A seawater hydrogen production device using tubular PEM electrolysis and its working method

Abstract

The present application discloses a tubular PEM electrolysis seawater hydrogen production device and its working method. The seawater hydrogen production device includes an internal support structure, a moisture-permeable hollow fiber membrane bundle, an anode electrode tube, a membrane electrode assembly, a cathode electrode tube and a tube shell. The moisture-permeable hollow fiber membrane bundle of the present application converts seawater into water vapor and separates ions to achieve desalination of seawater, and the electrolysis of water vapor is completed through the anode electrode tube, membrane electrode assembly and cathode electrode tube arranged in the pipeline. The generated hydrogen is transported to the outside and collected by a hydrogen collection device. The present hydrogen production device is a tubular structure, and a moisture-permeable hollow fiber membrane bundle is used inside to generate steam. Compared with a flat moisture-permeable membrane, it provides more moisture-permeable area and increases the moisture permeability. It has a compact structure and can complete seawater desalination and electrolytic hydrogen production in sequence, reducing the footprint of the device.

Description

Technical Field

[0001] The present application relates to the technical field of hydrogen production by water electrolysis, and in particular to a tubular PEM electrolysis seawater hydrogen production device and a working method thereof. Background Art

[0002] At present, the existing water electrolysis hydrogen production technologies mainly include alkaline (ALK) hydrogen production, proton exchange membrane (PEM) hydrogen production and solid oxide (SOEC) electrolyzer hydrogen production. Alkaline electrolyzers need to operate in an alkaline electrolyte (KOH, NaOH, etc.) environment. They have the characteristics of simple structure, high abundance and easy acquisition of raw materials, low cost, etc., and after years of commercial operation, the technology is mature and stable. The proton exchange membrane electrolyzer uses a perfluorosulfonic acid proton exchange membrane with good chemical stability, proton conductivity, and gas separation as a diaphragm, dividing the water electrolysis process into two reaction areas, the cathode and the anode. It has the characteristics of high electrolysis efficiency, compact structure, and fast response time. It is an important direction for the development of water electrolysis technology. The solid oxide electrolyzer needs to operate at high temperature (600-1000℃) and is still in the laboratory research stage.

[0003] All of the aforementioned water electrolysis technologies require freshwater to be obtained and converted into a suitable electrolytic medium before electrolysis to produce hydrogen. Ocean water resources account for approximately 97% of the world's total water supply. Using seawater directly as an electrolyte for electrolysis can reduce reliance on freshwater resources. However, due to the high concentration of salt and various ions in seawater, the electrolysis process is prone to problems such as electrode scaling, catalyst corrosion, membrane fouling, and the formation of chlorine as a byproduct. This can lead to decreased electrolysis efficiency and electrolytic cell failure. Therefore, desalination treatment is required before electrolysis, which undoubtedly complicates the entire seawater hydrogen production system and takes up a large amount of space. Summary of the Invention

[0004] The purpose of this application is to solve at least one of the technical problems existing in the prior art and to provide a tubular PEM electrolysis seawater hydrogen production device and its working method, which can complete seawater desalination and electrolysis hydrogen production, and has a smaller size to reduce space occupation.

[0005] According to an embodiment of the present application, a seawater hydrogen production device using tubular PEM electrolysis is provided, comprising:

[0006] An inner support structure, comprising an inner support tube and a stopper, wherein the side of the inner support tube is hollowed out to allow gas to pass through, and the stopper is mounted on the end of the inner support tube and has a plurality of stopper holes;

[0007] A moisture-permeable hollow fiber membrane tube bundle, wherein the moisture-permeable hollow fiber membrane tube bundle is composed of a plurality of moisture-permeable hollow fiber membrane tubes and is disposed in the inner support tube, wherein the moisture-permeable hollow fiber membrane tubes pass through the limiting holes to complete fixation, and seawater passes through the interior of the moisture-permeable hollow fiber membrane tubes, and water vapor of the seawater can diffuse outward through the moisture-permeable hollow fiber membrane tubes;

[0008] an anode electrode tube, the anode electrode tube being sleeved on the outer side of the inner support tube, and the side of the anode electrode tube being hollowed out to allow gas to pass through;

[0009] A membrane electrode assembly, the membrane electrode assembly is tubular and is sleeved on the outside of the anode electrode tube, the membrane electrode assembly comprising an anode diffusion layer, an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer and a cathode diffusion layer attached in sequence from the inside out;

[0010] a cathode electrode tube, the cathode electrode tube being sleeved on the outside of the membrane electrode assembly, the side of the cathode electrode tube being hollowed out to allow gas to pass through;

[0011] a tube shell, wherein the tube shell is sleeved on the outer side of the cathode electrode tube, and a gap is left between the tube shell and the cathode electrode tube to allow gas to flow along the tube shell;

[0012] The water vapor of seawater enters the device through the moisture-permeable hollow fiber membrane tube, and the water vapor is electrolyzed in the membrane electrode assembly. Hydrogen flows out from the side of the cathode electrode tube and flows along the tube shell to the air outlet to be collected.

