which is hollow
  • the space between the outer wall of the fiber membrane layer and the mass transfer chamber of the hollow fiber membrane is the outer chamber of the hollow fiber membrane;
  • the tank body, the electrolyte solution circulation pipe, the electrolyte solution circulation pump and the hollow fiber membrane are connected in series, and the electrolyte solution circulation pump circulates the self-driven electrolyte solution , the electrolyte solution chamber is connected to the inner cavity of the hollow fiber membrane, and the self-driven electrolyte solution passes through the inner cavity of the hollow fiber membrane;
  • the hollow fiber membrane mass transfer chamber is connected in series with the non-pure aqueous solution circulation pipe, the non-pure aqueous solution circulation pump, and the non-pure aqueous solution tank;
  • the outer chamber of the hollow fiber membrane is connected to the non-pure aqueous solution chamber, and the non-pure aqueous solution passes through the outer chamber of the hollow fiber membrane; during the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces phase change and gasification of the non-pure aqueous solution to form water vapor. , water vapor directionally migrates to the electrolyte side through the fiber membrane, and is induced to liquefy phase change, providing pure water for electrolysis. This process transfers pure water from the outer chamber of the hollow fiber membrane to the inner cavity of the hollow fiber membrane without energy consumption, and at the same time, the hollow fiber membrane will Impurities in impure aqueous solutions are blocked out.
  • the flat membrane type electrolyte energy-free recycling regeneration module includes a flat membrane mass transfer chamber, a double-layer flat membrane, a flat membrane inner chamber, a flat membrane outer chamber, a shunt manifold, a non-pure aqueous solution tank, a non-pure aqueous solution tank, and a flat membrane external chamber.
  • the aqueous solution chamber, the non-pure aqueous solution circulation pipe and the non-pure aqueous solution circulation pump; the flat membrane mass transfer chamber is arranged with multiple sets of parallel double-layer flat membranes.
  • a single set of double-layer flat membranes is composed of two membrane layers arranged in parallel.
  • the side is sealed, and its top and bottom surfaces are connected to the shunt manifold respectively;
  • the narrow gap in the middle of the double-layer flat membrane is the inner cavity of the flat membrane, and the space between the outer wall of the membrane layer of the double-layer flat membrane and the flat membrane mass transfer chamber is the flat membrane External room.
  • the tank body, electrolyte solution circulation pipeline, electrolyte solution circulation pump, shunt manifold and double-layer flat membrane are connected in series.
  • the electrolyte solution circulation pump circulates the self-driven electrolyte solution to connect the electrolyte solution chamber to the inner cavity of the flat membrane.
  • the self-driven electrolyte solution flows from the flat membrane to The inner chamber passes through; the flat membrane mass transfer chamber is connected in series with the non-pure water solution circulation pipe, the non-pure water solution circulation pump, and the non-pure water solution tank; the non-pure water solution circulation pump is used to circulate the non-pure water solution, and the flat membrane outer chamber is connected with the non-pure water solution chamber.
  • the non-pure aqueous solution passes through the outer chamber of the flat membrane; during the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces the phase change and gasification of the non-pure aqueous solution to form water vapor, and the water vapor directionally migrates to the electrolyte side through the fiber membrane. It is induced to undergo a liquefaction phase change to provide pure water for electrolysis. This process transfers water from the outer chamber of the flat membrane to the inner chamber of the flat membrane without energy consumption. At the same time, the double-layer flat membrane blocks impurities in impure water.
  • the electrolyte solution chamber is connected to the outer chamber of the flat membrane (or the outer chamber of the hollow fiber membrane), and the self-driven electrolyte solution passes through the outer chamber of the flat membrane (or the outer chamber of the hollow fiber membrane); the inner chamber of the flat membrane (or the inner chamber of the hollow fiber membrane) is connected to the non- In the pure water solution chamber, the impure aqueous solution passes through the inner cavity of the flat membrane (or the inner cavity of the hollow fiber membrane).
  • the self-driven electrolyte solution induces the phase change and vaporization of the impure aqueous solution to form water vapor.
  • the invention is based on the interfacial vapor pressure difference between the self-driven electrolyte and the non-pure aqueous solution, inducing the vaporization phase change of the non-pure aqueous solution.
  • the water vapor directionally migrates to the electrolyte side through the water vapor mass transfer membrane, and at the same time the liquefaction phase change is absorbed by the electrolyte.
  • the hydrogen process provides pure moisture.
  • the electrolyte is in a static state.
  • the in-situ direct electrolysis hydrogen production device without desalination of the non-pure aqueous solution is directly immersed in the non-pure aqueous solution.
  • the non-pure aqueous solution phase changes and vaporizes to produce water vapor.
  • the water vapor passes through the energy-free water vapor.
  • the mass transfer layer directionally migrates to the electrolyte side, and is then liquefied by phase change induced by the self-driven electrolyte to form liquid water.
  • the hydrophobic effect of the energy-free water vapor mass transfer layer effectively blocks impurities in the non-pure aqueous solution.
  • the electrolyte solution is synchronously electrolyzed to produce hydrogen.
  • the water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous and efficient hydrogen production.
  • the electrolyte is pumped to the electrolyte energy-free circulation regeneration module, and under the same principle as above, the water is transferred from the impure aqueous solution to the electrolyte solution, thereby maintaining a stable hydrogen production process.
  • the present invention does not require a desalination process, it greatly reduces the costs of construction, operation, manpower, maintenance, etc., and is not limited by time and space, greatly broadening the source range of hydrogen energy; it uses a self-driven electrolyte to induce the phase change of water vapor liquefaction to form
  • the electrolyte solution greatly improves the conductivity of the electrolysis system and avoids the problem of low concentration of H + and OH - in hydrogen production from non-pure aqueous solutions and low cathode and anode transmission efficiency; in the present invention, the self-driven electrolyte induces water vapor phase change and liquefaction.
  • the energy supply module provides electric energy for the electrolysis unit.
  • the electricity generated from renewable energy sources such as solar energy and wind energy or thermal power and hydropower is stored in the energy supply module to provide electric energy for the hydrogen production reaction.
  • the hydrogen production reaction of electrical energy comes Widely available and easy to store.
  • the electrolysis unit of the present invention is suitable for a wider range of hydrogen production electrolysis structures.
  • the arrangement of the anode catalytic layer in the anode solution chamber and the cathode catalytic layer in the cathode solution chamber is beneficial to increasing the rate of the electrolysis reaction.
  • the compactness of the internal plates and catalytic layers greatly improves the stability of the entire electrolysis unit.
  • Available anode catalytic electrodes include: nickel-molybdenum foam, nickel-iron foam, FexCoyNiz catalyst, ruthenium-iridium, NiFe-LDH, NiFeCu alloy catalyst, etc. (selected according to the actual acidity and alkalinity of the electrolyte); available hydrogen evolution catalysts include: platinum mesh, Nickel-plated platinum mesh, etc. (select according to the actual acidity and alkalinity of the electrolyte).
  • the membrane layer of the hollow fiber membrane, double-layer flat membrane and (no energy consumption) water vapor mass transfer layer can be any material with waterproof and breathable properties, such as: porous TPU membrane, PDMS membrane, PTFE membrane with waterproof and breathable properties.
  • a waterproof and breathable layer prepared by spraying, screen printing, electrospinning, etc. from graphene, PVDF, PTFE, etc.
  • the self-driving electrolyte solution is a 10-50wt% KOH solution or a 10-40wt% H 2 SO 4 solution. Specifically, it can be a 10wt% KOH solution, a 15wt% KOH solution, a 20wt% KOH solution, or a 25wt% KOH solution.
  • the invention is based on the interfacial vapor pressure difference between the self-driven electrolyte and the non-pure aqueous solution, inducing the vaporization phase change of the non-pure aqueous solution, and directional migration to the electrolyte side through the water vapor mass transfer membrane, and at the same time the liquefaction phase change is absorbed by the electrolyte, thus providing hydrogen production.
  • the process provides pure moisture.
  • the electrolyte is in a static state.
  • the in-situ direct electrolysis hydrogen production device without desalination of the non-pure aqueous solution is directly immersed in the non-pure aqueous solution.
  • the non-pure aqueous solution phase changes and vaporizes to produce water vapor.
  • the water vapor passes through the energy-free water vapor.
  • the mass transfer layer directionally migrates to the electrolyte side, and is then liquefied by phase change induced by the self-driven electrolyte to form liquid water.
  • the hydrophobic effect of the energy-free water vapor mass transfer layer effectively blocks impurities in the non-pure aqueous solution.
  • the electrolyte solution is synchronously electrolyzed to produce hydrogen.
  • the water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous and efficient hydrogen production.
  • the electrolyte is pumped to the electrolyte energy-free circulation regeneration module, and under the same principle as above, the water is transferred from the impure aqueous solution to the electrolyte solution, thereby maintaining a stable hydrogen production process.
  • the present invention does not require a desalination process, it greatly reduces the costs of construction, operation, manpower, maintenance, etc., and is not limited by time and space, greatly broadening the source range of hydrogen energy; it uses a self-driven electrolyte to induce the phase change of water vapor liquefaction to form
  • the electrolyte solution greatly improves the conductivity of the electrolysis system and avoids the problem of low concentration of H + and OH - in hydrogen production from non-pure aqueous solutions and low cathode and anode transmission efficiency; in the present invention, the self-driven electrolyte induces water vapor phase change and liquefaction.
  • the non-pure aqueous solution can be directly used. Driven by the pressure difference at the interface between the electrolyte and the aqueous solution, the non-pure aqueous solution vaporizes and undergoes phase change to form water vapor. The water vapor is directed through the energy-free water vapor mass transfer layer and is then self-driven. The electrolyte induces phase change and liquefies to form an electrolyte solution.
  • the hydrophobic effect of the energy-free water vapor mass transfer layer effectively blocks impurities in the impure aqueous solution; the electrolyte solution undergoes simultaneous electrolysis to produce hydrogen; the water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation.
  • the present invention does not require a desalination process, which greatly reduces the costs of construction, operation, manpower, maintenance, etc., and It is not limited by time and space, greatly broadening the source range of hydrogen energy; using a self-driven electrolyte to induce the liquefaction phase change of water vapor to form an electrolyte solution, greatly improving the conductivity of the electrolysis system and avoiding the need for H + and OH in hydrogen production from non-pure aqueous solutions -The problem of low cathode and anode transmission efficiency due to small concentration; in the present invention, the water vapor phase change induced by the self-driven electrolyte to liquefy is impurity-free water, thus breaking through the oxidation of chlorine ions to produce Cl 2 or ClO in direct hydrogen production from non-pure aqueous solutions - Bottlenecks such as
  • the present invention is a green, non-toxic and environmentally friendly process system.
  • the energy supply module provides electric energy for the electrolysis unit. Electricity generated from renewable energy sources such as solar energy and wind energy or thermal power and hydropower is stored in the energy supply module to provide electric energy for the hydrogen production reaction.
  • the source of electric energy for the hydrogen production reaction is wide and Easy to store;
  • the electrolysis device can be a static or dynamic structure, which has wide practicability and is conducive to the development of future intensive energy systems; in addition, the compact structure greatly reduces manufacturing costs and land costs;
  • a space is formed between the bracket and the porous mesh trough (tank body) for storing the self-driven electrolyte solution, thereby effectively ensuring the supply of raw materials for the electrolysis reaction;
  • the porous mesh trough (tank body) and the non-energy-consuming mass transfer layer are convenient for preventing non-stop The impurities in the pure aqueous solution pass through, further ensuring the electrolysis effect and reducing pollution;
  • the hydrogen collection pipe transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle.
  • the hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen; the hydrogen scrubber is used to remove particulate matter or gas pollutants, thereby further collecting The purity of the hydrogen gas. It can realize the separation of hydrogen and oxygen when multiple groups of electrolysis units are used in series and parallel, and can collect hydrogen and oxygen well.
  • the present invention can realize efficient and stable hydrogen energy conversion without side reactions under high voltage and high current density.
  • the present invention uses a self-driven electrolyte to induce the liquefaction phase change of water vapor to form an electrolyte solution, which greatly improves the conductivity of the electrolysis system and avoids the problem of low concentration of H+ and OH- in seawater hydrogen production and low cathode and anode transmission efficiency.
  • the water vapor phase change liquefied by the self-driven electrolyte in the present invention is impurity-free water, it breaks through the bottleneck of direct seawater hydrogen production that is restricted by seawater composition over time, climate, human activities and other factors.
  • this system method can It is used for electrolytic hydrogen production in any non-pure water environment such as river water, lake water, sludge, swamps, rivers, etc., which greatly broadens the source range of hydrogen energy and is not limited by time and space.
  • the solution system does not contain impurity ions such as calcium ions and magnesium ions, and there will be no calcium and magnesium precipitation during long-term operation, reducing the risk of later stages. Be clear about maintenance costs.
  • the device of the present invention multiple groups of electrolysis units can be used in series and parallel, which increases the hydrogen production per unit time of the device system and is conducive to large-scale utilization.
  • the device of the present invention is relatively light and compact, and can be truly used in situ in seas, lakes, and rivers, which is beneficial to saving land resources.
  • Figure 1 is a schematic structural diagram of an in-situ direct electrolysis hydrogen production device (static hydrogen production) without desalination of non-pure aqueous solution according to the present invention
  • FIG. 2 is a schematic structural diagram of an in-situ direct electrolysis hydrogen production device (dynamic hydrogen production) without desalination of non-pure aqueous solutions according to the present invention
  • the electrolyte energy-free cycle regeneration module is a hollow fiber membrane type electrolyte energy-free cycle regeneration module.
  • FIG. 3 is a schematic structural diagram of an in-situ direct electrolysis hydrogen production device (dynamic hydrogen production) without desalination of non-pure aqueous solutions according to the present invention
  • the electrolyte energy-free cycle regeneration module is a flat membrane type electrolyte energy-free cycle regeneration module.
  • Figure 4-1 is a schematic diagram of the combined structure of the electrolysis unit in Figures 2-3.
  • Figure 4-2 is a schematic diagram of the split structure of the electrolysis unit in Figures 2-3.
  • Figure 5 is a schematic structural diagram of the electrolysis stack in Figures 2-3.
  • Figure 6-1 is a schematic diagram of the hollow fiber membrane structure in Figures 2-3.
  • Figure 6-2 is a schematic diagram of the flat membrane structure in Figures 2-3.
  • Figure 6-3 is a schematic diagram of the flat membrane structure in Figures 2-3.
  • FIG. 6 The marks and corresponding parts names in Figure 2- Figure 6 are: 1-energy supply module, 2-insulation slot, 3-anode plate, 4-anode catalytic layer, 5-separator, 6-cathode catalytic layer, 7-cathode plate, 8-anode solution chamber, 9-cathode solution chamber, 10-electrolysis unit, 11-bracket, 12-tank body, 13-upper end cover, 14-electrolyte solution chamber, 15-electrolysis stack, 16- Hydrogen collection pipe, 17-Hydrogen scrubber, 18-Hydrogen dryer, 19-Hydrogen storage, 20-Oxygen collection pipe, 21-Oxygen scrubber, 22-Oxygen dryer, 23-Oxygen storage, 24-Electrolyte incompetence Consumption circulation regeneration module, 25-impure aqueous solution tank, 26-impure aqueous solution chamber, 27-electrolyte solution circulation pipe, 28-impure
  • an in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution is used for static hydrogen production from electrolyte.
  • the device includes:
  • Energy supply module used to provide electric energy for the hydrogen production reaction. Electricity generated from renewable energy sources such as solar energy and wind energy, or thermal power and hydropower storage can be stored in the energy supply module. The electric energy for the hydrogen production reaction has a wide range of sources and is easy to store.
  • An electrolysis unit connected to the energy supply module includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber.
  • the anode plate and the cathode plate are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber;
  • multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack, for Hydrogen production reaction produces hydrogen gas;
  • Bracket used to fix the electrolysis stack
  • Porous mesh trough used to place the bracket.
  • the inner wall of the porous mesh trough is close to the water vapor mass transfer layer.
  • the water vapor mass transfer layer forms a concave space to form an electrolyte solution chamber for storing self-driven electrolyte solution;
  • the collection device is connected to the electrolysis unit to collect hydrogen and oxygen produced by electrolysis.
  • the electrolysis unit also includes an anode catalytic layer located in the anode solution chamber and a cathode catalytic layer located in the cathode solution chamber; the anode plate, the anode catalytic layer and the flow channel gap of the insulating slot form an anode solution chamber,
  • the anode solution chamber is filled with self-driven electrolyte solution;
  • the flow channel gap between the cathode plate and the cathode catalytic layer forms a cathode solution chamber, and the cathode solution chamber is filled with self-driven electrolyte solution; the electrolyte solution immerses the electrolysis stack.
  • the collection device includes a hydrogen collection pipe and an oxygen collection pipe; a hydrogen scrubber, a hydrogen dryer and a hydrogen storage device are connected in sequence behind the hydrogen collection pipe; an oxygen scrubber, an oxygen dryer and a hydrogen storage device are connected in sequence behind the oxygen collection pipe.
  • Oxygen reservoir The hydrogen collection tube transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle, and the hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen.
  • Hydrogen scrubbers are used to remove particulate matter or gaseous contaminants, thereby further improving the purity of the collected hydrogen.
  • an upper end cover is set on the porous mesh trough, and an interface is provided on the upper end cover for the hydrogen collection pipe, the oxygen collection pipe and the conductive wire of the energy supply module to pass through, and the interfaces are sealed and connected; when electrolytic hydrogen production , part of the porous mesh trough is immersed in the non-pure water solution, which generates a vapor pressure difference at the interface of the water vapor mass transfer layer, inducing gas generation in the non-pure water solution.
  • phase change and is directed to the electrolyte side through the water vapor mass transfer layer, and is induced to liquefy and absorb by the electrolyte under the action of the vapor pressure difference; the electrolyte is synchronously electrolyzed, further maintaining the interfacial vapor pressure difference between the impure aqueous solution and the electrolyte, thereby forming Stable hydrogen production process without additional energy consumption.
  • the porous mesh trough body and the water vapor mass transfer layer attached to the inner wall are sealed and connected with the upper end cover to form a sealed space, which is isolated from the outside air.
  • An electrolyte solution chamber is formed between the bracket, the porous mesh groove and the adjoining water vapor mass transfer layer, which is used to store the self-driven electrolyte solution.
  • the self-driven electrolyte solution enters the anode solution chamber through the anode plate 3 and infiltrates the anode catalytic layer and separator. Cathode catalytic layer and cathode solution chamber.
  • the porous mesh tank of the device is partially immersed in seawater, and the height of the seawater is controlled to be lower than the A-A surface.
  • the self-driven electrolyte solution induces water vapor mass transfer phase change to liquefy to obtain water, while the energy-free water vapor mass transfer layer blocks impure water impurities.
  • the self-driving electrolyte solution is a 10-50wt% KOH solution or a 10-40wt% H 2 SO 4 solution.
  • the cathode conduits of multiple groups of electrolysis units are connected and integrated to form a hydrogen collection pipe.
  • the produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber 17 and the hydrogen dryer, removes the water vapor entrained in the hydrogen, and is collected through the pipeline into the hydrogen storage for storage and further utilization.
  • the generated OH - is transferred to the anode catalytic layer 4 through the separator/ion exchange membrane, and an oxidation reaction occurs to generate oxygen.
  • the reaction formula is as follows:
  • the oxygen generated by the oxygen evolution reaction is collected through the oxygen collection pipe 20, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank.
  • reaction formula is as follows:
  • the oxygen produced by the oxygen evolution reaction is collected through the oxygen collection pipe, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank.
  • the generated H + is transferred to the cathode catalytic layer through the separator/ion exchange membrane 5, and a reduction reaction occurs to generate hydrogen.
  • the reaction formula is as follows: 2H + +2e - ⁇ H 2
  • the produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber and the hydrogen dryer, and removes the water vapor entrained in the hydrogen. It is collected through the pipeline and entered into the hydrogen storage tank for storage and further utilization.
  • the device can be directly immersed in an impure aqueous solution.
  • the impure aqueous solution (seawater, lake water, river water, industrial wastewater, etc.) vaporizes and phase changes to form water vapor, and the water vapor passes through in a directed manner.
  • the energy-free water vapor mass transfer layer is then liquefied by phase change induced by the self-driven electrolyte to form an electrolyte solution.
  • the hydrophobic effect of the energy-free water vapor mass transfer layer effectively blocks impurities in the impure aqueous solution; the electrolyte solution undergoes simultaneous electrolysis to produce hydrogen; the electrolyte solution
  • the water in the system is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation and driving of the system without additional energy consumption, thereby achieving continuous, efficient and stable hydrogen production.