[0013] According to an embodiment of the present application, further, the tubular PEM electrolysis seawater hydrogen production device also includes at least one of an air gap and a hygroscopic medium, the air gap or the hygroscopic medium is arranged between the moisture permeable hollow fiber membrane tube bundle and the anode electrode tube, and the hygroscopic medium is used to absorb water vapor generated from the moisture permeable hollow fiber membrane tube bundle.

[0014] According to an embodiment of the present application, further, the end of the inner support tube and the side surface of the limiting member are both provided with threads, and the limiting member and the inner support tube are connected to each other through the threads.

[0015] According to an embodiment of the present application, further, the moisture permeable hollow fiber membrane tubes in the moisture permeable hollow fiber membrane tube bundle are distributed in an array.

[0016] According to an embodiment of the present application, further, the PEM electrolysis seawater hydrogen production device also includes a solar panel, a water pump and a voltage regulator, the water pump is used to drive seawater into the moisture permeable hollow fiber membrane tube bundle, the voltage regulator is electrically connected to the anode electrode tube and the cathode electrode tube, and the solar panel is electrically connected to the water pump and the voltage regulator to provide electrical energy.

[0017] According to an embodiment of the present application, further, the PEM electrolysis seawater hydrogen production device also includes a connecting plate, and there are multiple PEM electrolysis seawater hydrogen production devices and they are all connected to each other through the connecting plate.

[0018] According to an embodiment of the present application, a method for operating the seawater hydrogen production device using PEM electrolysis is provided, comprising:

[0019] Seawater enters the tubular PEM electrolysis seawater hydrogen production device, and its liquid water is isolated in the tube by the moisture permeable hollow fiber membrane tube, and water vapor passes through the moisture permeable hollow fiber membrane tube and enters the interior of the tubular PEM electrolysis seawater hydrogen production device;

[0020] Water vapor flows from the side of the moisture-permeable hollow fiber membrane tube, passes through the anode electrode tube and enters the membrane electrode assembly;

[0021] The anode electrode tube and the cathode electrode tube are energized respectively, and water vapor is electrolyzed in the membrane electrode assembly;

[0022] Oxygen generated by water vapor electrolysis returns through the anode catalyst layer to the gap between the anode electrode tube and the fiber membrane tube bundle, and flows out along the pipeline to the air outlet;

[0023] The hydrogen generated by water vapor electrolysis enters the gap between the cathode electrode tube and the tube shell through the cathode catalyst layer and flows out along the pipeline to the end;

[0024] The external hydrogen collection device collects the generated hydrogen to complete the preparation of hydrogen.

[0025] The beneficial effects of the embodiments of the present application include at least the following: the present application converts seawater into water vapor and separates it from ions through a moisture-permeable hollow fiber membrane bundle, thereby achieving seawater desalination, and electrolyzes the water vapor through the anode electrode tube, membrane electrode assembly, and cathode electrode tube disposed within the pipeline, with the generated hydrogen being transported to the outside and collected by a hydrogen collection device. The present hydrogen production device is a tubular structure that uses a moisture-permeable hollow fiber membrane bundle to generate steam. Compared to a flat moisture-permeable membrane, this device provides more moisture-permeable area and increases the moisture permeability. It has a compact structure and can sequentially complete seawater desalination and electrolytic hydrogen production, reducing the device's footprint. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] To more clearly illustrate the technical solutions in the embodiments of this application, the following briefly describes the drawings required for describing the embodiments. Obviously, the drawings described are only part of the embodiments of this application, not all of them. Those skilled in the art can also derive other design solutions and drawings based on these drawings without inventive effort.