  • the impurities in the impure aqueous solution are effectively blocked by the hydrophobic effect of the energy-free water vapor mass transfer layer.
  • the self-driven electrolyte induces the phase change of water vapor to liquefy to obtain water to form an electrolyte solution, and hydrogen is produced through the chemical principle of catalytic electrolysis.
  • the hydrogen production process based on catalytic electrolysis is as follows: the electrolyte solution chamber and anode solution chamber store the self-driven electrolyte solution, and Through the diaphragm, the cathode solution chamber is immersed, and after the system is immersed in the aqueous solution, hydrogen is produced through electrolysis, inducing electrolyte cycle regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation drive of the system without additional energy consumption.
  • electrolysis After electrolysis starts, the water undergoes a reduction reaction at the cathode catalytic electrode to produce hydrogen, and an oxygen evolution reaction occurs at the anode catalytic electrode.
  • the separator/ion exchange membrane is used to transfer hydroxide radicals or protons.
  • PTFE porous waterproof and breathable membrane is used as the energy-free water vapor mass transfer layer
  • 140kg 30wt% potassium hydroxide solution is used as the electrolyte solution
  • nickel molybdenum foam is used as the anode catalyst
  • nickel platinum-plated mesh is used as the cathode catalyst
  • the polysulfone membrane is used as the separator.
  • the test was carried out under the condition of 250mA/ cm2 , and the experimental results are shown in Figure 7. As shown in Figure 7, the device has been operating stably in Shenzhen Bay seawater for 1600 hours.
  • the actual voltage of the stack is about 2.1V
  • the energy consumption is about 5kWh/Nm 3 H 2
  • Energy supply module used to provide electrical energy for the hydrogen production reaction
  • An electrolysis unit connected to the energy supply module includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber.
  • the anode plate and the cathode plate are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber;
  • multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack, for Hydrogen production reaction produces hydrogen gas;
  • Bracket used to fix the electrolysis stack
  • Tank body with frame used to place the bracket, forming an electrolyte solution chamber in the gap between the bracket and the tank body, used to store self-driven electrolyte solution;
  • the collection device is connected to the electrolysis unit to collect the hydrogen produced by electrolysis.
  • the electrolysis unit also includes an anode catalytic layer located in the anode solution chamber and a cathode catalytic layer located in the cathode solution chamber; the anode plate, the anode catalytic layer and the flow channel gap of the insulating slot form an anode solution chamber,
  • the anode solution chamber is filled with self-driven electrolyte solution;
  • the flow channel gap between the cathode plate and the cathode catalytic layer forms a cathode solution chamber, and the cathode solution chamber is filled with self-driven electrolyte solution; the electrolyte solution immerses the electrolysis stack.
  • the collection device includes a hydrogen collection pipe and an oxygen collection pipe; a hydrogen scrubber, a hydrogen dryer and a hydrogen storage device are connected in sequence behind the hydrogen collection pipe; an oxygen scrubber, an oxygen dryer and an oxygen storage device are connected in sequence behind the oxygen collection pipe. storage.
  • the hydrogen collection pipe transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle, and the hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen.
  • Hydrogen scrubbers are used to remove particulate matter or gaseous contaminants, thereby further improving the purity of the collected hydrogen.
  • the upper end cover When used for dynamic hydrogen production, there is an upper end cover at the upper end of the tank body.
  • the upper end cover is provided with an interface for the hydrogen collection pipe, the oxygen collection pipe and the conductive wire of the energy supply module to pass through, and the interfaces are sealed and connected.
  • An electrolyte energy-free cycle regeneration module is also provided on one side of the tank.
  • the electrolyte energy-free cycle regeneration module is connected to the tank through an electrolyte solution circulation pipeline with an electrolyte solution circulation pump; the electrolyte energy-free cycle regeneration module is a hollow fiber membrane type. Electrolyte energy-free recycling regeneration module.
  • the hollow fiber membrane type electrolyte energy-free recycling regeneration module includes a hollow fiber membrane mass transfer cabin, a hollow fiber membrane, a hollow fiber membrane inner cavity, a hollow fiber membrane outer chamber, a non-pure aqueous solution tank, a non-pure aqueous solution chamber, and a non-pure aqueous solution chamber.
  • Aqueous solution circulation pipeline and non-pure aqueous solution circulation pump; multiple parallel hollow fiber membranes are densely arranged in the hollow fiber membrane mass transfer chamber.
  • the flowable solution space inside the hollow fiber membrane membrane layer is the hollow fiber membrane inner cavity, and the hollow fiber membrane membrane membrane
  • the space between the outer wall of the layer and the hollow fiber membrane mass transfer chamber is the outer chamber of the hollow fiber membrane; the tank body, the electrolyte solution circulation pipe, the electrolyte solution circulation pump and the hollow fiber membrane are connected in series.
  • the electrolyte solution circulation pump circulates the self-driven electrolyte solution to make the electrolyte
  • the solution chamber is connected to the inner cavity of the hollow fiber membrane, and the self-driven electrolyte solution passes through the inner cavity of the hollow fiber membrane;
  • the hollow fiber membrane mass transfer chamber is connected in series with the non-pure aqueous solution circulation pipe, the non-pure aqueous solution circulation pump, and the non-pure aqueous solution tank; the non-pure aqueous solution
  • the circulation pump is used to circulate non-pure water solution.
  • the outer chamber of the hollow fiber membrane is connected with the non-pure water solution chamber.
  • the non-pure water solution passes through the outer chamber of the hollow fiber membrane.
  • the self-driven electrolyte solution induces The phase change of the impure aqueous solution vaporizes to form water vapor.
  • the water vapor directionally migrates to the electrolyte side through the fiber membrane and is induced to liquefy and phase change, providing pure water for electrolysis.
  • This process involves no energy consumption from the outer chamber of the hollow fiber membrane to the inner cavity of the hollow fiber membrane. Pure water is transferred while the hollow fiber membrane blocks out impurities in impure aqueous solutions.
  • the tank body, electrolyte solution circulation pipeline, electrolyte solution circulation pump, shunt manifold and double-layer flat membrane are connected in series.
  • the solution circulation pump circulates the self-driven electrolyte solution, so that the electrolyte solution chamber is connected to the inner cavity of the flat membrane, and the self-driven electrolyte solution passes through the inner cavity of the flat membrane; the flat membrane mass transfer chamber and the non-pure water solution circulation pipeline, the non-pure water solution circulation pump, and the non-pure water solution circulation pump
  • the aqueous solution tanks are connected in series; the impure aqueous solution circulation pump is used to circulate the impure aqueous solution.
  • the outer chamber of the flat membrane is connected with the impure aqueous solution chamber, and the impure aqueous solution passes through the outer chamber of the flat membrane; during the two-way circulation process, under the action of the interface vapor pressure difference, , the self-driven electrolyte solution induces the phase change and vaporization of the non-pure aqueous solution to form water vapor.
  • the water vapor is directionally migrated to the electrolyte side through the fiber membrane, and is induced to liquefy and phase change, providing pure water for electrolysis. This process moves from the outer chamber of the flat membrane to the flat membrane.
  • the inner cavity transfers water without energy consumption, and the double-layer flat membrane blocks impurities in impure water.
  • the electrolyte solution chamber is connected to the outer chamber of the hollow fiber membrane, and the self-driven electrolyte solution passes through the outer chamber of the hollow fiber membrane; the inner chamber of the hollow fiber membrane is connected to the non-pure aqueous solution chamber, and the non-pure aqueous solution passes through the inner chamber of the hollow fiber membrane.
  • the self-driven electrolyte solution induces phase change and vaporization of the impure aqueous solution to form water vapor.
  • the water vapor directionally migrates to the electrolyte side through the membrane and is induced to liquefy and phase change, providing pure water for electrolysis. This process is performed by hollow fibers.
  • the inner chamber of the membrane transfers water to the outer chamber of the hollow fiber membrane without energy consumption.
  • the cathode conduits of multiple groups of electrolysis units are connected and integrated to form a hydrogen collection pipe.
  • the produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber 17 and the hydrogen dryer, removes the water vapor entrained in the hydrogen, and is collected through the pipeline into the hydrogen storage for storage and further utilization.
  • the generated OH - is transferred to the anode catalytic layer 4 through the separator/ion exchange membrane, and an oxidation reaction occurs to generate oxygen.
  • the reaction formula is as follows:
  • the oxygen generated by the oxygen evolution reaction is collected through the oxygen collection pipe 20, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank.
  • reaction formula is as follows:
  • the oxygen produced by the oxygen evolution reaction is collected through the oxygen collection pipe, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank.
  • the generated H + is transferred to the cathode catalytic layer through the separator/ion exchange membrane 5, and a reduction reaction occurs to generate hydrogen.
  • the reaction formula is as follows: 2H + +2e - ⁇ H 2
  • the produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber and the hydrogen dryer, and removes the water vapor entrained in the hydrogen. It is collected through the pipeline and entered into the hydrogen storage tank for storage and further utilization.
  • the electrolyte solution is synchronously electrolyzed to produce hydrogen.
  • the water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous and efficient hydrogen production.
  • the electrolyte is pumped to the electrolyte energy-free circulation regeneration module, and under the same principle as above, the water is transferred from the impure aqueous solution to the electrolyte solution, thereby maintaining a stable hydrogen production process.
  • the energy supply module provides electric energy for the electrolysis unit. Electricity generated from renewable energy sources such as solar energy and wind energy or thermal power and hydropower is stored in the energy supply module to provide electric energy for the hydrogen production reaction.
  • the electric energy for the hydrogen production reaction has a wide range of sources and is easy to store.
  • the electrolysis unit of the present invention is suitable for a wider range of hydrogen production electrolysis structures.
  • the arrangement of the anode catalytic layer in the anode solution chamber and the cathode catalytic layer in the cathode solution chamber is beneficial to increasing the rate of the electrolysis reaction.
  • the compactness of the internal plates and catalytic layers greatly improves the stability of the entire electrolysis unit.
  • Available anode catalytic electrodes include: nickel-molybdenum foam, nickel-iron foam, FexCoyNiz catalyst, ruthenium-iridium, NiFe-LDH, NiFeCu alloy catalyst, etc. (selected according to the actual acidity and alkalinity of the electrolyte); available hydrogen evolution catalysts include: platinum mesh, Nickel-plated platinum mesh, etc. (select according to the actual acidity and alkalinity of the electrolyte).
  • the hollow fiber membrane can be any material with waterproof and breathable properties.
  • Energy supply module used to provide electrical energy for the hydrogen production reaction
  • An electrolysis unit connected to the energy supply module includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber.
  • the anode plate and the cathode The polar plates are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber; multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack for hydrogen production reaction to generate hydrogen;
  • Bracket used to fix the electrolysis stack
  • Tank body with frame used to place the bracket, forming an electrolyte solution chamber in the gap between the bracket and the tank body, used to store self-driven electrolyte solution;
  • the collection device is connected to the electrolysis unit to collect the hydrogen produced by electrolysis.
  • the electrolysis unit also includes an anode catalytic layer located in the anode solution chamber and a cathode catalytic layer located in the cathode solution chamber; the anode plate, the anode catalytic layer and the flow channel gap of the insulating slot form an anode solution chamber,
  • the anode solution chamber is filled with self-driven electrolyte solution;
  • the flow channel gap between the cathode plate and the cathode catalytic layer forms a cathode solution chamber, and the cathode solution chamber is filled with self-driven electrolyte solution; the electrolyte solution immerses the electrolysis stack.
  • the collection device includes a hydrogen collection pipe and an oxygen collection pipe; a hydrogen scrubber, a hydrogen dryer and a hydrogen storage device are connected in sequence behind the hydrogen collection pipe; an oxygen scrubber, an oxygen dryer and an oxygen storage device are connected in sequence behind the oxygen collection pipe. storage.
  • the hydrogen collection pipe transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle, and the hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen.
  • Hydrogen scrubbers are used to remove particulate matter or gaseous contaminants, thereby further improving the purity of the collected hydrogen.
  • the upper end cover When used for dynamic hydrogen production, there is an upper end cover at the upper end of the tank body.
  • the upper end cover is provided with an interface for the hydrogen collection pipe, the oxygen collection pipe and the conductive wire of the energy supply module to pass through, and the interfaces are sealed and connected.
  • An electrolyte energy-free cycle regeneration module is also provided on one side of the tank.
  • the electrolyte energy-free cycle regeneration module is connected to the tank through an electrolyte solution circulation pipeline with an electrolyte solution circulation pump; the electrolyte energy-free cycle regeneration module is a flat membrane type electrolyte. No energy consumption recycling module.
  • the flat membrane type electrolyte energy-free recycling regeneration module includes a flat membrane mass transfer chamber, a double-layer flat membrane, a flat membrane inner cavity, a flat membrane outer chamber, a shunt manifold, a non-pure aqueous solution tank, and a non-pure aqueous solution chamber.
  • a single set of double-layer flat membranes is composed of two membrane layers arranged in parallel, and both sides are sealed.
  • the narrow gap in the middle of the double-layer flat membrane is the inner cavity of the flat membrane, and the space between the outer wall of the membrane layer of the double-layer flat membrane and the flat membrane mass transfer chamber is the outer chamber of the flat membrane.
  • the tank body, electrolyte solution circulation pipeline, electrolyte solution circulation pump, shunt manifold and double-layer flat membrane are connected in series.
  • the electrolyte solution circulation pump circulates the self-driven electrolyte solution to connect the electrolyte solution chamber to the inner cavity of the flat membrane.
  • the self-driven electrolyte solution flows from the flat membrane to The inner chamber passes through; the flat membrane mass transfer chamber is connected in series with the non-pure water solution circulation pipe, the non-pure water solution circulation pump, and the non-pure water solution tank; the non-pure water solution circulation pump is used to circulate the non-pure water solution, and the flat membrane outer chamber is connected with the non-pure water solution chamber.
  • the non-pure aqueous solution passes through the outer chamber of the flat membrane; during the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces the phase change and gasification of the non-pure aqueous solution to form water vapor, and the water vapor directionally migrates to the electrolyte side through the fiber membrane. It is induced to undergo a liquefaction phase change to provide pure water for electrolysis. This process transfers water from the outer chamber of the flat membrane to the inner chamber of the flat membrane without energy consumption. At the same time, the double-layer flat membrane blocks impurities in impure water.
  • the electrolyte solution chamber is connected to the outer chamber of the flat membrane, and the self-driven electrolyte solution passes through the outer chamber of the flat membrane; the inner chamber of the flat membrane is connected to the non-pure aqueous solution chamber, and the non-pure aqueous solution passes through the inner chamber of the flat membrane.
  • the interface vapor pressure difference Under the action, the self-driven electrolyte solution induces the phase change of the non-pure aqueous solution to vaporize to form water vapor.
  • the water vapor directionally migrates to the electrolyte side through the membrane and is induced to liquefy and phase change to provide pure water for electrolysis. This process moves from the inner cavity of the flat membrane to the flat plate.
  • the outer chamber of the membrane transfers moisture without energy consumption.
  • the cathode conduits of multiple groups of electrolysis units are connected and integrated to form a hydrogen collection pipe.
  • the produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber 17 and the hydrogen dryer, removes the water vapor entrained in the hydrogen, and is collected through the pipeline into the hydrogen storage tank for storage and next generation. step utilization.
  • the generated OH - is transferred to the anode catalytic layer 4 through the separator/ion exchange membrane, and an oxidation reaction occurs to generate oxygen.
  • the reaction formula is as follows:
  • the oxygen generated by the oxygen evolution reaction is collected through the oxygen collection pipe 20, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank.
  • reaction formula is as follows:
  • the oxygen produced by the oxygen evolution reaction is collected through the oxygen collection pipe, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank.
  • the generated H + is transferred to the cathode catalytic layer through the separator/ion exchange membrane 5, and a reduction reaction occurs to generate hydrogen.
  • the reaction formula is as follows: 2H + +2e - ⁇ H 2
  • the produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber and the hydrogen dryer, and removes the water vapor entrained in the hydrogen. It is collected through the pipeline and entered into the hydrogen storage tank for storage and further utilization.
  • the electrolyte solution is synchronously electrolyzed to produce hydrogen.
  • the water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous and efficient hydrogen production.
  • the energy supply module provides electric energy for the electrolysis unit. Electricity generated from renewable energy sources such as solar energy and wind energy or thermal power and hydropower is stored in the energy supply module to provide electric energy for the hydrogen production reaction.
  • the electric energy for the hydrogen production reaction has a wide range of sources and is easy to store.
  • the electrolysis unit of the present invention is suitable for a wider range of hydrogen production electrolysis structures.
  • the arrangement of the anode catalytic layer in the anode solution chamber and the cathode catalytic layer in the cathode solution chamber is beneficial to increasing the rate of the electrolysis reaction.
  • the compactness of the internal plates and catalytic layers greatly improves the stability of the entire electrolysis unit.
  • Available anode catalytic electrodes include: nickel-molybdenum foam, nickel-iron foam, FexCoyNiz catalyst, ruthenium-iridium, NiFe-LDH, NiFeCu alloy catalyst, etc. (selected according to the actual acidity and alkalinity of the electrolyte); available hydrogen evolution catalysts include: platinum mesh, Nickel-plated platinum mesh, etc. (select according to the actual acidity and alkalinity of the electrolyte).
  • the membrane layer of the flat membrane can be any material with waterproof and breathable properties.
  • the entire system device described in this application can be designed as an integrated device recommended for portability or large-scale preparation according to the demand for hydrogen production. It can be used in any non-pure environment including sludge, swamps, rivers, lakes, and industrial wastewater. It can be used in a water system environment and can carry out continuous in-situ hydrogen production without being restricted by time and space. At the same time, the system device can be coupled with wind power and photovoltaic to realize energy conversion of unstable renewable energy, and the hydrogen energy formed is conducive to stable storage.
  • the electrolytic assembly method used in the patent of this invention can be a single group or multiple groups, and can be connected in parallel or in series. It is not only suitable for regular shapes, but can also be replaced with special shapes in the future to adapt to different regional environments.
  • the invention is mainly used for immersed electrolysis hydrogen production in non-pure water, and can also be used for non-immersed hydrogen production, or for directly capturing moisture in the atmosphere.
  • this invention can also couple renewable energy sources such as wind power, photovoltaic, and nuclear energy to achieve green hydrogen production.
  • the present invention constructs a seawater-free in-situ direct electrolysis hydrogen production system without desalination, which can promote water vapor transfer from various impure water systems such as seawater, river water, lake water, silt, swamps, etc. through the interface pressure difference between seawater and electrolytes.
  • the substance is liquefied by phase change induced by the self-driven electrolyte, and the collected water is used to produce hydrogen under the electrolysis reaction.
  • This invention fundamentally solves the problems of complex ion components causing the failure of ion exchange membranes, deactivation of catalysts, and the generation of alkaline precipitation and toxic gases. At the same time, it will help future hydrogen energy conversion not be limited by time and space, and become the source of impure water. Provide strong technical support for direct hydrogen production.
  • the in-situ direct electrolysis hydrogen production system without desalination of non-pure aqueous solutions achieves the overall desalination-free seawater through three main processes: energy input through the power supply module, self-driven electrolyte-induced water vapor mass transfer phase change liquefaction, spontaneous acquisition of impurity-free water, and electrolysis catalytic hydrogen production.
  • Direct electrolysis of hydrogen First, the power supply module provides power for the electrolysis hydrogen production module.
  • the energy source of the power supply module can be converted into electrical energy from renewable energy sources such as solar energy and wind energy, or it can directly utilize thermal power, hydropower, etc.
  • the in-situ direct electrolysis hydrogen production device without desalination is immersed in the water.
  • the system provides electrical energy through the power supply module, obtains water through the self-driven electrolyte to induce water vapor mass transfer and liquefaction phase change, and then uses the principle of catalytic electrolysis to produce hydrogen.
  • this system can realize a dynamic and continuous process of hydrogen production without temporal and spatial differences in any aqueous solution environment; on the other hand, it can realize energy conversion and stable storage of non-stable renewable energy, providing technical means for the construction of future energy systems.