[0027] Figure 1This is a three-dimensional diagram of the seawater hydrogen production device using PEM electrolysis in this application;

[0028] Figure 2 This is a cross-sectional view of the seawater hydrogen production device using PEM electrolysis in the present application;

[0029] Figure 3 This is a schematic diagram of the connection between the moisture-permeable hollow fiber membrane bundle 200 and the stopper 120 in the seawater hydrogen production device using PEM electrolysis of the present application;

[0030] Figure 4 This is a three-dimensional diagram of the inner support tube 110 in the seawater hydrogen production device using PEM electrolysis of the present application;

[0031] Figure 5 It is a three-dimensional diagram of the anode electrode tube 300 in the seawater hydrogen production device using PEM electrolysis of the present application;

[0032] Figure 6 It is a three-dimensional diagram of the membrane electrode assembly 400 in the seawater hydrogen production device using PEM electrolysis of the present application;

[0033] Figure 7 This is a three-dimensional diagram of the cathode electrode tube 500 in the seawater hydrogen production device using PEM electrolysis in this application.

[0034] Figure 8 It is a three-dimensional diagram of the shell and tube 600 in the seawater hydrogen production device using PEM electrolysis of the present application;

[0035] Figure 9 This is a schematic diagram of connecting multiple hydrogen production devices through a connecting plate 800 in the seawater hydrogen production device using PEM electrolysis of the present application;

[0036] Figure 10 This is a comparison chart of the electrolysis performance of the seawater hydrogen production device using PEM electrolysis in this application, using fresh water, flat membrane, and moisture-permeable hollow fiber membrane bundle;

[0037] Figure 11 This is a distribution diagram of a moisture permeable hollow fiber membrane bundle 200 of a seawater hydrogen production device using PEM electrolysis in the present application;

[0038] Figure 12 This is a comparison chart of the effects of the hygroscopic medium 700 on the electrolysis energy of the tubular PEM electrolysis seawater hydrogen production device at different temperatures.

[0039] Figure numerals: 100 - internal support structure, 110 - internal support tube, 120 - limiter, 200 - moisture permeable hollow fiber membrane tube bundle, 300 - anode electrode tube, 400 - membrane electrode assembly, 410 - anode catalyst layer, 420 - proton exchange membrane, 430 - cathode catalyst layer, 440 - anode diffusion layer, 450 - cathode diffusion layer, 500 - cathode electrode tube, 600 - tube shell, 700 - moisture absorbing medium, 800 - connecting plate. DETAILED DESCRIPTION

[0040] This section will describe the specific embodiments of the present application in detail. The preferred embodiments of the present application are shown in the accompanying drawings. The purpose of the accompanying drawings is to supplement the description of the text part of the specification with graphics, so that people can intuitively and vividly understand each technical feature and overall technical solution of the present application, but it cannot be understood as a limitation on the scope of protection of the present application.

[0041] In the description of this application, it should be understood that descriptions involving orientations, such as up, down, front, back, left, right, etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings. They are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, they cannot be understood as limitations on this application.

[0042] In the description of this application, "several" means one or more, "many" means more than two, "greater than," "less than," and "exceed" are understood to exclude the number itself, while "above," "below," and "within" are understood to include the number itself. The terms "first" and "second" are used solely to distinguish technical features and are not to be construed as indicating or implying relative importance, or as implicitly specifying the number or order of the technical features indicated.

[0043] In the description of this application, unless otherwise clearly defined, terms such as setting, installing, and connecting should be understood in a broad sense, and technicians in the relevant technical field can reasonably determine the specific meanings of the above terms in this application based on the specific content of the technical solution.

[0044] This application proposes a tubular PEM electrolysis seawater hydrogen production device and its operating method. A moisture-permeable hollow fiber membrane bundle 200 is used to convert seawater into water vapor and separate it from ions, achieving seawater desalination. The anode electrode tube 300, membrane electrode assembly 400, and cathode electrode tube 500 disposed within the pipeline complete the electrolysis of the water vapor. The generated hydrogen is transported to the outside through a tube shell 600 and collected by a hydrogen collection device. This hydrogen production device has a tubular structure, using a moisture-permeable hollow fiber membrane bundle to generate steam. Compared to a flat moisture-permeable membrane, this device provides more moisture permeability and increases the moisture permeability. It has a compact structure and can sequentially complete seawater desalination and electrolytic hydrogen production, reducing the device's footprint.