Abstract

Disclosed in the present invention are a desalination-free in-situ direct electrolytic hydrogen production device for a non-pure-water solution, and a use method. The desalination-free in-situ direct electrolytic hydrogen production device comprises an electrolysis system, a water vapor mass transfer layer, a collecting device and a containing device for containing a self-driving electrolyte solution, wherein the water vapor mass transfer layer isolates the electrolysis system from a non-pure-water solution to be electrolyzed, and the water vapor mass transfer layer can make water molecules of said non-pure-water solution enter the electrolysis system by means of phase change migration and can prevent solid and liquid substances in the non-pure-water solution from passing through; and the collecting device is in communication with the electrolysis system and is used for respectively collecting hydrogen and oxygen generated by electrolysis. The present invention solves the problems of incapability of in-situ hydrogen production due to space-time limitations, low electrolytic efficiency, high energy consumption, great increase of cost, catalyst corrosion, membrane blockage, etc., in the existing direct hydrogen production technology for a non-pure-water solution.

Description

一种非纯水溶液无淡化原位直接电解制氢装置及使用方法A device and method of using in-situ direct electrolysis hydrogen production from non-pure aqueous solution without desalination 技术领域Technical field
本发明属于电解制氢技术领域，具体为一种非纯水溶液无淡化原位直接电解制氢装置及使用方法。The invention belongs to the technical field of electrolytic hydrogen production, and is specifically a device and a method of using in-situ direct electrolysis hydrogen production from non-pure aqueous solution without desalination.
背景技术Background technique
氢能具有来源广、可储存、用途多、零碳零污染及能量密度大等优势，是未来能源领域的关键组成部分。目前电解水获取氢能有两种。其一是利用自然界的海水、河水或湖水等直接进行电解制氢，其存在以下问题：Hydrogen energy has the advantages of wide source, storability, multiple uses, zero carbon and zero pollution, and high energy density. It is a key component of the future energy field. There are currently two methods of electrolyzing water to obtain hydrogen energy. One is to use natural seawater, river water or lake water to directly produce hydrogen through electrolysis, which has the following problems:
(1)成分复杂，且组分会随季节、气候、温度、地域和人为活动等因素而变化，因此，不同区域的非纯水直接制氢电解装置不能直接兼容；(1) The composition is complex, and the composition changes with factors such as season, climate, temperature, region, and human activities. Therefore, non-pure water direct hydrogen production electrolysis devices in different regions are not directly compatible;
(2)溶液中富含Cl-，在电解反应中，Cl-可以在析氧反应中被氧化，产生有毒、对环境有害、有腐蚀的ClO-和Cl2；(2) The solution is rich in Cl - . In the electrolysis reaction, Cl - can be oxidized in the oxygen evolution reaction, producing toxic, environmentally harmful, and corrosive ClO - and Cl 2 ;
(3)非纯水溶液直接制氢时H+和OH-离子浓度微小，或缓冲分子无法运输分别在阴极和阳极的OH-和H+，导致电解效率低，因此需要额外使用添加剂或使用离子交换膜，从而成本大幅增加；(3) When hydrogen is directly produced from non-pure aqueous solutions, the concentrations of H + and OH - ions are very small, or the buffer molecules cannot transport OH - and H + at the cathode and anode respectively, resulting in low electrolysis efficiency, so additional additives or ion exchange are required. membrane, thereby significantly increasing the cost;
(4)非纯水溶液中的杂质离子、微生物、有机质等复杂成分，容易堵塞污染离子交换膜、甚至导致膜失活，从而大幅增加后期维护成本；(4) Complex components such as impurity ions, microorganisms, and organic matter in non-pure aqueous solutions can easily block and contaminate the ion exchange membrane, and even cause membrane deactivation, thereby significantly increasing subsequent maintenance costs;
(4)由于电解时的局部pH差异可能导致与钙镁离子等产生沉淀，需要使用酸进行沉淀处理，产生额外成本。(4) Due to the local pH difference during electrolysis, it may cause precipitation with calcium and magnesium ions, etc., which requires the use of acid for precipitation treatment, resulting in additional costs.
其二是将非纯水溶液进行淡化/净化处理，制取纯水后用于电解制氢。仍然以海水为例，需通过海水淡化过程，该方法需要在海岸建立海水淡化厂，从建设、运营、人力、维护等方面大幅提升成本；且难以大规模利用海上风电耦合形成原位一体化绿氢生产体系，实现可再生能源的稳定储存。The second is to desalinize/purify the non-pure water solution and prepare pure water for electrolysis to produce hydrogen. Still taking seawater as an example, a seawater desalination process is required. This method requires the establishment of a seawater desalination plant on the coast, which greatly increases the cost in terms of construction, operation, manpower, maintenance, etc.; and it is difficult to use offshore wind power coupling on a large scale to form an in-situ integrated green plant. Hydrogen production system to achieve stable storage of renewable energy.
发明内容Contents of the invention
本发明的目的是针对现有技术的不足，解决现有非纯水溶液直接制氢技术存在的受时空限制不能原位制氢、电解效率低、能耗高、成本大幅增加、催化剂腐蚀和膜堵塞等问题；提供一种非纯水溶液无淡化原位直接电解制氢装置及使用方法，本发明将非纯水溶液无淡化原位直接电解制氢装置无需淡化/净化的直接利用非纯水溶液制氢，在电解质和非纯水溶液界面压力差推动作用下，水汽通过无能耗水汽传质层，被自驱动电解质诱导相变液化形成电解质溶液，同时无能耗水汽传质层的疏水作用将非纯水溶液中的杂质有效阻隔。电解质溶液同步电解制氢，电解质溶液中的水不断被电解消耗，诱导电解质循环再生，维持界面压力差，实现系统无额外能耗的自循环激发驱动，从而实现连续高效稳定产氢。The purpose of the present invention is to address the shortcomings of the existing technology and solve the problems of the existing direct hydrogen production technology from non-pure aqueous solutions, which are limited by time and space and cannot produce hydrogen in situ, low electrolysis efficiency, high energy consumption, substantial increase in cost, catalyst corrosion and membrane clogging. and other problems; provide an in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solutions and a method of use. The present invention directly uses non-pure aqueous solutions to produce hydrogen without desalination/purification. Driven by the pressure difference at the interface between the electrolyte and the non-pure aqueous solution, the water vapor passes through the energy-free water vapor mass transfer layer and is liquefied by the phase change induced by the self-driven electrolyte to form an electrolyte solution. At the same time, the hydrophobic effect of the energy-free water vapor mass transfer layer removes the water vapor in the non-pure aqueous solution. Impurities are effectively blocked. The electrolyte solution is synchronously electrolyzed to produce hydrogen. The water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous, efficient and stable hydrogen production.
为了实现以上发明目的，本发明的具体技术方案为：In order to achieve the above objects, the specific technical solutions of the present invention are:
一种非纯水溶液无淡化原位直接电解制氢装置，有两种模式，分别为用于电解液静态制氢和动态循环电解液制氢。An in-situ direct electrolysis hydrogen production device without desalination from non-pure aqueous solutions has two modes: static hydrogen production from electrolyte and dynamic hydrogen production from electrolyte.
一种非纯水溶液无淡化原位直接电解制氢装置，用于电解液静态制氢，该装置包括：An in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution, used for static hydrogen production from electrolyte. The device includes:
供能模块：用于为制氢反应提供电能；Energy supply module: used to provide electrical energy for the hydrogen production reaction;
与供能模块连接的电解单元：所述电解单元包括相对设置的阳极溶液室、阴极溶液室，设于所述阳极溶液室内的阳极极板，设于所述阴极溶液室内的阴极极板，所述阳极极板与所述阴极极板分别与所述供能模块相连，所述阳极溶液室与所述阴极溶液室之间设有隔膜；多个电解单元串联或并联堆叠形成电解堆，用于制氢反应，产生氢气。电解单元中阳极极板串联或并联连接导线接至供能模块的正极，电解单元中阴极极板串联或并联连接导线接至供能模块的负极。An electrolysis unit connected to the energy supply module: the electrolysis unit includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber. The anode plate and the cathode plate are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber; multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack, for Hydrogen production reaction produces hydrogen gas. The anode plates in the electrolysis unit are connected in series or in parallel to the positive electrode of the energy supply module, and the cathode plates in the electrolysis unit are connected in series or in parallel to the negative electrode of the energy supply module.
支架：用于固定电解堆； Bracket: used to fix the electrolysis stack;
多孔网槽：用于放置支架，多孔网槽内壁紧贴水汽传质层，水汽传质层形成一个凹形空间，形成电解质溶液室，用于存放自驱动电解质溶液；Porous mesh trough: used to place the bracket. The inner wall of the porous mesh trough is close to the water vapor mass transfer layer. The water vapor mass transfer layer forms a concave space to form an electrolyte solution chamber for storing self-driven electrolyte solution;
收集装置：收集装置与电解单元相连，用以收集电解产生的氢气和氧气。Collection device: The collection device is connected to the electrolysis unit to collect hydrogen and oxygen produced by electrolysis.
一种非纯水溶液无淡化原位直接电解制氢装置，用于动态循环电解液制氢，该装置包括：供能模块：用于为制氢反应提供电能；An in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution, used for dynamic circulation of electrolyte to produce hydrogen. The device includes: an energy supply module: used to provide electrical energy for the hydrogen production reaction;
与供能模块连接的电解单元：所述电解单元包括相对设置的阳极溶液室、阴极溶液室，设于所述阳极溶液室内的阳极极板，设于所述阴极溶液室内的阴极极板，所述阳极极板与所述阴极极板分别与所述供能模块相连，所述阳极溶液室与所述阴极溶液室之间设有隔膜；多个电解单元串联或并联堆叠形成电解堆，用于制氢反应，产生氢气；An electrolysis unit connected to the energy supply module: the electrolysis unit includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber. The anode plate and the cathode plate are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber; multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack, for Hydrogen production reaction produces hydrogen gas;
支架：用于固定电解堆；Bracket: used to fix the electrolysis stack;
带有框架的槽体：用于放置支架，在支架与槽体的空隙处形成电解质溶液室，用于存放自驱动电解质溶液；Tank body with frame: used to place the bracket, forming an electrolyte solution chamber in the gap between the bracket and the tank body, used to store self-driven electrolyte solution;
收集装置：收集装置与电解单元相连，用以收集电解产生的氢气。Collection device: The collection device is connected to the electrolysis unit to collect the hydrogen produced by electrolysis.
进一步的，所述电解单元还包括设于所述阳极溶液室内的阳极催化层、设于所述阴极溶液室内的阴极催化层；阳极极板、阳极催化层与绝缘卡槽的流道间隙形成阳极溶液室，阳极溶液室内充满自驱动电解质溶液；阴极极板与阴极催化层的流道间隙形成阴极溶液室，阴极溶液室内充满自驱动电解质溶液；电解质溶液浸没电解堆。Further, the electrolysis unit further includes an anode catalytic layer disposed in the anode solution chamber and a cathode catalytic layer disposed in the cathode solution chamber; the anode plate, the anode catalytic layer and the flow channel gap of the insulating slot form an anode. The anode solution chamber is filled with a self-driven electrolyte solution; the flow channel gap between the cathode plate and the cathode catalytic layer forms a cathode solution chamber, and the cathode solution chamber is filled with a self-driven electrolyte solution; the electrolyte solution is immersed in the electrolysis stack.
进一步的，所述的收集装置包括氢气收集管和氧气收集管；在氢气收集管后面依次连接有氢气洗涤器、氢气干燥器及氢气储存器；在氧气收集管后面依次连接有氧气洗涤器、氧气干燥器及氧气储存器。氢气收集管传输电解反应产生的氢气至氢气收集瓶，氢气干燥器干燥水蒸气等水汽物，提高了收集到的氢气的纯度。氢气洗涤器用以去除颗粒物或气体污染物，从而进一步收集到的氢气的纯度。Further, the collection device includes a hydrogen collection pipe and an oxygen collection pipe; a hydrogen scrubber, a hydrogen dryer and a hydrogen storage are connected in sequence behind the hydrogen collection pipe; an oxygen scrubber, an oxygen storage tank are connected in sequence behind the oxygen collection pipe. Dryer and oxygen storage. The hydrogen collection pipe transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle, and the hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen. Hydrogen scrubbers are used to remove particulate matter or gaseous contaminants, thereby further improving the purity of the collected hydrogen.
进一步的，用于静态制氢时，在多孔网槽上设置上端盖，在上端盖上开设有供氢气收集管、氧气收集管和供能模块的导电线通过的接口，接口处密封连接；电解制氢时，多孔网槽的部分浸于非纯水溶液，在水汽传质层界面处产生蒸汽压差，诱导非纯水溶液发生气化相变，同时通过水汽传质层定向传递至电解质侧，并在蒸汽压差作用下被电解质诱导液化吸收；电解质被同步电解，进一步维持非纯水溶液与电解质间的界面蒸汽压差，从而形成无需额外淡化/净化耗能的稳定制氢过程。Further, when used for static hydrogen production, an upper end cover is provided on the porous mesh trough, and an interface is provided on the upper end cover for the hydrogen collection pipe, the oxygen collection pipe and the conductive wire of the energy supply module to pass through, and the interfaces are sealed and connected; electrolysis When producing hydrogen, part of the porous mesh tank is immersed in the impure water solution, which generates a vapor pressure difference at the interface of the water vapor mass transfer layer, inducing the gasification phase change of the impure aqueous solution. At the same time, it is directionally transmitted to the electrolyte side through the water vapor mass transfer layer, and It is induced to liquefy and absorb by the electrolyte under the action of vapor pressure difference; the electrolyte is electrolyzed simultaneously, further maintaining the interfacial vapor pressure difference between the non-pure aqueous solution and the electrolyte, thereby forming a stable hydrogen production process without additional desalination/purification energy consumption.
更进一步的，当多孔网槽部分浸于非纯水溶液时，多孔网槽槽体及内壁贴合的水汽传质层与上端盖密封连接并形成密闭空间，与外界空气隔绝。Furthermore, when the porous mesh trough is partially immersed in a non-pure aqueous solution, the porous mesh trough body and the water vapor mass transfer layer attached to the inner wall are sealed and connected with the upper end cover to form a sealed space, which is isolated from the outside air.
进一步的，用于动态制氢时，在槽体的上端有上端盖，上端盖上开设有供氢气收集管、氧气收集管和供能模块的导电线通过的接口，接口处密封连接。Further, when used for dynamic hydrogen production, there is an upper end cover at the upper end of the tank body. The upper end cover is provided with interfaces for the hydrogen collection pipe, the oxygen collection pipe and the conductive wires of the energy supply module to pass through, and the interfaces are sealed and connected.
更进一步的，在槽体的一侧还设置有电解质无能耗循环再生模块，电解质无能耗循环再生模块通过带有电解质溶液循环泵的电解质溶液循环管道与槽体连通；电解质无能耗循环再生模块根据膜组件类型，分为中空纤维膜型电解质无能耗循环再生模块与平板膜型电解质无能耗循环再生模块两种。Furthermore, an electrolyte energy-free circulation regeneration module is also provided on one side of the tank body. The electrolyte energy-free circulation regeneration module is connected to the tank body through an electrolyte solution circulation pipeline with an electrolyte solution circulation pump; the electrolyte energy-free circulation regeneration module is based on Membrane module types are divided into two types: hollow fiber membrane electrolyte energy-free recycling regeneration module and flat membrane electrolyte energy-free recycling regeneration module.
作为优选，所述的中空纤维膜型电解质无能耗循环再生模块包括中空纤维膜传质舱、中空纤维膜、中空纤维膜内腔、中空纤维膜外部室、非纯水溶液槽体、非纯水溶液室、非纯水溶液循环管道和非纯水溶液循环泵；中空纤维膜传质舱内密集设置有多根并联的中空纤维膜，中空纤维膜膜层内部的可流通溶液空间为中空纤维膜内腔，中空纤维膜膜层外壁与中空纤维膜传质舱之间的空间为中空纤维膜外部室；槽体、电解质溶液循环管道、电解质溶液循环泵和中空纤维膜串联，电解质溶液循环泵循环自驱动电解质溶液，使电解质溶液室连通中空纤维膜内腔，自驱动电解质溶液从中空纤维膜内腔通过；中空纤维膜传质舱与非纯水溶液循环管道、非纯水溶液循环泵、非纯水溶液槽体串联；非纯水溶液循环泵用于循环非纯水溶液， 中空纤维膜外部室与非纯水溶液室连通，非纯水溶液从中空纤维膜外部室通过；双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过纤维膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由中空纤维膜外部室向中空纤维膜内腔无能耗转移纯净水分，同时中空纤维膜将非纯水溶液中的杂质阻挡在外。Preferably, the hollow fiber membrane type electrolyte energy-free recycling regeneration module includes a hollow fiber membrane mass transfer chamber, a hollow fiber membrane, a hollow fiber membrane inner cavity, a hollow fiber membrane outer chamber, a non-pure aqueous solution tank, and a non-pure aqueous solution chamber. , non-pure aqueous solution circulation pipeline and non-pure aqueous solution circulation pump; a plurality of parallel hollow fiber membranes are densely arranged in the hollow fiber membrane mass transfer chamber, and the flowable solution space inside the hollow fiber membrane membrane layer is the hollow fiber membrane inner cavity, which is hollow The space between the outer wall of the fiber membrane layer and the mass transfer chamber of the hollow fiber membrane is the outer chamber of the hollow fiber membrane; the tank body, the electrolyte solution circulation pipe, the electrolyte solution circulation pump and the hollow fiber membrane are connected in series, and the electrolyte solution circulation pump circulates the self-driven electrolyte solution , the electrolyte solution chamber is connected to the inner cavity of the hollow fiber membrane, and the self-driven electrolyte solution passes through the inner cavity of the hollow fiber membrane; the hollow fiber membrane mass transfer chamber is connected in series with the non-pure aqueous solution circulation pipe, the non-pure aqueous solution circulation pump, and the non-pure aqueous solution tank; Non-pure aqueous solution circulation pump is used to circulate non-pure aqueous solutions. The outer chamber of the hollow fiber membrane is connected to the non-pure aqueous solution chamber, and the non-pure aqueous solution passes through the outer chamber of the hollow fiber membrane; during the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces phase change and gasification of the non-pure aqueous solution to form water vapor. , water vapor directionally migrates to the electrolyte side through the fiber membrane, and is induced to liquefy phase change, providing pure water for electrolysis. This process transfers pure water from the outer chamber of the hollow fiber membrane to the inner cavity of the hollow fiber membrane without energy consumption, and at the same time, the hollow fiber membrane will Impurities in impure aqueous solutions are blocked out.
作为优选，所述的平板膜型电解质无能耗循环再生模块包括平板膜传质舱、双层平板膜、平板膜内腔、平板膜外部室、分流管汇管、非纯水溶液槽体、非纯水溶液室、非纯水溶液循环管道和非纯水溶液循环泵；其平板膜传质舱内排列设置有多组并联的双层平板膜，单组双层平板膜由两张膜层平行排布，两侧面密封，其顶、底面分别与分流管汇管连接；双层平板膜中间的狭长间隙为平板膜内腔，双层平板膜的膜层外壁与平板膜传质舱之间的空间为平板膜外部室。Preferably, the flat membrane type electrolyte energy-free recycling regeneration module includes a flat membrane mass transfer chamber, a double-layer flat membrane, a flat membrane inner chamber, a flat membrane outer chamber, a shunt manifold, a non-pure aqueous solution tank, a non-pure aqueous solution tank, and a flat membrane external chamber. The aqueous solution chamber, the non-pure aqueous solution circulation pipe and the non-pure aqueous solution circulation pump; the flat membrane mass transfer chamber is arranged with multiple sets of parallel double-layer flat membranes. A single set of double-layer flat membranes is composed of two membrane layers arranged in parallel. The side is sealed, and its top and bottom surfaces are connected to the shunt manifold respectively; the narrow gap in the middle of the double-layer flat membrane is the inner cavity of the flat membrane, and the space between the outer wall of the membrane layer of the double-layer flat membrane and the flat membrane mass transfer chamber is the flat membrane External room.
槽体、电解质溶液循环管道、电解质溶液循环泵、分流管汇和双层平板膜串联，电解质溶液循环泵循环自驱动电解质溶液，使电解质溶液室连通平板膜内腔，自驱动电解质溶液从平板膜内腔通过；平板膜传质舱与非纯水溶液循环管道、非纯水溶液循环泵、非纯水溶液槽体串联；非纯水溶液循环泵用于循环非纯水溶液，平板膜外部室与非纯水溶液室连通，非纯水溶液从平板膜外部室通过；双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过纤维膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由平板膜外部室向平板膜内腔无能耗转移水分，同时双层平板膜将非纯水中的杂质阻挡在外。The tank body, electrolyte solution circulation pipeline, electrolyte solution circulation pump, shunt manifold and double-layer flat membrane are connected in series. The electrolyte solution circulation pump circulates the self-driven electrolyte solution to connect the electrolyte solution chamber to the inner cavity of the flat membrane. The self-driven electrolyte solution flows from the flat membrane to The inner chamber passes through; the flat membrane mass transfer chamber is connected in series with the non-pure water solution circulation pipe, the non-pure water solution circulation pump, and the non-pure water solution tank; the non-pure water solution circulation pump is used to circulate the non-pure water solution, and the flat membrane outer chamber is connected with the non-pure water solution chamber. connected, the non-pure aqueous solution passes through the outer chamber of the flat membrane; during the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces the phase change and gasification of the non-pure aqueous solution to form water vapor, and the water vapor directionally migrates to the electrolyte side through the fiber membrane. It is induced to undergo a liquefaction phase change to provide pure water for electrolysis. This process transfers water from the outer chamber of the flat membrane to the inner chamber of the flat membrane without energy consumption. At the same time, the double-layer flat membrane blocks impurities in impure water.
电解质溶液室连通平板膜外部室(或中空纤维膜外部室)，自驱动电解质溶液从平板膜外部室(或中空纤维膜外部室)通过；平板膜内腔(或中空纤维膜内腔)连通非纯水溶液室，非纯水溶液从平板膜内腔(或中空纤维膜内腔)通过，双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由平板膜内腔(或中空纤维膜内腔)向平板膜外部室(或中空纤维膜外部室)无能耗转移水分。The electrolyte solution chamber is connected to the outer chamber of the flat membrane (or the outer chamber of the hollow fiber membrane), and the self-driven electrolyte solution passes through the outer chamber of the flat membrane (or the outer chamber of the hollow fiber membrane); the inner chamber of the flat membrane (or the inner chamber of the hollow fiber membrane) is connected to the non- In the pure water solution chamber, the impure aqueous solution passes through the inner cavity of the flat membrane (or the inner cavity of the hollow fiber membrane). During the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces the phase change and vaporization of the impure aqueous solution to form water vapor. Water vapor directionally migrates to the electrolyte side through the membrane and is induced to undergo a liquefaction phase change to provide pure water for electrolysis. This process moves from the inner cavity of the flat membrane (or the inner cavity of the hollow fiber membrane) to the outer chamber of the flat membrane (or the outer chamber of the hollow fiber membrane). ) transfers moisture without energy consumption.
本发明基于自驱动电解质与非纯水溶液间的界面蒸汽压差，诱导非纯水溶液气化相变，水蒸气通过水汽传质膜定向迁移至电解质侧，并同时液化相变被电解质吸收，为制氢过程提供纯净水分。静态制氢装置中，电解质处于静止状态。将非纯水溶液无淡化原位直接电解制氢装置直接浸于非纯水溶液中，在电解质和非纯水溶液界面压力差推动作用下，非纯水溶液相变气化产生水蒸气，水汽通过无能耗水汽传质层定向迁移至电解质侧，然后被自驱动电解质诱导相变液化形成液态水，同时无能耗水汽传质层的疏水作用将非纯水溶液中的杂质有效阻隔。电解质溶液同步进行电解制氢，电解质溶液中的水不断被电解消耗，诱导电解质循环再生，维持界面压力差，实现系统无额外能耗的自循环激发驱动，从而实现连续高效产氢。动态制氢装置中，电解液被泵送至电解质无能耗循环再生模块，并在上述同样的原理下，实现水分从非纯水溶液中向电解质溶液中的迁移，从而维持稳定的制氢过程。The invention is based on the interfacial vapor pressure difference between the self-driven electrolyte and the non-pure aqueous solution, inducing the vaporization phase change of the non-pure aqueous solution. The water vapor directionally migrates to the electrolyte side through the water vapor mass transfer membrane, and at the same time the liquefaction phase change is absorbed by the electrolyte. The hydrogen process provides pure moisture. In a static hydrogen production device, the electrolyte is in a static state. The in-situ direct electrolysis hydrogen production device without desalination of the non-pure aqueous solution is directly immersed in the non-pure aqueous solution. Driven by the pressure difference at the interface between the electrolyte and the non-pure aqueous solution, the non-pure aqueous solution phase changes and vaporizes to produce water vapor. The water vapor passes through the energy-free water vapor. The mass transfer layer directionally migrates to the electrolyte side, and is then liquefied by phase change induced by the self-driven electrolyte to form liquid water. At the same time, the hydrophobic effect of the energy-free water vapor mass transfer layer effectively blocks impurities in the non-pure aqueous solution. The electrolyte solution is synchronously electrolyzed to produce hydrogen. The water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous and efficient hydrogen production. In the dynamic hydrogen production device, the electrolyte is pumped to the electrolyte energy-free circulation regeneration module, and under the same principle as above, the water is transferred from the impure aqueous solution to the electrolyte solution, thereby maintaining a stable hydrogen production process.
由于本发明无需淡化工艺，极大的缩小了建设、运营、人力、维护等方面成本，且不受时空限制，极大的拓宽了氢能的来源范围；利用自驱动电解质诱导水汽液化相变形成电解质溶液，大幅提升了电解体系的电导率，避免了非纯水溶液制氢中H+和OH-浓度小在阴阳极传输效率低的问题；本发明中自驱动电解质诱导水汽相变液化的均为无杂质水分，因此突破了直接非纯水溶液制氢中氯离子被氧化产生Cl2或ClO-等腐蚀和有毒物质的瓶颈，产生腐蚀和有毒物质较少。从而解决现有技术存在的受时空限制不能原位制氢、电解效率低、能耗高、成本大幅增加、产生腐蚀和有毒物质较多等问题。Since the present invention does not require a desalination process, it greatly reduces the costs of construction, operation, manpower, maintenance, etc., and is not limited by time and space, greatly broadening the source range of hydrogen energy; it uses a self-driven electrolyte to induce the phase change of water vapor liquefaction to form The electrolyte solution greatly improves the conductivity of the electrolysis system and avoids the problem of low concentration of H + and OH - in hydrogen production from non-pure aqueous solutions and low cathode and anode transmission efficiency; in the present invention, the self-driven electrolyte induces water vapor phase change and liquefaction. There is no impurity moisture, so it breaks through the bottleneck of chlorine ions being oxidized to produce Cl 2 or ClO - and other corrosive and toxic substances in direct hydrogen production from non-pure aqueous solutions, and produces less corrosive and toxic substances. This solves the problems existing in the existing technology such as the inability to produce hydrogen in situ due to time and space constraints, low electrolysis efficiency, high energy consumption, significant increase in cost, and the generation of corrosion and toxic substances.
作为一种优选的技术方案，供能模块为电解单元提供电能，太阳能、风能等可再生能源产生的电力或火电、水电储存在供能模块中，用于为制氢反应提供电能，制氢反应的电能来 源广泛且易储存。As a preferred technical solution, the energy supply module provides electric energy for the electrolysis unit. The electricity generated from renewable energy sources such as solar energy and wind energy or thermal power and hydropower is stored in the energy supply module to provide electric energy for the hydrogen production reaction. The hydrogen production reaction of electrical energy comes Widely available and easy to store.
本发明的电解单元适用于较广范围的制氢电解结构。The electrolysis unit of the present invention is suitable for a wider range of hydrogen production electrolysis structures.
阳极溶液室内的阳极催化层、阴极溶液室内的阴极催化层的设置，这有利于提高电解反应的速率。内部极板和催化层紧凑化，大幅提高了整个电解单元的稳定性。The arrangement of the anode catalytic layer in the anode solution chamber and the cathode catalytic layer in the cathode solution chamber is beneficial to increasing the rate of the electrolysis reaction. The compactness of the internal plates and catalytic layers greatly improves the stability of the entire electrolysis unit.
可用的阳极催化电极包括：泡沫镍钼、泡沫镍铁、FexCoyNiz型催化剂、钌铱、NiFe-LDH、NiFeCu合金催化剂等(根据实际电解质酸碱性进行选择)；可用的析氢催化剂包括：铂金网、镍镀铂网等(根据实际电解质酸碱性进行选择)。Available anode catalytic electrodes include: nickel-molybdenum foam, nickel-iron foam, FexCoyNiz catalyst, ruthenium-iridium, NiFe-LDH, NiFeCu alloy catalyst, etc. (selected according to the actual acidity and alkalinity of the electrolyte); available hydrogen evolution catalysts include: platinum mesh, Nickel-plated platinum mesh, etc. (select according to the actual acidity and alkalinity of the electrolyte).
中空纤维膜、双层平板膜及(无能耗)水汽传质层的膜层，可以为任何具有防水透气性能的材料，如：具有防水、透气性能的多孔TPU膜、PDMS膜、PTFE膜中的一种或石墨烯、PVDF、PTFE等通过喷涂、丝网印刷、静电纺丝等方式制备的防水透气层。自驱动电解质溶液为10-50wt％的KOH溶液或10-40wt％的H2SO4溶液，具体可为10wt％的KOH溶液、15wt％的KOH溶液，20wt％的KOH溶液，25wt％的KOH溶液，30wt％的KOH溶液，35wt％的KOH溶液，40wt％的KOH溶液，45wt％的KOH溶液，50wt％的KOH溶液，10wt％的H2SO4溶液，15wt％的H2SO4溶液，20wt％的H2SO4溶液，25wt％的H2SO4溶液，30wt％的H2SO4溶液，35wt％的H2SO4溶液，40wt％的H2SO4溶液。The membrane layer of the hollow fiber membrane, double-layer flat membrane and (no energy consumption) water vapor mass transfer layer can be any material with waterproof and breathable properties, such as: porous TPU membrane, PDMS membrane, PTFE membrane with waterproof and breathable properties. A waterproof and breathable layer prepared by spraying, screen printing, electrospinning, etc. from graphene, PVDF, PTFE, etc. The self-driving electrolyte solution is a 10-50wt% KOH solution or a 10-40wt% H 2 SO 4 solution. Specifically, it can be a 10wt% KOH solution, a 15wt% KOH solution, a 20wt% KOH solution, or a 25wt% KOH solution. , 30wt% KOH solution, 35wt% KOH solution, 40wt% KOH solution, 45wt% KOH solution, 50wt% KOH solution, 10wt% H 2 SO 4 solution, 15wt% H 2 SO 4 solution, 20wt % H2SO4 solution , 25wt% H2SO4 solution , 30wt% H2SO4 solution, 35wt% H2SO4 solution, 40wt % H2SO4 solution.
本发明基于自驱动电解质与非纯水溶液间的界面蒸汽压差，诱导非纯水溶液气化相变，并通过水汽传质膜定向迁移至电解质侧，并同时液化相变被电解质吸收，为制氢过程提供纯净水分。静态制氢装置中，电解质处于静止状态。将非纯水溶液无淡化原位直接电解制氢装置直接浸于非纯水溶液中，在电解质和非纯水溶液界面压力差推动作用下，非纯水溶液相变气化产生水蒸气，水汽通过无能耗水汽传质层定向迁移至电解质侧，然后被自驱动电解质诱导相变液化形成液态水，同时无能耗水汽传质层的疏水作用将非纯水溶液中的杂质有效阻隔。电解质溶液同步进行电解制氢，电解质溶液中的水不断被电解消耗，诱导电解质循环再生，维持界面压力差，实现系统无额外能耗的自循环激发驱动，从而实现连续高效产氢。动态制氢装置中，电解液被泵送至电解质无能耗循环再生模块，并在上述同样的原理下，实现水分从非纯水溶液中向电解质溶液中的迁移，从而维持稳定的制氢过程。The invention is based on the interfacial vapor pressure difference between the self-driven electrolyte and the non-pure aqueous solution, inducing the vaporization phase change of the non-pure aqueous solution, and directional migration to the electrolyte side through the water vapor mass transfer membrane, and at the same time the liquefaction phase change is absorbed by the electrolyte, thus providing hydrogen production. The process provides pure moisture. In a static hydrogen production device, the electrolyte is in a static state. The in-situ direct electrolysis hydrogen production device without desalination of the non-pure aqueous solution is directly immersed in the non-pure aqueous solution. Driven by the pressure difference at the interface between the electrolyte and the non-pure aqueous solution, the non-pure aqueous solution phase changes and vaporizes to produce water vapor. The water vapor passes through the energy-free water vapor. The mass transfer layer directionally migrates to the electrolyte side, and is then liquefied by phase change induced by the self-driven electrolyte to form liquid water. At the same time, the hydrophobic effect of the energy-free water vapor mass transfer layer effectively blocks impurities in the non-pure aqueous solution. The electrolyte solution is synchronously electrolyzed to produce hydrogen. The water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous and efficient hydrogen production. In the dynamic hydrogen production device, the electrolyte is pumped to the electrolyte energy-free circulation regeneration module, and under the same principle as above, the water is transferred from the impure aqueous solution to the electrolyte solution, thereby maintaining a stable hydrogen production process.
由于本发明无需淡化工艺，极大的缩小了建设、运营、人力、维护等方面成本，且不受时空限制，极大的拓宽了氢能的来源范围；利用自驱动电解质诱导水汽液化相变形成电解质溶液，大幅提升了电解体系的电导率，避免了非纯水溶液制氢中H+和OH-浓度小在阴阳极传输效率低的问题；本发明中自驱动电解质诱导水汽相变液化的均为无杂质水分，因此突破了直接非纯水溶液制氢中氯离子被氧化产生Cl2或ClO-等腐蚀和有毒物质的瓶颈，产生腐蚀和有毒物质较少。从而解决现有技术存在的受时空限制不能原位制氢、电解效率低、能耗高、成本大幅增加、产生腐蚀和有毒物质较多等问题。Since the present invention does not require a desalination process, it greatly reduces the costs of construction, operation, manpower, maintenance, etc., and is not limited by time and space, greatly broadening the source range of hydrogen energy; it uses a self-driven electrolyte to induce the phase change of water vapor liquefaction to form The electrolyte solution greatly improves the conductivity of the electrolysis system and avoids the problem of low concentration of H + and OH - in hydrogen production from non-pure aqueous solutions and low cathode and anode transmission efficiency; in the present invention, the self-driven electrolyte induces water vapor phase change and liquefaction. There is no impurity moisture, so it breaks through the bottleneck of chlorine ions being oxidized to produce Cl 2 or ClO - and other corrosive and toxic substances in direct hydrogen production from non-pure aqueous solutions, and produces less corrosive and toxic substances. This solves the problems existing in the existing technology such as the inability to produce hydrogen in situ due to time and space constraints, low electrolysis efficiency, high energy consumption, significant increase in cost, and the generation of corrosion and toxic substances.
与现有技术相加比，本发明的积极效果体现在：Compared with the existing technology, the positive effects of the present invention are reflected in:
(一)本发明中，可直接利用非纯水溶液，在电解质和水溶液界面压力差推动作用下，非纯水溶液气化相变形成水蒸气，水汽定向通过无能耗水汽传质层，然后被自驱动电解质诱导相变液化形成电解质溶液，同时无能耗水汽传质层的疏水作用将非纯水溶液中的杂质有效阻隔；电解质溶液进行同步电解制氢；电解质溶液中的水不断被电解消耗，诱导电解质循环再生，维持界面压力差，实现系统无额外能耗的自循环激发驱动，从而实现连续高效稳定产氢；本发明无需淡化工艺，极大的缩小了建设、运营、人力、维护等方面成本，且不受时空限制，极大的拓宽了氢能的来源范围；利用自驱动电解质诱导水汽液化相变形成电解质溶液，大幅提升了电解体系的电导率，避免了非纯水溶液制氢中H+和OH-浓度小在阴阳极传输效率低的问题；本发明中自驱动电解质诱导水汽相变液化的均为无杂质水分，因此突破了直接非纯水溶液制氢中氯离子被氧化产生Cl2或ClO-等腐蚀和有毒物质的瓶颈，产生腐蚀和有毒物质较少。从而解决现有技术存在的受时空限制不能原位制氢、电解效率低、能耗高、成本大幅增 加、产生腐蚀和有毒物质较多等问题，本发明是绿色、无毒、环保的工艺体系。(1) In the present invention, the non-pure aqueous solution can be directly used. Driven by the pressure difference at the interface between the electrolyte and the aqueous solution, the non-pure aqueous solution vaporizes and undergoes phase change to form water vapor. The water vapor is directed through the energy-free water vapor mass transfer layer and is then self-driven. The electrolyte induces phase change and liquefies to form an electrolyte solution. At the same time, the hydrophobic effect of the energy-free water vapor mass transfer layer effectively blocks impurities in the impure aqueous solution; the electrolyte solution undergoes simultaneous electrolysis to produce hydrogen; the water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation. Regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation drive of the system without additional energy consumption, thereby achieving continuous, efficient and stable hydrogen production; the present invention does not require a desalination process, which greatly reduces the costs of construction, operation, manpower, maintenance, etc., and It is not limited by time and space, greatly broadening the source range of hydrogen energy; using a self-driven electrolyte to induce the liquefaction phase change of water vapor to form an electrolyte solution, greatly improving the conductivity of the electrolysis system and avoiding the need for H + and OH in hydrogen production from non-pure aqueous solutions -The problem of low cathode and anode transmission efficiency due to small concentration; in the present invention, the water vapor phase change induced by the self-driven electrolyte to liquefy is impurity-free water, thus breaking through the oxidation of chlorine ions to produce Cl 2 or ClO in direct hydrogen production from non-pure aqueous solutions - Bottlenecks such as corrosive and toxic substances produce less corrosive and toxic substances. This solves the existing technology problems of being unable to produce hydrogen in situ due to time and space constraints, low electrolysis efficiency, high energy consumption, and substantial increase in costs. In addition, there are problems such as corrosion and more toxic substances. The present invention is a green, non-toxic and environmentally friendly process system.
(二)供能模块为电解单元提供电能，太阳能、风能等可再生能源产生的电力或火电、水电储存在供能模块中，用于为制氢反应提供电能，制氢反应的电能来源广泛且易储存；(2) The energy supply module provides electric energy for the electrolysis unit. Electricity generated from renewable energy sources such as solar energy and wind energy or thermal power and hydropower is stored in the energy supply module to provide electric energy for the hydrogen production reaction. The source of electric energy for the hydrogen production reaction is wide and Easy to store;
(1)适用于较广范围的制氢电解结构；(1) Applicable to a wide range of hydrogen production electrolysis structures;
(2)有利于提高电解反应的速率；(2) It is helpful to increase the rate of electrolysis reaction;
(3)使得内部极板和催化层紧凑化，大幅提高了整个电解单元的稳定性；(3) The internal plates and catalytic layers are compacted, which greatly improves the stability of the entire electrolysis unit;
(4)电解装置可以为静态或动态结构，实用性广，有利于未来密集型能源体系开发；此外紧凑的结构大幅减小了制造成本和土地成本；(4) The electrolysis device can be a static or dynamic structure, which has wide practicability and is conducive to the development of future intensive energy systems; in addition, the compact structure greatly reduces manufacturing costs and land costs;
(5)支架与多孔网槽(槽体)之间形成用于存放自驱动电解质溶液的空间，从而有效保证电解反应的原料供应；多孔网槽(槽体)和无能耗传质层便于阻止非纯水溶液中的杂质通过，进一步保证电解效果和降低污染；(5) A space is formed between the bracket and the porous mesh trough (tank body) for storing the self-driven electrolyte solution, thereby effectively ensuring the supply of raw materials for the electrolysis reaction; the porous mesh trough (tank body) and the non-energy-consuming mass transfer layer are convenient for preventing non-stop The impurities in the pure aqueous solution pass through, further ensuring the electrolysis effect and reducing pollution;
(6)氢气收集管传输电解反应产生的氢气至氢气收集瓶，氢气干燥器干燥水蒸气等水汽物，提高了收集到的氢气的纯度；氢气洗涤器用以去除颗粒物或气体污染物，从而进一步收集到的氢气的纯度。可以实现多组电解单元串并联使用下的氢氧分离，良好收集氢气和氧气(6) The hydrogen collection pipe transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle. The hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen; the hydrogen scrubber is used to remove particulate matter or gas pollutants, thereby further collecting The purity of the hydrogen gas. It can realize the separation of hydrogen and oxygen when multiple groups of electrolysis units are used in series and parallel, and can collect hydrogen and oxygen well.
(三)装置的巧妙原理，使得该原理可以直接集成在现有成熟的电解装别中，极大的减小了系统工程和研发成本。(3) The ingenious principle of the device allows the principle to be directly integrated into existing mature electrolysis devices, greatly reducing system engineering and research and development costs.