[0045] Example 1

[0046] Reference Figure 1 and Figure 2The tubular PEM electrolysis seawater hydrogen production device in the embodiment of the first aspect of the present application includes an internal support structure 100, a moisture-permeable hollow fiber membrane bundle 200, an anode electrode tube 300, a membrane electrode assembly 400, a cathode electrode tube 500, and a tube shell 600. The internal support structure 100 and tube shell 600 both provide support and protection. The moisture-permeable hollow fiber membrane bundle 200 is used to desalinate seawater and generate water vapor. The anode electrode tube 300, membrane electrode assembly 400, and cathode electrode tube 500 collectively perform electrolysis of the water vapor to produce hydrogen.

[0047] Specifically, refer to Figure 3 and Figure 4 The inner support structure 100 includes an inner support tube 110 and a limiter 120. The side of the inner support tube 110 is hollowed out to allow gas to pass through. The limiter 120 is installed at the end of the inner support tube 110. The limiter 120 is provided with a plurality of limit holes. The moisture permeable hollow fiber membrane tube bundle 200 is composed of a plurality of moisture permeable hollow fiber membrane tubes, which pass through the limiter holes to complete the fixation. It is worth noting that seawater passes through the inside of the moisture permeable hollow fiber membrane tube, and the water vapor of the seawater can diffuse outward through the moisture permeable hollow fiber membrane tube. The tube wall of the moisture permeable hollow fiber membrane tube is a waterproof and breathable membrane, and the material is mainly PTFE and PVDF.

[0048] Furthermore, the materials selected for the inner support structure 100 mainly include rigid materials such as metal materials (including but not limited to stainless steel, titanium alloy, copper alloy, nickel alloy, etc.), inorganic non-metallic materials (including but not limited to glass, ceramic, cement, etc.), organic non-metallic materials (including but not limited to plastic, rubber, etc.). The inner support tube 110 has an inner diameter of 20-50mm, a thickness of 1-3mm, and a height of 100-300mm. The side is a mesh hollow structure, and the size of a single hollow is generally not less than 5×5mm. 2 , hollow partition width 1-3mm.

[0049] Furthermore, threads are provided on the end of the inner support tube 110 and the side of the limiting member 120 , and the limiting member 120 and the inner support tube 110 are connected to each other through the threads, thereby facilitating subsequent disassembly and assembly.

[0050] Furthermore, the moisture permeable hollow fiber membrane tubes in the moisture permeable hollow fiber membrane tube bundle 200 are distributed in an array, and the diameter of a single moisture permeable hollow fiber membrane tube is 1-3 mm, and the tube pore spacing is 2-6 mm.

[0051] The anode electrode tube 300 is sleeved on the outer side of the inner support tube 110 and is made of titanium alloy with a thickness of 0.5-2 mm. Figure 5 The side of the anode electrode tube 300 is hollowed out to allow gas to pass through, and the hollow structure corresponds to the hollow structure of the inner support tube 110.

[0052] Reference Figure 6 The membrane electrode assembly 400 is tubular and is sheathed on the outside of the anode electrode tube 300. The membrane electrode assembly 400 includes an anode catalyst layer 410, a proton exchange membrane 420, and a cathode catalyst layer 430, which are attached in sequence from the inside out. Specifically, the catalyst in the anode catalyst layer 410 is mainly IrO2, which catalyzes the oxidation reaction of water molecules in the electrolysis reaction, decomposing water to produce O2 and H + The proton exchange membrane 420 is made of perfluorosulfonic acid, allowing only water molecules and protons to pass through, transporting protons from the anode to the cathode. The catalyst in the cathode catalyst layer 430 is primarily a Pt / C mixture in a certain ratio, where protons undergo a reduction reaction to synthesize H2.

[0053] The cathode electrode tube 500 is sleeved on the outside of the membrane electrode assembly 400 and is made of titanium alloy with a thickness of 0.5-2 mm. Figure 7 The side of the cathode electrode tube 500 is hollowed out to allow gas to pass through the side. The side is a mesh hollow structure, and the size of a single hollow is generally not less than 1×20mm. 2 , hollow partition width 1-3mm.

[0054] The tube shell 600 is sleeved on the outside of the cathode electrode tube 500, and a gap is left between the tube shell 600 and the cathode electrode tube 500 to allow gas to flow along the tube shell 600. Figure 8 The side of the tube shell 600 is also provided with an air outlet for discharging the produced hydrogen.

[0055] Furthermore, the material of the tube shell 600 is selected from rigid materials such as metal materials (including but not limited to stainless steel, titanium alloy, copper alloy, nickel alloy, etc.), inorganic non-metallic materials (including but not limited to glass, ceramic, cement, etc.), and organic non-metallic materials (including but not limited to plastic, rubber, etc.).