(四)本发明可以实现在高电压、高电流密度下，无副反应的高效稳定的氢能转换。(4) The present invention can realize efficient and stable hydrogen energy conversion without side reactions under high voltage and high current density.
(五)本发明利用自驱动电解质诱导水汽液化相变形成电解质溶液，大幅提升了电解体系的电导率，避免了海水制氢中H+和OH-浓度小在阴阳极传输效率低的问题。(5) The present invention uses a self-driven electrolyte to induce the liquefaction phase change of water vapor to form an electrolyte solution, which greatly improves the conductivity of the electrolysis system and avoids the problem of low concentration of H+ and OH- in seawater hydrogen production and low cathode and anode transmission efficiency.
(六)由于本发明中自驱动电解质诱导水汽相变液化的均为无杂质水分，因此突破了直接海水制氢受到海水成分随时间、气候、人类活动等因素制约的瓶颈，同时该系统方法可以用于河水、湖水、污泥、沼泽、河流等任何非纯水环境中的电解制氢，极大的拓宽了氢能的来源范围，同时不受时空限制。(6) Since the water vapor phase change liquefied by the self-driven electrolyte in the present invention is impurity-free water, it breaks through the bottleneck of direct seawater hydrogen production that is restricted by seawater composition over time, climate, human activities and other factors. At the same time, this system method can It is used for electrolytic hydrogen production in any non-pure water environment such as river water, lake water, sludge, swamps, rivers, etc., which greatly broadens the source range of hydrogen energy and is not limited by time and space.
(七)由于本发明中自驱动电解质诱导水汽相变液化的均为无杂质水分，因此溶液体系中不含有钙离子、镁离子等杂质离子，长时间运行不会存在钙镁沉淀，减少了后期清晰维护成本。(7) Since the water vapor phase change liquefied by the self-driven electrolyte in the present invention is all impurity-free water, the solution system does not contain impurity ions such as calcium ions and magnesium ions, and there will be no calcium and magnesium precipitation during long-term operation, reducing the risk of later stages. Be clear about maintenance costs.
(八)本发明装置中可以实现多组电解单元串并联使用，提升了装置系统的单位时间产氢量，有利于大规模利用。同时本发明装置相对轻便小巧，可以真正实现在海上、湖泊、河流中原位使用，利于节省陆地资源。(8) In the device of the present invention, multiple groups of electrolysis units can be used in series and parallel, which increases the hydrogen production per unit time of the device system and is conducive to large-scale utilization. At the same time, the device of the present invention is relatively light and compact, and can be truly used in situ in seas, lakes, and rivers, which is beneficial to saving land resources.
附图说明Description of drawings
图1为本发明所述的一种非纯水溶液无淡化原位直接电解制氢装置(静态制氢)的结构示意图；Figure 1 is a schematic structural diagram of an in-situ direct electrolysis hydrogen production device (static hydrogen production) without desalination of non-pure aqueous solution according to the present invention;
图1中标记及相应的零部件名称：1-供能模块，2-绝缘卡槽，3-阳极极板，4-阳极催化层，5-隔膜，6-阴极催化层，7-阴极极板，8-阳极溶液室，9-阴极溶液室，10-电解单元，11-支架，13-上端盖，14-电解质溶液室，15-电解堆，16-氢气收集管，17-氢气洗涤器，18-氢气干燥器，19-氢气储存器，20-氧气收集管，21-氧气洗涤器，22-氧气干燥器，23-氧气储存器，40-水汽传质层，41-多孔网槽。Marks and corresponding parts names in Figure 1: 1-energy supply module, 2-insulation slot, 3-anode plate, 4-anode catalytic layer, 5-separator, 6-cathode catalytic layer, 7-cathode plate , 8-anode solution chamber, 9-cathode solution chamber, 10-electrolysis unit, 11-bracket, 13-upper end cover, 14-electrolyte solution chamber, 15-electrolysis stack, 16-hydrogen collection pipe, 17-hydrogen scrubber, 18-Hydrogen dryer, 19-Hydrogen storage, 20-Oxygen collection pipe, 21-Oxygen scrubber, 22-Oxygen dryer, 23-Oxygen storage, 40-Water vapor mass transfer layer, 41-Porous mesh tank.
图2为本发明所述的一种非纯水溶液无淡化原位直接电解制氢装置(动态制氢)的结构示意图；其中电解质无能耗循环再生模块为中空纤维膜型电解质无能耗循环再生模块Figure 2 is a schematic structural diagram of an in-situ direct electrolysis hydrogen production device (dynamic hydrogen production) without desalination of non-pure aqueous solutions according to the present invention; the electrolyte energy-free cycle regeneration module is a hollow fiber membrane type electrolyte energy-free cycle regeneration module.
图3为本发明所述的一种非纯水溶液无淡化原位直接电解制氢装置(动态制氢)的结构示意图；其中电解质无能耗循环再生模块为平板膜型电解质无能耗循环再生模块Figure 3 is a schematic structural diagram of an in-situ direct electrolysis hydrogen production device (dynamic hydrogen production) without desalination of non-pure aqueous solutions according to the present invention; the electrolyte energy-free cycle regeneration module is a flat membrane type electrolyte energy-free cycle regeneration module.
图4-1为图2-图3中电解单元的组合结构示意图。Figure 4-1 is a schematic diagram of the combined structure of the electrolysis unit in Figures 2-3.
图4-2为图2-图3中电解单元的拆分结构示意图。 Figure 4-2 is a schematic diagram of the split structure of the electrolysis unit in Figures 2-3.
图5为图2-图3中电解堆的结构示意图Figure 5 is a schematic structural diagram of the electrolysis stack in Figures 2-3.
图6-1为图2-图3中中空纤维膜型结构示意图Figure 6-1 is a schematic diagram of the hollow fiber membrane structure in Figures 2-3.
图6-2为图2-图3中平板膜型结构示意图Figure 6-2 is a schematic diagram of the flat membrane structure in Figures 2-3.
图6-3为图2-图3中平板膜型结构示意图Figure 6-3 is a schematic diagram of the flat membrane structure in Figures 2-3.
图7静态海水无淡化原位直接电解制氢装置的制氢稳定性图Figure 7 Hydrogen production stability diagram of static seawater in-situ direct electrolysis hydrogen production device without desalination
图2-图6附图中标记及相应的零部件名称：1-供能模块，2-绝缘卡槽，3-阳极极板，4-阳极催化层，5-隔膜，6-阴极催化层，7-阴极极板，8-阳极溶液室，9-阴极溶液室，10-电解单元，11-支架，12-槽体，13-上端盖，14-电解质溶液室，15-电解堆，16-氢气收集管，17-氢气洗涤器，18-氢气干燥器，19-氢气储存器，20-氧气收集管，21-氧气洗涤器，22-氧气干燥器，23-氧气储存器，24-电解质无能耗循环再生模块，25-非纯水溶液槽体，26-非纯水溶液室，27-电解质溶液循环管道，28-非纯水溶液循环管道，29-电解质溶液循环泵，30-非纯水溶液循环泵，31-中空纤维膜传质舱，32-中空纤维膜，33-中空纤维膜内腔，34-中空纤维膜外部室，35-平板膜传质舱，36-双层平板膜，37-平板膜内腔，38-平板膜外部室，39-分流管汇管。The marks and corresponding parts names in Figure 2-Figure 6 are: 1-energy supply module, 2-insulation slot, 3-anode plate, 4-anode catalytic layer, 5-separator, 6-cathode catalytic layer, 7-cathode plate, 8-anode solution chamber, 9-cathode solution chamber, 10-electrolysis unit, 11-bracket, 12-tank body, 13-upper end cover, 14-electrolyte solution chamber, 15-electrolysis stack, 16- Hydrogen collection pipe, 17-Hydrogen scrubber, 18-Hydrogen dryer, 19-Hydrogen storage, 20-Oxygen collection pipe, 21-Oxygen scrubber, 22-Oxygen dryer, 23-Oxygen storage, 24-Electrolyte incompetence Consumption circulation regeneration module, 25-impure aqueous solution tank, 26-impure aqueous solution chamber, 27-electrolyte solution circulation pipe, 28-impure aqueous solution circulation pipe, 29-electrolyte solution circulation pump, 30-impure aqueous solution circulation pump, 31-Hollow fiber membrane mass transfer cabin, 32-Hollow fiber membrane, 33-Hollow fiber membrane inner cavity, 34-Hollow fiber membrane outer chamber, 35-Flat membrane mass transfer cabin, 36-Double-layer flat membrane, 37-Flat membrane Inner chamber, 38-flat membrane outer chamber, 39-shunt manifold.
具体实施方式Detailed ways
为了使本发明的发明目的、技术方案及优点更加清楚明白，下面结合具体实施方式对本发明作进一步的详细描述，但不应将此理解为本发明上述主题的范围仅限于下述实施例。在不脱离本发明上述技术思想情况下，根据本领域普通技术知识和惯用手段，做出各种替换和变更，均应包括在本发明的范围内。In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be described in further detail below in conjunction with specific embodiments. However, this should not be understood to mean that the scope of the above subject matter of the present invention is limited to the following examples. Without departing from the above-mentioned technical ideas of the present invention, various substitutions and changes can be made based on common technical knowledge and common means in the art, and all of them should be included in the scope of the present invention.
实施例1：Example 1:
如图1所示，一种非纯水溶液无淡化原位直接电解制氢装置，用于电解液静态制氢，该装置包括：As shown in Figure 1, an in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution is used for static hydrogen production from electrolyte. The device includes:
供能模块：用于为制氢反应提供电能，太阳能、风能等可再生能源产生的电力或火电、水电储可存在供能模块中，制氢反应的电能来源广泛且易储存。Energy supply module: used to provide electric energy for the hydrogen production reaction. Electricity generated from renewable energy sources such as solar energy and wind energy, or thermal power and hydropower storage can be stored in the energy supply module. The electric energy for the hydrogen production reaction has a wide range of sources and is easy to store.
与供能模块连接的电解单元：所述电解单元包括相对设置的阳极溶液室、阴极溶液室，设于所述阳极溶液室内的阳极极板，设于所述阴极溶液室内的阴极极板，所述阳极极板与所述阴极极板分别与所述供能模块相连，所述阳极溶液室与所述阴极溶液室之间设有隔膜；多个电解单元串联或并联堆叠形成电解堆，用于制氢反应，产生氢气；An electrolysis unit connected to the energy supply module: the electrolysis unit includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber. The anode plate and the cathode plate are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber; multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack, for Hydrogen production reaction produces hydrogen gas;
支架：用于固定电解堆；Bracket: used to fix the electrolysis stack;
多孔网槽：用于放置支架，多孔网槽内壁紧贴水汽传质层，水汽传质层形成一个凹形空间，形成电解质溶液室，用于存放自驱动电解质溶液；Porous mesh trough: used to place the bracket. The inner wall of the porous mesh trough is close to the water vapor mass transfer layer. The water vapor mass transfer layer forms a concave space to form an electrolyte solution chamber for storing self-driven electrolyte solution;
收集装置：收集装置与电解单元相连，用以收集电解产生的氢气和氧气。Collection device: The collection device is connected to the electrolysis unit to collect hydrogen and oxygen produced by electrolysis.
所述电解单元还包括设于所述阳极溶液室内的阳极催化层、设于所述阴极溶液室内的阴极催化层；阳极极板、阳极催化层与绝缘卡槽的流道间隙形成阳极溶液室，阳极溶液室内充满自驱动电解质溶液；阴极极板与阴极催化层的流道间隙形成阴极溶液室，阴极溶液室内充满自驱动电解质溶液；电解质溶液浸没电解堆。The electrolysis unit also includes an anode catalytic layer located in the anode solution chamber and a cathode catalytic layer located in the cathode solution chamber; the anode plate, the anode catalytic layer and the flow channel gap of the insulating slot form an anode solution chamber, The anode solution chamber is filled with self-driven electrolyte solution; the flow channel gap between the cathode plate and the cathode catalytic layer forms a cathode solution chamber, and the cathode solution chamber is filled with self-driven electrolyte solution; the electrolyte solution immerses the electrolysis stack.
所述的收集装置包括氢气收集管和氧气收集管；在氢气收集管后面依次连接有氢气洗涤器、氢气干燥器及氢气储存器；在氧气收集管后面依次连接有氧气洗涤器、氧气干燥器及氧气储存器。氢气收集管传输电解反应产生的氢气至氢气收集瓶，氢气干燥器干燥水蒸气等水汽物，提高了收集到的氢气的纯度。氢气洗涤器用以去除颗粒物或气体污染物，从而进一步收集到的氢气的纯度。用于静态制氢时，在多孔网槽上设置上端盖，在上端盖上开设有供氢气收集管、氧气收集管和供能模块的导电线通过的接口，接口处密封连接；电解制氢时，多孔网槽的部分浸于非纯水溶液，在水汽传质层界面处产生蒸汽压差，诱导非纯水溶液发生气 化相变，同时通过水汽传质层定向传递至电解质侧，并在蒸汽压差作用下被电解质诱导液化吸收；电解质被同步电解，进一步维持非纯水溶液与电解质间的界面蒸汽压差，从而形成不额外能耗的稳定制氢过程。The collection device includes a hydrogen collection pipe and an oxygen collection pipe; a hydrogen scrubber, a hydrogen dryer and a hydrogen storage device are connected in sequence behind the hydrogen collection pipe; an oxygen scrubber, an oxygen dryer and a hydrogen storage device are connected in sequence behind the oxygen collection pipe. Oxygen reservoir. The hydrogen collection tube transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle, and the hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen. Hydrogen scrubbers are used to remove particulate matter or gaseous contaminants, thereby further improving the purity of the collected hydrogen. When used for static hydrogen production, an upper end cover is set on the porous mesh trough, and an interface is provided on the upper end cover for the hydrogen collection pipe, the oxygen collection pipe and the conductive wire of the energy supply module to pass through, and the interfaces are sealed and connected; when electrolytic hydrogen production , part of the porous mesh trough is immersed in the non-pure water solution, which generates a vapor pressure difference at the interface of the water vapor mass transfer layer, inducing gas generation in the non-pure water solution. phase change, and is directed to the electrolyte side through the water vapor mass transfer layer, and is induced to liquefy and absorb by the electrolyte under the action of the vapor pressure difference; the electrolyte is synchronously electrolyzed, further maintaining the interfacial vapor pressure difference between the impure aqueous solution and the electrolyte, thereby forming Stable hydrogen production process without additional energy consumption.
更进一步的，当多孔网槽部分浸于非纯水溶液时，多孔网槽槽体及内壁贴合的水汽传质层与上端盖密封连接并形成密闭空间，与外界空气隔绝。Furthermore, when the porous mesh trough is partially immersed in a non-pure aqueous solution, the porous mesh trough body and the water vapor mass transfer layer attached to the inner wall are sealed and connected with the upper end cover to form a sealed space, which is isolated from the outside air.
支架与多孔网槽及紧贴着的水汽传质层之间形成电解质溶液室，用于存放自驱动电解质溶液，自驱动电解质溶液通过阳极极板3进入阳极溶液室，浸润阳极催化层和隔膜进入阴极催化层和阴极溶液室。当进行电解反应时，装置多孔网槽部分浸入海水中，控制海水的高度低于A-A面。自驱动电解质溶液诱导水汽传质相变液化获取水分，同时无能耗水汽传质层将非纯水杂质阻挡在外。An electrolyte solution chamber is formed between the bracket, the porous mesh groove and the adjoining water vapor mass transfer layer, which is used to store the self-driven electrolyte solution. The self-driven electrolyte solution enters the anode solution chamber through the anode plate 3 and infiltrates the anode catalytic layer and separator. Cathode catalytic layer and cathode solution chamber. When the electrolysis reaction is carried out, the porous mesh tank of the device is partially immersed in seawater, and the height of the seawater is controlled to be lower than the A-A surface. The self-driven electrolyte solution induces water vapor mass transfer phase change to liquefy to obtain water, while the energy-free water vapor mass transfer layer blocks impure water impurities.
自驱动电解质溶液为10-50wt％的KOH溶液或10-40wt％的H2SO4溶液。The self-driving electrolyte solution is a 10-50wt% KOH solution or a 10-40wt% H 2 SO 4 solution.
当自驱动电解质溶液呈碱性时，则在阴极催化层6表面发生还原析氢反应，反应式如下：
2H2O+2e-→H2+2OH- When the self-driving electrolyte solution is alkaline, a reduction and hydrogen evolution reaction occurs on the surface of the cathode catalytic layer 6, and the reaction formula is as follows:
2H 2 O+2e - →H 2 +2OH -
电解单元中阴极极板内部开设有阴极溶液室，并有孔连接阴极导管，多组电解单元的阴极导管连接汇集于一体形成氢气收集管。产出的氢气通过氢气收集管流通，通过氢气洗涤器17和氢气干燥器，脱出氢气中夹带的水汽，经过管道收集进入氢气储存器，进行储存和下一步利用。产生的OH-通过隔膜/离子交换膜传递至阳极催化层4，发生氧化反应产生氧气，反应式如下：
There is a cathode solution chamber inside the cathode plate in the electrolysis unit, and there are holes to connect the cathode conduits. The cathode conduits of multiple groups of electrolysis units are connected and integrated to form a hydrogen collection pipe. The produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber 17 and the hydrogen dryer, removes the water vapor entrained in the hydrogen, and is collected through the pipeline into the hydrogen storage for storage and further utilization. The generated OH - is transferred to the anode catalytic layer 4 through the separator/ion exchange membrane, and an oxidation reaction occurs to generate oxygen. The reaction formula is as follows:
析氧反应产生的氧气通过氧气收集管20汇集，并经过氧气洗涤器和氧气干燥器，收集至氧气储存器。The oxygen generated by the oxygen evolution reaction is collected through the oxygen collection pipe 20, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank.
当自驱动电解质溶液呈酸性时，则在阳极催化层表面发生氧化析氧反应，反应式如下：
When the self-driven electrolyte solution is acidic, an oxidation and oxygen evolution reaction occurs on the surface of the anode catalytic layer. The reaction formula is as follows:
析氧反应产生的氧气通过氧气收集管汇集，并经过氧气洗涤器和氧气干燥器，收集至氧气储存器。产生的H+通过隔膜/离子交换膜5传递至阴极催化层，发生还原反应产生氢气，反应式如下：
2H++2e-→H2 The oxygen produced by the oxygen evolution reaction is collected through the oxygen collection pipe, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank. The generated H + is transferred to the cathode catalytic layer through the separator/ion exchange membrane 5, and a reduction reaction occurs to generate hydrogen. The reaction formula is as follows:
2H + +2e - →H 2
产出的氢气通过氢气收集管流通，通过氢气洗涤器和氢气干燥器，脱出氢气中夹带的水汽，经过管道收集进入氢气储存器，进行储存和下一步利用。The produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber and the hydrogen dryer, and removes the water vapor entrained in the hydrogen. It is collected through the pipeline and entered into the hydrogen storage tank for storage and further utilization.
本发明中，该装置可直接浸入非纯水溶液中，在电解质和水溶液界面压力差推动作用下，非纯水溶液(海水、湖水、河水、工业废水等)气化相变形成水蒸气，水汽定向通过无能耗水汽传质层，然后被自驱动电解质诱导相变液化形成电解质溶液，同时无能耗水汽传质层的疏水作用将非纯水溶液中的杂质有效阻隔；电解质溶液进行同步电解制氢；电解质溶液中的水不断被电解消耗，诱导电解质循环再生，维持界面压力差，实现系统无额外能耗的自循环激发驱动，从而实现连续高效稳定产氢。通过无能耗水汽传质层的疏水作用将非纯水溶液中的杂质有效阻隔，通过自驱动电解质诱导水汽相变液化获取水分，形成电解质溶液，并通过催化电解的化学原理制备氢气。In the present invention, the device can be directly immersed in an impure aqueous solution. Driven by the pressure difference at the interface between the electrolyte and the aqueous solution, the impure aqueous solution (seawater, lake water, river water, industrial wastewater, etc.) vaporizes and phase changes to form water vapor, and the water vapor passes through in a directed manner. The energy-free water vapor mass transfer layer is then liquefied by phase change induced by the self-driven electrolyte to form an electrolyte solution. At the same time, the hydrophobic effect of the energy-free water vapor mass transfer layer effectively blocks impurities in the impure aqueous solution; the electrolyte solution undergoes simultaneous electrolysis to produce hydrogen; the electrolyte solution The water in the system is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation and driving of the system without additional energy consumption, thereby achieving continuous, efficient and stable hydrogen production. The impurities in the impure aqueous solution are effectively blocked by the hydrophobic effect of the energy-free water vapor mass transfer layer. The self-driven electrolyte induces the phase change of water vapor to liquefy to obtain water to form an electrolyte solution, and hydrogen is produced through the chemical principle of catalytic electrolysis.
基于催化电解的制氢流程如下：电解质溶液室和阳极溶液室存放自驱动电解质溶液，并 通过隔膜浸润至阴极溶液室，将系统浸没至水溶液后，通过电解制氢，诱导电解质循环再生，维持界面压力差，实现系统无额外能耗的自循环激发驱动。开始电解后，水分在阴极催化电极发生还原反应产生氢气，在阳极催化电极上发生析氧反应，隔膜/离子交换膜用于传递氢氧根或者质子。The hydrogen production process based on catalytic electrolysis is as follows: the electrolyte solution chamber and anode solution chamber store the self-driven electrolyte solution, and Through the diaphragm, the cathode solution chamber is immersed, and after the system is immersed in the aqueous solution, hydrogen is produced through electrolysis, inducing electrolyte cycle regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation drive of the system without additional energy consumption. After electrolysis starts, the water undergoes a reduction reaction at the cathode catalytic electrode to produce hydrogen, and an oxygen evolution reaction occurs at the anode catalytic electrode. The separator/ion exchange membrane is used to transfer hydroxide radicals or protons.
具体操作：采用了PTFE多孔防水透气膜作为无能耗水汽传质层，140kg 30wt％氢氧化钾溶液作为电解质溶液，泡沫镍钼作为阳极催化剂，镍镀铂网作为阴极催化剂，聚砜膜作为隔膜，在250mA/cm2条件下进行测试，实验结果如图7。如图7该装置在深圳湾海水中稳定运行1600h，电堆实际电压约2.1V，能耗约5kWh/Nm3H2，约产生386L/h的H2。表明该装置能够在不额外耗能的条件下稳定制氢，能耗与电解纯净水相似。Specific operation: PTFE porous waterproof and breathable membrane is used as the energy-free water vapor mass transfer layer, 140kg 30wt% potassium hydroxide solution is used as the electrolyte solution, nickel molybdenum foam is used as the anode catalyst, nickel platinum-plated mesh is used as the cathode catalyst, and the polysulfone membrane is used as the separator. The test was carried out under the condition of 250mA/ cm2 , and the experimental results are shown in Figure 7. As shown in Figure 7, the device has been operating stably in Shenzhen Bay seawater for 1600 hours. The actual voltage of the stack is about 2.1V, the energy consumption is about 5kWh/Nm 3 H 2 , and it produces about 386L/h H 2 . It shows that the device can stably produce hydrogen without consuming additional energy, and the energy consumption is similar to that of electrolysis of pure water.
电解液静态制氢的其他实施例，方法步骤同实施例1，区别见表1：


In other embodiments of static hydrogen production from electrolyte, the method steps are the same as those in Embodiment 1. The differences are shown in Table 1:


实施例2:Example 2:
一种非纯水溶液无淡化原位直接电解制氢装置，用于动态循环电解液制氢，该装置具体结构见图2所述，包括：An in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution, used for dynamic circulation of electrolyte to produce hydrogen. The specific structure of the device is shown in Figure 2, including:
供能模块：用于为制氢反应提供电能；Energy supply module: used to provide electrical energy for the hydrogen production reaction;
与供能模块连接的电解单元：所述电解单元包括相对设置的阳极溶液室、阴极溶液室，设于所述阳极溶液室内的阳极极板，设于所述阴极溶液室内的阴极极板，所述阳极极板与所述阴极极板分别与所述供能模块相连，所述阳极溶液室与所述阴极溶液室之间设有隔膜；多个电解单元串联或并联堆叠形成电解堆，用于制氢反应，产生氢气；An electrolysis unit connected to the energy supply module: the electrolysis unit includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber. The anode plate and the cathode plate are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber; multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack, for Hydrogen production reaction produces hydrogen gas;
支架：用于固定电解堆；Bracket: used to fix the electrolysis stack;
带有框架的槽体：用于放置支架，在支架与槽体的空隙处形成电解质溶液室，用于存放自驱动电解质溶液；Tank body with frame: used to place the bracket, forming an electrolyte solution chamber in the gap between the bracket and the tank body, used to store self-driven electrolyte solution;
收集装置：收集装置与电解单元相连，用以收集电解产生的氢气。Collection device: The collection device is connected to the electrolysis unit to collect the hydrogen produced by electrolysis.
所述电解单元还包括设于所述阳极溶液室内的阳极催化层、设于所述阴极溶液室内的阴极催化层；阳极极板、阳极催化层与绝缘卡槽的流道间隙形成阳极溶液室，阳极溶液室内充满自驱动电解质溶液；阴极极板与阴极催化层的流道间隙形成阴极溶液室，阴极溶液室内充满自驱动电解质溶液；电解质溶液浸没电解堆。The electrolysis unit also includes an anode catalytic layer located in the anode solution chamber and a cathode catalytic layer located in the cathode solution chamber; the anode plate, the anode catalytic layer and the flow channel gap of the insulating slot form an anode solution chamber, The anode solution chamber is filled with self-driven electrolyte solution; the flow channel gap between the cathode plate and the cathode catalytic layer forms a cathode solution chamber, and the cathode solution chamber is filled with self-driven electrolyte solution; the electrolyte solution immerses the electrolysis stack.
所述收集装置包括氢气收集管和氧气收集管；在氢气收集管后面依次连接有氢气洗涤器、氢气干燥器及氢气储存器；在氧气收集管后面依次连接有氧气洗涤器、氧气干燥器及氧气储存器。氢气收集管传输电解反应产生的氢气至氢气收集瓶，氢气干燥器干燥水蒸气等水汽物，提高了收集到的氢气的纯度。氢气洗涤器用以去除颗粒物或气体污染物，从而进一步收集到的氢气的纯度。The collection device includes a hydrogen collection pipe and an oxygen collection pipe; a hydrogen scrubber, a hydrogen dryer and a hydrogen storage device are connected in sequence behind the hydrogen collection pipe; an oxygen scrubber, an oxygen dryer and an oxygen storage device are connected in sequence behind the oxygen collection pipe. storage. The hydrogen collection pipe transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle, and the hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen. Hydrogen scrubbers are used to remove particulate matter or gaseous contaminants, thereby further improving the purity of the collected hydrogen.
用于动态制氢时，在槽体的上端有上端盖，上端盖上开设有供氢气收集管、氧气收集管和供能模块的导电线通过的接口，接口处密封连接。When used for dynamic hydrogen production, there is an upper end cover at the upper end of the tank body. The upper end cover is provided with an interface for the hydrogen collection pipe, the oxygen collection pipe and the conductive wire of the energy supply module to pass through, and the interfaces are sealed and connected.
在槽体的一侧还设置有电解质无能耗循环再生模块，电解质无能耗循环再生模块通过带有电解质溶液循环泵的电解质溶液循环管道与槽体连通；电解质无能耗循环再生模块为中空纤维膜型电解质无能耗循环再生模块。An electrolyte energy-free cycle regeneration module is also provided on one side of the tank. The electrolyte energy-free cycle regeneration module is connected to the tank through an electrolyte solution circulation pipeline with an electrolyte solution circulation pump; the electrolyte energy-free cycle regeneration module is a hollow fiber membrane type. Electrolyte energy-free recycling regeneration module.
所述的中空纤维膜型电解质无能耗循环再生模块包括中空纤维膜传质舱、中空纤维膜、中空纤维膜内腔、中空纤维膜外部室、非纯水溶液槽体、非纯水溶液室、非纯水溶液循环管道和非纯水溶液循环泵；中空纤维膜传质舱内密集设置有多根并联的中空纤维膜，中空纤维膜膜层内部的可流通溶液空间为中空纤维膜内腔，中空纤维膜膜层外壁与中空纤维膜传质舱之间的空间为中空纤维膜外部室；槽体、电解质溶液循环管道、电解质溶液循环泵和中空纤维膜串联，电解质溶液循环泵循环自驱动电解质溶液，使电解质溶液室连通中空纤维膜内腔，自驱动电解质溶液从中空纤维膜内腔通过；中空纤维膜传质舱与非纯水溶液循环管道、非纯水溶液循环泵、非纯水溶液槽体串联；非纯水溶液循环泵用于循环非纯水溶液，中空纤维膜外部室与非纯水溶液室连通，非纯水溶液从中空纤维膜外部室通过；双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过纤维膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由中空纤维膜外部室向中空纤维膜内腔无能耗转移纯净水分，同时中空纤维膜将非纯水溶液中的杂质阻挡在外。The hollow fiber membrane type electrolyte energy-free recycling regeneration module includes a hollow fiber membrane mass transfer cabin, a hollow fiber membrane, a hollow fiber membrane inner cavity, a hollow fiber membrane outer chamber, a non-pure aqueous solution tank, a non-pure aqueous solution chamber, and a non-pure aqueous solution chamber. Aqueous solution circulation pipeline and non-pure aqueous solution circulation pump; multiple parallel hollow fiber membranes are densely arranged in the hollow fiber membrane mass transfer chamber. The flowable solution space inside the hollow fiber membrane membrane layer is the hollow fiber membrane inner cavity, and the hollow fiber membrane membrane The space between the outer wall of the layer and the hollow fiber membrane mass transfer chamber is the outer chamber of the hollow fiber membrane; the tank body, the electrolyte solution circulation pipe, the electrolyte solution circulation pump and the hollow fiber membrane are connected in series. The electrolyte solution circulation pump circulates the self-driven electrolyte solution to make the electrolyte The solution chamber is connected to the inner cavity of the hollow fiber membrane, and the self-driven electrolyte solution passes through the inner cavity of the hollow fiber membrane; the hollow fiber membrane mass transfer chamber is connected in series with the non-pure aqueous solution circulation pipe, the non-pure aqueous solution circulation pump, and the non-pure aqueous solution tank; the non-pure aqueous solution The circulation pump is used to circulate non-pure water solution. The outer chamber of the hollow fiber membrane is connected with the non-pure water solution chamber. The non-pure water solution passes through the outer chamber of the hollow fiber membrane. During the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces The phase change of the impure aqueous solution vaporizes to form water vapor. The water vapor directionally migrates to the electrolyte side through the fiber membrane and is induced to liquefy and phase change, providing pure water for electrolysis. This process involves no energy consumption from the outer chamber of the hollow fiber membrane to the inner cavity of the hollow fiber membrane. Pure water is transferred while the hollow fiber membrane blocks out impurities in impure aqueous solutions.
槽体、电解质溶液循环管道、电解质溶液循环泵、分流管汇和双层平板膜串联，电解质 溶液循环泵循环自驱动电解质溶液，使电解质溶液室连通平板膜内腔，自驱动电解质溶液从平板膜内腔通过；平板膜传质舱与非纯水溶液循环管道、非纯水溶液循环泵、非纯水溶液槽体串联；非纯水溶液循环泵用于循环非纯水溶液，平板膜外部室与非纯水溶液室连通，非纯水溶液从平板膜外部室通过；双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过纤维膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由平板膜外部室向平板膜内腔无能耗转移水分，同时双层平板膜将非纯水中的杂质阻挡在外。The tank body, electrolyte solution circulation pipeline, electrolyte solution circulation pump, shunt manifold and double-layer flat membrane are connected in series. The solution circulation pump circulates the self-driven electrolyte solution, so that the electrolyte solution chamber is connected to the inner cavity of the flat membrane, and the self-driven electrolyte solution passes through the inner cavity of the flat membrane; the flat membrane mass transfer chamber and the non-pure water solution circulation pipeline, the non-pure water solution circulation pump, and the non-pure water solution circulation pump The aqueous solution tanks are connected in series; the impure aqueous solution circulation pump is used to circulate the impure aqueous solution. The outer chamber of the flat membrane is connected with the impure aqueous solution chamber, and the impure aqueous solution passes through the outer chamber of the flat membrane; during the two-way circulation process, under the action of the interface vapor pressure difference, , the self-driven electrolyte solution induces the phase change and vaporization of the non-pure aqueous solution to form water vapor. The water vapor is directionally migrated to the electrolyte side through the fiber membrane, and is induced to liquefy and phase change, providing pure water for electrolysis. This process moves from the outer chamber of the flat membrane to the flat membrane. The inner cavity transfers water without energy consumption, and the double-layer flat membrane blocks impurities in impure water.
电解质溶液室连通中空纤维膜外部室，自驱动电解质溶液从中空纤维膜外部室通过；中空纤维膜内腔连通非纯水溶液室，非纯水溶液从中空纤维膜内腔通过，双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由中空纤维膜内腔向中空纤维膜外部室无能耗转移水分。The electrolyte solution chamber is connected to the outer chamber of the hollow fiber membrane, and the self-driven electrolyte solution passes through the outer chamber of the hollow fiber membrane; the inner chamber of the hollow fiber membrane is connected to the non-pure aqueous solution chamber, and the non-pure aqueous solution passes through the inner chamber of the hollow fiber membrane. During the two-way circulation, Under the action of interfacial vapor pressure difference, the self-driven electrolyte solution induces phase change and vaporization of the impure aqueous solution to form water vapor. The water vapor directionally migrates to the electrolyte side through the membrane and is induced to liquefy and phase change, providing pure water for electrolysis. This process is performed by hollow fibers. The inner chamber of the membrane transfers water to the outer chamber of the hollow fiber membrane without energy consumption.
当自驱动电解质溶液呈碱性时，则在阴极催化层6表面发生还原析氢反应，反应式如下：
2H2O+2e-→H2+2OH- When the self-driven electrolyte solution is alkaline, a reduction and hydrogen evolution reaction occurs on the surface of the cathode catalytic layer 6, and the reaction formula is as follows:
2H 2 O+2e - →H 2 +2OH -
电解单元中阴极极板内部开设有阴极溶液室，并有孔连接阴极导管，多组电解单元的阴极导管连接汇集于一体形成氢气收集管。产出的氢气通过氢气收集管流通，通过氢气洗涤器17和氢气干燥器，脱出氢气中夹带的水汽，经过管道收集进入氢气储存器，进行储存和下一步利用。产生的OH-通过隔膜/离子交换膜传递至阳极催化层4，发生氧化反应产生氧气，反应式如下：
There is a cathode solution chamber inside the cathode plate in the electrolysis unit, and there are holes to connect the cathode conduits. The cathode conduits of multiple groups of electrolysis units are connected and integrated to form a hydrogen collection pipe. The produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber 17 and the hydrogen dryer, removes the water vapor entrained in the hydrogen, and is collected through the pipeline into the hydrogen storage for storage and further utilization. The generated OH - is transferred to the anode catalytic layer 4 through the separator/ion exchange membrane, and an oxidation reaction occurs to generate oxygen. The reaction formula is as follows:
析氧反应产生的氧气通过氧气收集管20汇集，并经过氧气洗涤器和氧气干燥器，收集至氧气储存器。The oxygen generated by the oxygen evolution reaction is collected through the oxygen collection pipe 20, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank.
当自驱动电解质溶液呈酸性时，则在阳极催化层表面发生氧化析氧反应，反应式如下：
When the self-driven electrolyte solution is acidic, an oxidation and oxygen evolution reaction occurs on the surface of the anode catalytic layer. The reaction formula is as follows:
析氧反应产生的氧气通过氧气收集管汇集，并经过氧气洗涤器和氧气干燥器，收集至氧气储存器。产生的H+通过隔膜/离子交换膜5传递至阴极催化层，发生还原反应产生氢气，反应式如下：
2H++2e-→H2 The oxygen produced by the oxygen evolution reaction is collected through the oxygen collection pipe, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank. The generated H + is transferred to the cathode catalytic layer through the separator/ion exchange membrane 5, and a reduction reaction occurs to generate hydrogen. The reaction formula is as follows:
2H + +2e - →H 2
产出的氢气通过氢气收集管流通，通过氢气洗涤器和氢气干燥器，脱出氢气中夹带的水汽，经过管道收集进入氢气储存器，进行储存和下一步利用。The produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber and the hydrogen dryer, and removes the water vapor entrained in the hydrogen. It is collected through the pipeline and entered into the hydrogen storage tank for storage and further utilization.
电解质溶液同步进行电解制氢，电解质溶液中的水不断被电解消耗，诱导电解质循环再生，维持界面压力差，实现系统无额外能耗的自循环激发驱动，从而实现连续高效产氢。动态制氢装置中，电解液被泵送至电解质无能耗循环再生模块，并在上述同样的原理下，实现水分从非纯水溶液中向电解质溶液中的迁移，从而维持稳定的制氢过程。The electrolyte solution is synchronously electrolyzed to produce hydrogen. The water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous and efficient hydrogen production. In the dynamic hydrogen production device, the electrolyte is pumped to the electrolyte energy-free circulation regeneration module, and under the same principle as above, the water is transferred from the impure aqueous solution to the electrolyte solution, thereby maintaining a stable hydrogen production process.
供能模块为电解单元提供电能，太阳能、风能等可再生能源产生的电力或火电、水电储存在供能模块中，用于为制氢反应提供电能，制氢反应的电能来源广泛且易储存。The energy supply module provides electric energy for the electrolysis unit. Electricity generated from renewable energy sources such as solar energy and wind energy or thermal power and hydropower is stored in the energy supply module to provide electric energy for the hydrogen production reaction. The electric energy for the hydrogen production reaction has a wide range of sources and is easy to store.
本发明的电解单元适用于较广范围的制氢电解结构。The electrolysis unit of the present invention is suitable for a wider range of hydrogen production electrolysis structures.
阳极溶液室内的阳极催化层、阴极溶液室内的阴极催化层的设置，这有利于提高电解反应的速率。内部极板和催化层紧凑化，大幅提高了整个电解单元的稳定性。 The arrangement of the anode catalytic layer in the anode solution chamber and the cathode catalytic layer in the cathode solution chamber is beneficial to increasing the rate of the electrolysis reaction. The compactness of the internal plates and catalytic layers greatly improves the stability of the entire electrolysis unit.
可用的阳极催化电极包括：泡沫镍钼、泡沫镍铁、FexCoyNiz型催化剂、钌铱、NiFe-LDH、NiFeCu合金催化剂等(根据实际电解质酸碱性进行选择)；可用的析氢催化剂包括：铂金网、镍镀铂网等(根据实际电解质酸碱性进行选择)。Available anode catalytic electrodes include: nickel-molybdenum foam, nickel-iron foam, FexCoyNiz catalyst, ruthenium-iridium, NiFe-LDH, NiFeCu alloy catalyst, etc. (selected according to the actual acidity and alkalinity of the electrolyte); available hydrogen evolution catalysts include: platinum mesh, Nickel-plated platinum mesh, etc. (select according to the actual acidity and alkalinity of the electrolyte).
中空纤维膜可以为任何具有防水透气性能的材料。The hollow fiber membrane can be any material with waterproof and breathable properties.
动态循环电解液制氢的其他实施例，方法步骤同实施例2，区别见表2：
In other embodiments of hydrogen production from dynamic circulating electrolyte, the method steps are the same as those in Embodiment 2. The differences are shown in Table 2:
经试验论证，选择的湖水、海水或河水不同，对本申请效果无明显影响。After experimental verification, the selected lake water, sea water or river water has no obvious impact on the effect of this application.
实施例3：Example 3:
一种非纯水溶液无淡化原位直接电解制氢装置，用于动态循环电解液制氢，该装置具体结构见图3所述，包括：An in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution, used for dynamic circulation of electrolyte to produce hydrogen. The specific structure of the device is shown in Figure 3, including:
供能模块：用于为制氢反应提供电能；Energy supply module: used to provide electrical energy for the hydrogen production reaction;
与供能模块连接的电解单元：所述电解单元包括相对设置的阳极溶液室、阴极溶液室，设于所述阳极溶液室内的阳极极板，设于所述阴极溶液室内的阴极极板，所述阳极极板与所述阴 极极板分别与所述供能模块相连，所述阳极溶液室与所述阴极溶液室之间设有隔膜；多个电解单元串联或并联堆叠形成电解堆，用于制氢反应，产生氢气；An electrolysis unit connected to the energy supply module: the electrolysis unit includes an anode solution chamber and a cathode solution chamber arranged oppositely, an anode plate located in the anode solution chamber, and a cathode plate located in the cathode solution chamber. The anode plate and the cathode The polar plates are respectively connected to the energy supply module, and a diaphragm is provided between the anode solution chamber and the cathode solution chamber; multiple electrolysis units are stacked in series or in parallel to form an electrolysis stack for hydrogen production reaction to generate hydrogen;
支架：用于固定电解堆；Bracket: used to fix the electrolysis stack;
带有框架的槽体：用于放置支架，在支架与槽体的空隙处形成电解质溶液室，用于存放自驱动电解质溶液；Tank body with frame: used to place the bracket, forming an electrolyte solution chamber in the gap between the bracket and the tank body, used to store self-driven electrolyte solution;
收集装置：收集装置与电解单元相连，用以收集电解产生的氢气。Collection device: The collection device is connected to the electrolysis unit to collect the hydrogen produced by electrolysis.
所述电解单元还包括设于所述阳极溶液室内的阳极催化层、设于所述阴极溶液室内的阴极催化层；阳极极板、阳极催化层与绝缘卡槽的流道间隙形成阳极溶液室，阳极溶液室内充满自驱动电解质溶液；阴极极板与阴极催化层的流道间隙形成阴极溶液室，阴极溶液室内充满自驱动电解质溶液；电解质溶液浸没电解堆。The electrolysis unit also includes an anode catalytic layer located in the anode solution chamber and a cathode catalytic layer located in the cathode solution chamber; the anode plate, the anode catalytic layer and the flow channel gap of the insulating slot form an anode solution chamber, The anode solution chamber is filled with self-driven electrolyte solution; the flow channel gap between the cathode plate and the cathode catalytic layer forms a cathode solution chamber, and the cathode solution chamber is filled with self-driven electrolyte solution; the electrolyte solution immerses the electrolysis stack.
所述收集装置包括氢气收集管和氧气收集管；在氢气收集管后面依次连接有氢气洗涤器、氢气干燥器及氢气储存器；在氧气收集管后面依次连接有氧气洗涤器、氧气干燥器及氧气储存器。氢气收集管传输电解反应产生的氢气至氢气收集瓶，氢气干燥器干燥水蒸气等水汽物，提高了收集到的氢气的纯度。氢气洗涤器用以去除颗粒物或气体污染物，从而进一步收集到的氢气的纯度。The collection device includes a hydrogen collection pipe and an oxygen collection pipe; a hydrogen scrubber, a hydrogen dryer and a hydrogen storage device are connected in sequence behind the hydrogen collection pipe; an oxygen scrubber, an oxygen dryer and an oxygen storage device are connected in sequence behind the oxygen collection pipe. storage. The hydrogen collection pipe transmits the hydrogen produced by the electrolysis reaction to the hydrogen collection bottle, and the hydrogen dryer dries water vapor and other water vapor substances, improving the purity of the collected hydrogen. Hydrogen scrubbers are used to remove particulate matter or gaseous contaminants, thereby further improving the purity of the collected hydrogen.
用于动态制氢时，在槽体的上端有上端盖，上端盖上开设有供氢气收集管、氧气收集管和供能模块的导电线通过的接口，接口处密封连接。When used for dynamic hydrogen production, there is an upper end cover at the upper end of the tank body. The upper end cover is provided with an interface for the hydrogen collection pipe, the oxygen collection pipe and the conductive wire of the energy supply module to pass through, and the interfaces are sealed and connected.
在槽体的一侧还设置有电解质无能耗循环再生模块，电解质无能耗循环再生模块通过带有电解质溶液循环泵的电解质溶液循环管道与槽体连通；电解质无能耗循环再生模块为平板膜型电解质无能耗循环再生模块。An electrolyte energy-free cycle regeneration module is also provided on one side of the tank. The electrolyte energy-free cycle regeneration module is connected to the tank through an electrolyte solution circulation pipeline with an electrolyte solution circulation pump; the electrolyte energy-free cycle regeneration module is a flat membrane type electrolyte. No energy consumption recycling module.
所述的平板膜型电解质无能耗循环再生模块包括平板膜传质舱、双层平板膜、平板膜内腔、平板膜外部室、分流管汇管、非纯水溶液槽体、非纯水溶液室、非纯水溶液循环管道和非纯水溶液循环泵；其平板膜传质舱内排列设置有多组并联的双层平板膜，单组双层平板膜由两张膜层平行排布，两侧面密封，其顶、底面分别与分流管汇管连接；双层平板膜中间的狭长间隙为平板膜内腔，双层平板膜的膜层外壁与平板膜传质舱之间的空间为平板膜外部室。The flat membrane type electrolyte energy-free recycling regeneration module includes a flat membrane mass transfer chamber, a double-layer flat membrane, a flat membrane inner cavity, a flat membrane outer chamber, a shunt manifold, a non-pure aqueous solution tank, and a non-pure aqueous solution chamber. Non-pure water solution circulation pipeline and non-pure water solution circulation pump; multiple sets of parallel double-layer flat membranes are arranged in the flat membrane mass transfer chamber. A single set of double-layer flat membranes is composed of two membrane layers arranged in parallel, and both sides are sealed. Its top and bottom surfaces are connected to the shunt manifold respectively; the narrow gap in the middle of the double-layer flat membrane is the inner cavity of the flat membrane, and the space between the outer wall of the membrane layer of the double-layer flat membrane and the flat membrane mass transfer chamber is the outer chamber of the flat membrane.
槽体、电解质溶液循环管道、电解质溶液循环泵、分流管汇和双层平板膜串联，电解质溶液循环泵循环自驱动电解质溶液，使电解质溶液室连通平板膜内腔，自驱动电解质溶液从平板膜内腔通过；平板膜传质舱与非纯水溶液循环管道、非纯水溶液循环泵、非纯水溶液槽体串联；非纯水溶液循环泵用于循环非纯水溶液，平板膜外部室与非纯水溶液室连通，非纯水溶液从平板膜外部室通过；双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过纤维膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由平板膜外部室向平板膜内腔无能耗转移水分，同时双层平板膜将非纯水中的杂质阻挡在外。The tank body, electrolyte solution circulation pipeline, electrolyte solution circulation pump, shunt manifold and double-layer flat membrane are connected in series. The electrolyte solution circulation pump circulates the self-driven electrolyte solution to connect the electrolyte solution chamber to the inner cavity of the flat membrane. The self-driven electrolyte solution flows from the flat membrane to The inner chamber passes through; the flat membrane mass transfer chamber is connected in series with the non-pure water solution circulation pipe, the non-pure water solution circulation pump, and the non-pure water solution tank; the non-pure water solution circulation pump is used to circulate the non-pure water solution, and the flat membrane outer chamber is connected with the non-pure water solution chamber. Connected, the non-pure aqueous solution passes through the outer chamber of the flat membrane; during the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces the phase change and gasification of the non-pure aqueous solution to form water vapor, and the water vapor directionally migrates to the electrolyte side through the fiber membrane. It is induced to undergo a liquefaction phase change to provide pure water for electrolysis. This process transfers water from the outer chamber of the flat membrane to the inner chamber of the flat membrane without energy consumption. At the same time, the double-layer flat membrane blocks impurities in impure water.
电解质溶液室连通平板膜外部室，自驱动电解质溶液从平板膜外部室通过；平板膜内腔连通非纯水溶液室，非纯水溶液从平板膜内腔通过，双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由平板膜内腔向平板膜外部室无能耗转移水分。The electrolyte solution chamber is connected to the outer chamber of the flat membrane, and the self-driven electrolyte solution passes through the outer chamber of the flat membrane; the inner chamber of the flat membrane is connected to the non-pure aqueous solution chamber, and the non-pure aqueous solution passes through the inner chamber of the flat membrane. During the two-way circulation process, the interface vapor pressure difference Under the action, the self-driven electrolyte solution induces the phase change of the non-pure aqueous solution to vaporize to form water vapor. The water vapor directionally migrates to the electrolyte side through the membrane and is induced to liquefy and phase change to provide pure water for electrolysis. This process moves from the inner cavity of the flat membrane to the flat plate. The outer chamber of the membrane transfers moisture without energy consumption.
当自驱动电解质溶液呈碱性时，则在阴极催化层6表面发生还原析氢反应，反应式如下：
2H2O+2e-→H2+2OH- When the self-driven electrolyte solution is alkaline, a reduction and hydrogen evolution reaction occurs on the surface of the cathode catalytic layer 6, and the reaction formula is as follows:
2H 2 O+2e - →H 2 +2OH -
电解单元中阴极极板内部开设有阴极溶液室，并有孔连接阴极导管，多组电解单元的阴极导管连接汇集于一体形成氢气收集管。产出的氢气通过氢气收集管流通，通过氢气洗涤器17和氢气干燥器，脱出氢气中夹带的水汽，经过管道收集进入氢气储存器，进行储存和下一 步利用。产生的OH-通过隔膜/离子交换膜传递至阳极催化层4，发生氧化反应产生氧气，反应式如下：
There is a cathode solution chamber inside the cathode plate in the electrolysis unit, and there are holes to connect the cathode conduits. The cathode conduits of multiple groups of electrolysis units are connected and integrated to form a hydrogen collection pipe. The produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber 17 and the hydrogen dryer, removes the water vapor entrained in the hydrogen, and is collected through the pipeline into the hydrogen storage tank for storage and next generation. step utilization. The generated OH - is transferred to the anode catalytic layer 4 through the separator/ion exchange membrane, and an oxidation reaction occurs to generate oxygen. The reaction formula is as follows:
析氧反应产生的氧气通过氧气收集管20汇集，并经过氧气洗涤器和氧气干燥器，收集至氧气储存器。The oxygen generated by the oxygen evolution reaction is collected through the oxygen collection pipe 20, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank.
当自驱动电解质溶液呈酸性时，则在阳极催化层表面发生氧化析氧反应，反应式如下：
When the self-driven electrolyte solution is acidic, an oxidation and oxygen evolution reaction occurs on the surface of the anode catalytic layer. The reaction formula is as follows:
析氧反应产生的氧气通过氧气收集管汇集，并经过氧气洗涤器和氧气干燥器，收集至氧气储存器。产生的H+通过隔膜/离子交换膜5传递至阴极催化层，发生还原反应产生氢气，反应式如下：
2H++2e-→H2 The oxygen produced by the oxygen evolution reaction is collected through the oxygen collection pipe, passes through the oxygen scrubber and the oxygen dryer, and is collected into the oxygen storage tank. The generated H + is transferred to the cathode catalytic layer through the separator/ion exchange membrane 5, and a reduction reaction occurs to generate hydrogen. The reaction formula is as follows:
2H + +2e - →H 2
产出的氢气通过氢气收集管流通，通过氢气洗涤器和氢气干燥器，脱出氢气中夹带的水汽，经过管道收集进入氢气储存器，进行储存和下一步利用。The produced hydrogen flows through the hydrogen collection pipe, passes through the hydrogen scrubber and the hydrogen dryer, and removes the water vapor entrained in the hydrogen. It is collected through the pipeline and entered into the hydrogen storage tank for storage and further utilization.
电解质溶液同步进行电解制氢，电解质溶液中的水不断被电解消耗，诱导电解质循环再生，维持界面压力差，实现系统无额外能耗的自循环激发驱动，从而实现连续高效产氢。The electrolyte solution is synchronously electrolyzed to produce hydrogen. The water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous and efficient hydrogen production.
供能模块为电解单元提供电能，太阳能、风能等可再生能源产生的电力或火电、水电储存在供能模块中，用于为制氢反应提供电能，制氢反应的电能来源广泛且易储存。The energy supply module provides electric energy for the electrolysis unit. Electricity generated from renewable energy sources such as solar energy and wind energy or thermal power and hydropower is stored in the energy supply module to provide electric energy for the hydrogen production reaction. The electric energy for the hydrogen production reaction has a wide range of sources and is easy to store.
本发明的电解单元适用于较广范围的制氢电解结构。The electrolysis unit of the present invention is suitable for a wider range of hydrogen production electrolysis structures.
阳极溶液室内的阳极催化层、阴极溶液室内的阴极催化层的设置，这有利于提高电解反应的速率。内部极板和催化层紧凑化，大幅提高了整个电解单元的稳定性。The arrangement of the anode catalytic layer in the anode solution chamber and the cathode catalytic layer in the cathode solution chamber is beneficial to increasing the rate of the electrolysis reaction. The compactness of the internal plates and catalytic layers greatly improves the stability of the entire electrolysis unit.
可用的阳极催化电极包括：泡沫镍钼、泡沫镍铁、FexCoyNiz型催化剂、钌铱、NiFe-LDH、NiFeCu合金催化剂等(根据实际电解质酸碱性进行选择)；可用的析氢催化剂包括：铂金网、镍镀铂网等(根据实际电解质酸碱性进行选择)。Available anode catalytic electrodes include: nickel-molybdenum foam, nickel-iron foam, FexCoyNiz catalyst, ruthenium-iridium, NiFe-LDH, NiFeCu alloy catalyst, etc. (selected according to the actual acidity and alkalinity of the electrolyte); available hydrogen evolution catalysts include: platinum mesh, Nickel-plated platinum mesh, etc. (select according to the actual acidity and alkalinity of the electrolyte).
平板膜的膜层，可以为任何具有防水透气性能的材料。The membrane layer of the flat membrane can be any material with waterproof and breathable properties.
动态循环电解液制氢的其他实施例，方法步骤同实施例3，区别见表3：

In other embodiments of dynamic circulation electrolyte hydrogen production, the method steps are the same as those in Embodiment 3, and the differences are shown in Table 3:

经试验论证，选择的湖水、海水或河水不同，对本申请效果无明显影响。After experimental verification, the selected lake water, sea water or river water has no obvious impact on the effect of this application.
由上可以看出，本申请所描述的整个系统装置可以根据产氢量的需求设计成建议携带或大规模制备的集成装置，可以在包括污泥、沼泽、河流、湖泊、工业废水任何非纯水的体系环境中使用，且不受时间、空间的限制进行连续的原位产氢工作。同时该系统装置可以和风电、光伏耦合，实现非稳定可再生能源的能源转化，形成的氢能有利于稳定储存。It can be seen from the above that the entire system device described in this application can be designed as an integrated device recommended for portability or large-scale preparation according to the demand for hydrogen production. It can be used in any non-pure environment including sludge, swamps, rivers, lakes, and industrial wastewater. It can be used in a water system environment and can carry out continuous in-situ hydrogen production without being restricted by time and space. At the same time, the system device can be coupled with wind power and photovoltaic to realize energy conversion of unstable renewable energy, and the hydrogen energy formed is conducive to stable storage.
本发明专利所采用的电解组装方式，可以单组也可以多组，可以并联也可以串联，不仅适用于规则形状，未来也可以替换成异形，来适应于不同地区环境。The electrolytic assembly method used in the patent of this invention can be a single group or multiple groups, and can be connected in parallel or in series. It is not only suitable for regular shapes, but can also be replaced with special shapes in the future to adapt to different regional environments.
本发明主要应用于非纯水中的浸入式电解制氢，也可以用于非浸入式，或直接捕集大气中的水分。The invention is mainly used for immersed electrolysis hydrogen production in non-pure water, and can also be used for non-immersed hydrogen production, or for directly capturing moisture in the atmosphere.
本发明除了用火电电力以外，还可以耦合风电、光伏、核能等可再生能源，实现绿氢生产。In addition to using thermal power, this invention can also couple renewable energy sources such as wind power, photovoltaic, and nuclear energy to achieve green hydrogen production.
本发明构建了一种海水无淡化原位直接电解制氢系统，可以从海水、河水、湖水、淤泥、沼泽等各种非纯净水系统中，通过海水与电解质间的界面压力差，促进水汽传质并被自驱动电解质诱导相变液化，收集的水分在电解反应下生产氢气。该发明从根本上解决了离子成分复杂使离子交换膜失效、催化剂失活、产生碱性沉淀和有毒气体等问题；同时，有助于未来氢能源转化不受时空限制，为非纯水的原位直接制氢提供强有力技术支撑。The present invention constructs a seawater-free in-situ direct electrolysis hydrogen production system without desalination, which can promote water vapor transfer from various impure water systems such as seawater, river water, lake water, silt, swamps, etc. through the interface pressure difference between seawater and electrolytes. The substance is liquefied by phase change induced by the self-driven electrolyte, and the collected water is used to produce hydrogen under the electrolysis reaction. This invention fundamentally solves the problems of complex ion components causing the failure of ion exchange membranes, deactivation of catalysts, and the generation of alkaline precipitation and toxic gases. At the same time, it will help future hydrogen energy conversion not be limited by time and space, and become the source of impure water. Provide strong technical support for direct hydrogen production.
非纯水溶液无淡化原位直接电解制氢系统通过供电模块提供能源输入、自驱动电解质诱导水汽传质相变液化自发获取无杂质水分、电解催化制氢三个主要流程实现整体的海水无淡化原位直接电解制氢。首先，供电模块为电解制氢模块提供电力。供电模块的能量来源可以为太阳能、风能等可再生能源能源转化为电能，也可直接利用火电、水电等。其次，将海水无淡化原位直接电解制氢装置浸没水中，在水溶液和自驱动电解质界面压力差作用下，水汽通过无能耗水汽传质层进入电解系统，被自驱动电解质诱导相变液化形成电解质溶液，同时无能耗水汽传质层将溶液中的非水杂质有效阻隔。最终，在电解催化制氢模块中，在催化体系下对电解质溶液进行电解制氢。电解质溶液中的水不断被电解消耗，诱导电解质循环再生，维持界面压力差，实现系统无额外能耗的自循环激发驱动，从而实现连续高效产氢。 The in-situ direct electrolysis hydrogen production system without desalination of non-pure aqueous solutions achieves the overall desalination-free seawater through three main processes: energy input through the power supply module, self-driven electrolyte-induced water vapor mass transfer phase change liquefaction, spontaneous acquisition of impurity-free water, and electrolysis catalytic hydrogen production. Direct electrolysis of hydrogen. First, the power supply module provides power for the electrolysis hydrogen production module. The energy source of the power supply module can be converted into electrical energy from renewable energy sources such as solar energy and wind energy, or it can directly utilize thermal power, hydropower, etc. Secondly, the in-situ direct electrolysis hydrogen production device without desalination is immersed in the water. Under the pressure difference at the interface between the aqueous solution and the self-driven electrolyte, water vapor enters the electrolysis system through the energy-free water vapor mass transfer layer, and is induced by the self-driven electrolyte to undergo phase change and liquefy to form an electrolyte. solution, while the energy-free water vapor mass transfer layer effectively blocks non-aqueous impurities in the solution. Finally, in the electrolysis catalytic hydrogen production module, the electrolyte solution is electrolyzed to produce hydrogen under the catalytic system. The water in the electrolyte solution is continuously consumed by electrolysis, inducing electrolyte circulation and regeneration, maintaining the interface pressure difference, and realizing self-circulation excitation driving of the system without additional energy consumption, thereby achieving continuous and efficient hydrogen production.
整体技术效果：该系统通过供电模块提供电能，通过自驱动电解质诱导水汽传质液化相变获取水分，然后利用催化电解原理制取氢气。一方面，该系统能实现在任何水溶液环境中无时空差别的制氢动态连续过程；另一方面，可以对非稳定的可再生能源实现能源转化和稳定储存，为未来能源体系构建提供技术手段。Overall technical effect: The system provides electrical energy through the power supply module, obtains water through the self-driven electrolyte to induce water vapor mass transfer and liquefaction phase change, and then uses the principle of catalytic electrolysis to produce hydrogen. On the one hand, this system can realize a dynamic and continuous process of hydrogen production without temporal and spatial differences in any aqueous solution environment; on the other hand, it can realize energy conversion and stable storage of non-stable renewable energy, providing technical means for the construction of future energy systems.
本说明书中所有实施例公开的所有特征，或隐含公开的所有方法或过程中的步骤，除了互相排斥的特征和/或步骤以外，均可以以任何方式组合和/或扩展、替换。All features disclosed in all embodiments in this specification, or all steps in methods or processes implicitly disclosed, except for mutually exclusive features and/or steps, may be combined and/or extended or replaced in any manner.
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，依据本发明的技术实质，在本发明的精神和原则之内，对以上实施例所作的任何简单的修改、等同替换与改进等，均仍属于本发明技术方案的保护范围之内。 The above are only preferred embodiments of the present invention and do not limit the present invention in any form. According to the technical essence of the present invention and within the spirit and principles of the present invention, any simple modifications to the above embodiments may be made. Modifications, equivalent substitutions and improvements, etc., all still fall within the protection scope of the technical solution of the present invention.

Claims (11)

  1. 一种非纯水溶液无淡化原位直接电解制氢装置，用于电解液静态制氢，其特征在于该装置包括，A device for in-situ direct electrolysis of hydrogen production from non-pure aqueous solutions without desalination, which is used for static hydrogen production from electrolyte. It is characterized in that the device includes:
    供能模块(1)：用于为制氢反应提供电能；Energy supply module (1): used to provide electrical energy for the hydrogen production reaction;
    与供能模块(1)连接的电解单元(10)：所述电解单元(10)包括相对设置的阳极溶液室(8)、阴极溶液室(9)，设于所述阳极溶液室(8)内的阳极极板(3)，设于所述阴极溶液室(9)内的阴极极板(7)，所述阳极极板(3)与所述阴极极板(7)分别与所述供能模块(1)相连，所述阳极溶液室(8)与所述阴极溶液室(9)之间设有隔膜(5)；多个电解单元(10)串联或并联堆叠形成电解堆(15)，用于制氢反应，产生氢气；The electrolysis unit (10) connected to the energy supply module (1): the electrolysis unit (10) includes an anode solution chamber (8) and a cathode solution chamber (9) arranged oppositely, and is located in the anode solution chamber (8) The anode plate (3) in the cathode solution chamber (9) and the cathode plate (7) located in the cathode solution chamber (9), the anode plate (3) and the cathode plate (7) are respectively connected with the supply The energy module (1) is connected, and a diaphragm (5) is provided between the anode solution chamber (8) and the cathode solution chamber (9); multiple electrolysis units (10) are stacked in series or in parallel to form an electrolysis stack (15) , used in the hydrogen production reaction to produce hydrogen;
    支架(11)：用于固定电解堆(15)；Bracket (11): used to fix the electrolysis stack (15);
    多孔网槽(41)：用于放置支架(11)，多孔网槽(41)内壁紧贴水汽传质层(40)，水汽传质层(40)形成一个凹形空间，形成电解质溶液室(14)，用于存放自驱动电解质溶液；Porous mesh trough (41): used to place the bracket (11). The inner wall of the porous mesh trough (41) is close to the water vapor mass transfer layer (40). The water vapor mass transfer layer (40) forms a concave space to form an electrolyte solution chamber ( 14), used to store self-driven electrolyte solutions;
    收集装置：收集装置与电解单元(10)相连，用以收集电解产生的氢气和氧气。Collection device: The collection device is connected to the electrolysis unit (10) to collect hydrogen and oxygen produced by electrolysis.
  2. 一种非纯水溶液无淡化原位直接电解制氢装置，用于动态循环电解液制氢，其特征在于，该装置包括，A device for in-situ direct electrolysis of hydrogen production from non-pure aqueous solutions without desalination, which is used for dynamic circulation of electrolyte to produce hydrogen. It is characterized in that the device includes:
    供能模块(1)：用于为制氢反应提供电能；Energy supply module (1): used to provide electrical energy for the hydrogen production reaction;
    与供能模块(1)连接的电解单元(10)：所述电解单元(10)包括相对设置的阳极溶液室(8)、阴极溶液室(9)，设于所述阳极溶液室(8)内的阳极极板(3)，设于所述阴极溶液室(9)内的阴极极板(7)，所述阳极极板(3)与所述阴极极板(7)分别与所述供能模块(1)相连，所述阳极溶液室(8)与所述阴极溶液室(9)之间设有隔膜(5)；多个电解单元(10)串联或并联堆叠形成电解堆(15)，用于制氢反应，产生氢气；The electrolysis unit (10) connected to the energy supply module (1): the electrolysis unit (10) includes an anode solution chamber (8) and a cathode solution chamber (9) arranged oppositely, and is located in the anode solution chamber (8) The anode plate (3) in the cathode solution chamber (9) and the cathode plate (7) located in the cathode solution chamber (9), the anode plate (3) and the cathode plate (7) are respectively connected with the supply The energy module (1) is connected, and a diaphragm (5) is provided between the anode solution chamber (8) and the cathode solution chamber (9); multiple electrolysis units (10) are stacked in series or in parallel to form an electrolysis stack (15) , used in the hydrogen production reaction to produce hydrogen;
    支架(11)：用于固定电解堆(15)；Bracket (11): used to fix the electrolysis stack (15);
    槽体(12)：用于放置支架(11)，在支架(11)与槽体(12)的空隙处形成电解质溶液室(14)，用于存放自驱动电解质溶液；Tank body (12): used to place the bracket (11), and an electrolyte solution chamber (14) is formed in the gap between the bracket (11) and the tank body (12), used to store the self-driven electrolyte solution;
    收集装置：收集装置与电解单元(10)相连，用以收集电解产生的氢气和氧气。Collection device: The collection device is connected to the electrolysis unit (10) to collect hydrogen and oxygen produced by electrolysis.
  3. 如权利要求1或2所述的非纯水溶液无淡化原位直接电解制氢装置，其特征在于：所述电解单元(10)还包括设于所述阳极溶液室(8)内的阳极催化层(4)、设于所述阴极溶液室(9)内的阴极催化层(6)；阳极极板(3)、阳极催化层(4)与绝缘卡槽(2)的流道间隙形成阳极溶液室(8)，阳极溶液室(8)内充满自驱动电解质溶液；阴极极板(7)与阴极催化层(6)的流道间隙形成阴极溶液室(9)，阴极溶液室(9)内充满自驱动电解质溶液；电解质溶液刚好浸没电解堆(15)。The in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution according to claim 1 or 2, characterized in that: the electrolysis unit (10) further includes an anode catalytic layer located in the anode solution chamber (8) (4), the cathode catalytic layer (6) located in the cathode solution chamber (9); the flow channel gap between the anode plate (3), the anode catalytic layer (4) and the insulating slot (2) forms the anode solution Chamber (8), the anode solution chamber (8) is filled with self-driven electrolyte solution; the flow channel gap between the cathode plate (7) and the cathode catalytic layer (6) forms a cathode solution chamber (9), and the cathode solution chamber (9) Filled with self-driven electrolyte solution; the electrolyte solution just immerses the electrolysis stack (15).
  4. 如权利要求1或2所述的非纯水溶液无淡化原位直接电解制氢装置，其特征在于：所述的收集装置包括氢气收集管(16)和氧气收集管(20)；在氢气收集管(16)后面依次连接有氢气洗涤器(17)、氢气干燥器(18)及氢气储存器(19)；在氧气收集管(20)后面依次连接有氧气洗涤器(21)、氧气干燥器(22)及氧气储存器(23)。The in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution according to claim 1 or 2, characterized in that: the collection device includes a hydrogen collection pipe (16) and an oxygen collection pipe (20); in the hydrogen collection pipe A hydrogen scrubber (17), a hydrogen dryer (18) and a hydrogen storage tank (19) are connected in sequence behind (16); an oxygen scrubber (21), an oxygen dryer (20) are connected in sequence behind the oxygen collection pipe (20) 22) and oxygen storage (23).
  5. 如权利要求1所述的非纯水溶液无淡化原位直接电解制氢装置，其特征在于：在多孔网槽(41)上设置上端盖(13)，多孔网槽(41)和上端盖(13)之间密封链接；在上端盖(13)上开设有供氢气收集管(16)、氧气收集管(20)和供能模块(1)的导电线通过的接口，接口处密封连接；电解制氢时，多孔网槽(41)部分浸于非纯水溶液中，在水汽传质层(40)界面处产生蒸汽压差，诱导非纯水溶液发生气化相变，同时通过水汽传质层(40)定向传递至电解质侧，并在蒸汽压差作用下被电解质诱导液化吸收；电解质被同步电解，进一步维持非纯水溶液与电解质间的界面蒸汽压差，从而形成不额外耗能的稳定制氢过程。The in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution according to claim 1, characterized in that: an upper end cover (13) is provided on the porous mesh tank (41), and the porous mesh tank (41) and the upper end cover (13 ); the upper end cover (13) is provided with an interface for the conductive wires of the hydrogen collection pipe (16), the oxygen collection pipe (20) and the energy supply module (1) to pass through, and the interfaces are sealed and connected; the electrolytic production When hydrogen is used, the porous mesh groove (41) is partially immersed in the impure water solution, which generates a vapor pressure difference at the interface of the water vapor mass transfer layer (40), inducing the gasification phase change of the impure aqueous solution, and at the same time passes through the water vapor mass transfer layer (40) ) is directed to the electrolyte side, and is induced to liquefy and absorb by the electrolyte under the action of vapor pressure difference; the electrolyte is synchronously electrolyzed, further maintaining the interfacial vapor pressure difference between the impure aqueous solution and the electrolyte, thereby forming a stable hydrogen production process without additional energy consumption .
  6. 如权利要求5所述的非纯水溶液无淡化原位直接电解制氢装置，其特征在于：当多孔网槽(41)部分浸于非纯水溶液时，多孔网槽(41)槽体及内壁贴合的水汽传质层(40)与上端盖(13)形成密闭空间，与外界空气、液体隔绝。 The in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution according to claim 5, characterized in that: when the porous mesh tank (41) is partially immersed in the non-pure aqueous solution, the tank body and the inner wall of the porous mesh tank (41) are adhered to The combined water vapor mass transfer layer (40) and the upper end cover (13) form a closed space, which is isolated from outside air and liquid.
  7. 如权利要求2所述的非纯水溶液无淡化原位直接电解制氢装置，其特征在于：在槽体(12)的上端有上端盖(13)，槽体(12)和上端盖(13)之间密封链接；上端盖(13)上开设有供氢气收集管(16)、氧气收集管(20)和供能模块(1)的导电线通过的接口，接口处密封连接。The in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution according to claim 2, characterized in that: there is an upper end cover (13) at the upper end of the tank body (12), and the tank body (12) and the upper end cover (13) The upper end cover (13) is provided with an interface for the conductive wires of the hydrogen collection pipe (16), the oxygen collection pipe (20) and the energy supply module (1) to pass through, and the interfaces are sealed and connected.
  8. 如权利要求2所述的非纯水溶液无淡化原位直接电解制氢装置，其特征在于：在槽体(12)的一侧还设置有电解质无能耗循环再生模块(24)，电解质无能耗循环再生模块(24)通过带有电解质溶液循环泵(29)的电解质溶液循环管道(27)与槽体(12)连通；电解质无能耗循环再生模块(24)根据膜组件类型，分为中空纤维膜型电解质无能耗循环再生模块与平板膜型电解质无能耗循环再生模块两种。The in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution according to claim 2, characterized in that: an electrolyte energy-free circulation regeneration module (24) is also provided on one side of the tank (12), and the electrolyte energy-free circulation The regeneration module (24) is connected to the tank (12) through the electrolyte solution circulation pipe (27) with the electrolyte solution circulation pump (29); the electrolyte energy-free circulation regeneration module (24) is divided into hollow fiber membranes according to the type of membrane module. There are two types: type electrolyte energy-free recycling regeneration module and flat membrane type electrolyte energy-free recycling regeneration module.
  9. 如权利要求8所述的非纯水溶液无淡化原位直接电解制氢装置，其特征在于：所述的中空纤维膜型电解质无能耗循环再生模块包括中空纤维膜传质舱(31)、中空纤维膜(32)、中空纤维膜内腔(33)、中空纤维膜外部室(34)、非纯水溶液槽体(25)、非纯水溶液室(26)、非纯水溶液循环管道(28)和非纯水溶液循环泵(30)；中空纤维膜传质舱(31)内密集设置有多根并联的中空纤维膜(32)，中空纤维膜(32)膜层内部的可流通溶液空间为中空纤维膜内腔(33)，中空纤维膜(32)膜层外壁与中空纤维膜传质舱(31)之间的空间为中空纤维膜外部室(34)；槽体(12)、电解质溶液循环管道(27)、电解质溶液循环泵(29)和中空纤维膜(32)串联，电解质溶液循环泵(29)循环自驱动电解质溶液，使电解质溶液室(14)连通中空纤维膜内腔(33)，自驱动电解质溶液从中空纤维膜内腔(33)通过；中空纤维膜传质舱(31)与非纯水溶液循环管道(28)、非纯水溶液循环泵(30)、非纯水溶液槽体(25)串联；非纯水溶液循环泵(30)用于循环非纯水溶液，中空纤维膜外部室(34)与非纯水溶液室(26)连通，非纯水溶液从中空纤维膜外部室(34)通过；双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过纤维膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由中空纤维膜外部室(34)向中空纤维膜内腔(33)无能耗转移纯净水分，同时中空纤维膜(32)将非纯水溶液中的杂质阻挡在外。The in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution according to claim 8, characterized in that: the hollow fiber membrane type electrolyte energy-free recycling regeneration module includes a hollow fiber membrane mass transfer cabin (31), a hollow fiber membrane (32), hollow fiber membrane inner cavity (33), hollow fiber membrane outer chamber (34), non-pure aqueous solution tank (25), non-pure aqueous solution chamber (26), non-pure aqueous solution circulation pipe (28) and non-pure aqueous solution circulation pipe (28). Pure water solution circulation pump (30); a plurality of parallel hollow fiber membranes (32) are densely arranged in the hollow fiber membrane mass transfer chamber (31), and the flowable solution space inside the membrane layer of the hollow fiber membrane (32) is a hollow fiber membrane. The inner cavity (33), the space between the outer wall of the hollow fiber membrane (32) membrane layer and the hollow fiber membrane mass transfer chamber (31) is the hollow fiber membrane outer chamber (34); the tank body (12), the electrolyte solution circulation pipe ( 27), the electrolyte solution circulation pump (29) and the hollow fiber membrane (32) are connected in series. The electrolyte solution circulation pump (29) circulates the self-driven electrolyte solution, so that the electrolyte solution chamber (14) is connected to the hollow fiber membrane inner cavity (33), and the electrolyte solution circulation pump (29) automatically The electrolyte solution is driven to pass through the hollow fiber membrane inner cavity (33); the hollow fiber membrane mass transfer chamber (31) and the non-pure aqueous solution circulation pipe (28), the non-pure aqueous solution circulation pump (30), and the non-pure aqueous solution tank (25) Series connection; the non-pure aqueous solution circulation pump (30) is used to circulate the non-pure aqueous solution, the hollow fiber membrane outer chamber (34) is connected with the impure aqueous solution chamber (26), and the impure aqueous solution passes through the hollow fiber membrane outer chamber (34); bidirectional During the cycle, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces the phase change of the impure aqueous solution to vaporize to form water vapor. The water vapor migrates directionally to the electrolyte side through the fiber membrane and is induced to liquefy and phase change, providing pure water for electrolysis. , this process transfers pure water from the outer chamber (34) of the hollow fiber membrane to the inner cavity (33) of the hollow fiber membrane without energy consumption, and at the same time, the hollow fiber membrane (32) blocks impurities in the non-pure aqueous solution.
  10. 如权利要求8所述的非纯水溶液无淡化原位直接电解制氢装置，其特征在于：所述的平板膜型电解质无能耗循环再生模块包括平板膜传质舱(35)、双层平板膜(36)、平板膜内腔(37)、平板膜外部室(38)、分流管汇管(39)、非纯水溶液槽体(25)、非纯水溶液室(26)、非纯水溶液循环管道(28)和非纯水溶液循环泵(30)；其平板膜传质舱(35)内排列设置有多组并联的双层平板膜(36)，单组双层平板膜(36)由两张水汽传质层平行排布，两侧面密封，其顶、底面分别与分流管汇管(39)连接；双层平板膜(36)中间的狭长间隙为平板膜内腔(37)，双层平板膜(36)的膜层外壁与平板膜传质舱(35)之间的空间为平板膜外部室(38)；The in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution according to claim 8, characterized in that: the flat membrane type electrolyte energy-free recycling regeneration module includes a flat membrane mass transfer cabin (35), a double-layer flat membrane (36), flat membrane inner chamber (37), flat membrane outer chamber (38), shunt manifold (39), non-pure aqueous solution tank (25), non-pure aqueous solution chamber (26), non-pure aqueous solution circulation pipe (28) and a non-pure aqueous solution circulation pump (30); its flat membrane mass transfer chamber (35) is arranged with multiple sets of parallel double-layer flat membranes (36), and a single set of double-layer flat membranes (36) consists of two The water vapor mass transfer layer is arranged in parallel, sealed on both sides, and its top and bottom surfaces are connected to the shunt manifold (39) respectively; the narrow gap in the middle of the double-layer flat membrane (36) is the inner cavity (37) of the flat membrane, and the double-layer flat membrane The space between the outer wall of the membrane layer of the membrane (36) and the flat membrane mass transfer chamber (35) is the flat membrane outer chamber (38);
    槽体(12)、电解质溶液循环管道(27)、电解质溶液循环泵(29)、分流管汇(39)和双层平板膜(36)串联，电解质溶液循环泵(29)循环自驱动电解质溶液，使电解质溶液室(14)连通平板膜内腔(37)，自驱动电解质溶液从平板膜内腔(37)通过；平板膜传质舱(35)与非纯水溶液循环管道(28)、非纯水溶液循环泵(30)、非纯水溶液槽体(25)串联；非纯水溶液循环泵(30)用于循环非纯水溶液，平板膜外部室(38)与非纯水溶液室(26)连通，非纯水溶液从平板膜外部室(38)通过；双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过纤维膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由平板膜外部室(38)向平板膜内腔(37)无能耗转移水分，同时双层平板膜(36)将非纯水中的杂质阻挡在外。The tank body (12), electrolyte solution circulation pipe (27), electrolyte solution circulation pump (29), shunt manifold (39) and double-layer flat membrane (36) are connected in series, and the electrolyte solution circulation pump (29) circulates the self-driven electrolyte solution , the electrolyte solution chamber (14) is connected to the flat membrane inner cavity (37), and the self-driven electrolyte solution passes through the flat membrane inner cavity (37); the flat membrane mass transfer chamber (35) is connected with the non-pure aqueous solution circulation pipe (28), The pure water solution circulation pump (30) and the non-pure water solution tank (25) are connected in series; the non-pure water solution circulation pump (30) is used to circulate the non-pure water solution, and the flat membrane outer chamber (38) is connected with the non-pure water solution chamber (26). The non-pure aqueous solution passes through the outer chamber (38) of the flat membrane; during the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces phase change and gasification of the non-pure aqueous solution to form water vapor, and the water vapor directionally migrates to the electrolyte side through the fiber membrane , and is induced to liquefy phase change to provide pure water for electrolysis. This process transfers water from the outer chamber (38) of the flat membrane to the inner chamber (37) of the flat membrane without energy consumption. At the same time, the double-layer flat membrane (36) transfers impure water The impurities in it are blocked out.
  11. 如权利要求9或10所述的非纯水溶液无淡化原位直接电解制氢装置，其特征在于，电解质溶液与非纯水溶液的循环路径也可以调换，电解质溶液室(14)连通平板膜外部室(38) 或中空纤维膜外部室(34)，自驱动电解质溶液从平板膜外部室(38)或中空纤维膜外部室(34)通过；平板膜内腔(37)(或中空纤维膜内腔(33))连通非纯水溶液室(26)，非纯水溶液从平板膜内腔(37)或中空纤维膜内腔(33)通过，双向循环过程中，在界面蒸汽压差作用下，自驱动电解质溶液诱导非纯水溶液相变气化形成水汽，水汽通过膜定向迁移至电解质侧，并被诱导液化相变，为电解提供纯净的水分，该过程由平板膜内腔(37)或中空纤维膜内腔(33)向平板膜外部室(38)或中空纤维膜外部室(34)无能耗转移水分。 The in-situ direct electrolysis hydrogen production device without desalination of non-pure aqueous solution according to claim 9 or 10, characterized in that the circulation paths of the electrolyte solution and the non-pure aqueous solution can also be exchanged, and the electrolyte solution chamber (14) is connected to the outer chamber of the flat membrane (38) Or the hollow fiber membrane outer chamber (34), the self-driven electrolyte solution passes from the flat membrane outer chamber (38) or the hollow fiber membrane outer chamber (34); the flat membrane inner chamber (37) (or the hollow fiber membrane inner chamber (33) ) is connected to the non-pure aqueous solution chamber (26). The non-pure aqueous solution passes through the flat membrane inner cavity (37) or the hollow fiber membrane inner cavity (33). During the two-way circulation process, under the action of the interface vapor pressure difference, the self-driven electrolyte solution induces The phase change of the impure aqueous solution vaporizes to form water vapor. The water vapor directionally migrates to the electrolyte side through the membrane and is induced to undergo a liquefaction phase change to provide pure water for electrolysis. This process is carried out by the inner cavity of the flat membrane (37) or the inner cavity of the hollow fiber membrane ( 33) Transfer water to the flat membrane outer chamber (38) or the hollow fiber membrane outer chamber (34) without energy consumption.
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