[0056] Furthermore, each component in this tubular PEM electrolysis hydrogen production device is sealed with gaskets or sealing rings to prevent gas-liquid leakage and hydrogen-oxygen mixing. The components fit tightly together, and the internal support structure 100 and the tube shell 600 can withstand the pressure in the sealed environment and provide a certain degree of compression for the internal components.

[0057] Among them, after the seawater is heated (40-80℃), it is passed into the moisture-permeable hollow fiber membrane tube bundle 200. Water vapor enters the electrolysis device through the moisture-permeable hollow fiber membrane tube membrane and electrolysis occurs in the membrane electrode assembly 400. Hydrogen flows out from the side of the cathode electrode tube 500 and flows along the tube shell 600 to the pores for discharge and collection.

[0058] Furthermore, the membrane electrode assembly 400 includes an anode diffusion layer 440, which is disposed between the anode electrode tube 300 and the anode catalyst layer 410. The anode diffusion layer 440 is a titanium mesh, titanium felt, or titanium foam, and serves to collect current, separate water flow and air flow, and provide support.

[0059] Furthermore, the membrane electrode assembly 400 further includes a cathode diffusion layer 450, which is disposed between the cathode catalyst layer 430 and the cathode electrode tube 500. The cathode diffusion layer 450 is made of carbon paper, titanium mesh, titanium felt, or titanium foam, and serves to collect current and promote gas-liquid transfer.

[0060] To prepare the membrane electrode assembly 400, the anode and cathode catalyst slurries must first be prepared. These slurries contain a certain proportion of deionized water, isopropyl alcohol, a perfluorosulfonic acid solution, and a catalyst. The prepared anode and cathode catalyst slurries are then applied to both sides of the proton exchange membrane 420 by spraying or other methods. The anode and cathode catalyst layer materials are then assembled onto the anode and cathode catalyst layers by hot pressing or other methods, completing the membrane electrode assembly 400.

[0061] Furthermore, in this embodiment, an air gap is formed between the moisture-permeable hollow fiber membrane tube bundle 200 and the anode electrode tube 300, and no moisture-absorbing medium is placed therein.

[0062] Furthermore, the tubular PEM electrolysis seawater hydrogen production device also includes a solar panel, a water pump and a voltage stabilizer. The water pump is used to drive seawater into the moisture-permeable hollow fiber membrane tube bundle 200, and the seawater flows through the back of the solar panel. The solar panel can heat the seawater. The voltage stabilizer is electrically connected to the anode electrode tube 300 and the cathode electrode tube 500. The solar panel is electrically connected to the water pump and the voltage stabilizer to provide electrical energy, thereby saving energy consumption.

[0063] Furthermore, the present tubular PEM electrolysis seawater hydrogen production device further comprises a connecting plate 800, referring to Figure 9 There are multiple PEM electrolysis seawater hydrogen production devices and they are all connected to each other through a connecting plate 800.

[0064] The operating principle of this tubular PEM electrolysis hydrogen production system using seawater is as follows: Heated seawater comes into contact with a moisture-permeable hollow fiber membrane bundle 200. Because the water vapor partial pressure on the side of the membrane bundle in contact with the heated seawater is greater than on the electrolyzer side, water vapor, driven by pressure, is transported through the pores of the membrane bundle into the electrolyzer. Inside the electrolyzer, the incoming water vapor is transported through the air gap to the anode side of the membrane electrode. When power is applied to the anode electrode tube 300 and the cathode electrode tube 500, water comes into contact with the anode catalyst and undergoes electrolysis to produce O₂ and H₆. The generated O₂ is discharged from the electrolyzer through the end, while the H₆ is transported to the cathode side of the membrane electrode through the proton exchange membrane 420. Upon contact with the cathode catalyst, the H₆ undergoes a reduction reaction to produce H₂. The generated H₂ passes through the gaps in the cathode electrode tube 500 and is transported outside the electrolyzer for drying and collection.

[0065] In an embodiment of the present application, a method for operating the above-mentioned seawater hydrogen production device using PEM electrolysis includes the following steps:

[0066] S100. Seawater enters the PEM electrolysis seawater hydrogen production device, where the liquid water is isolated in the moisture permeable hollow fiber membrane bundle 200, and water vapor passes through the moisture permeable hollow fiber membrane tube into the device;

[0067] S200. Water vapor flows into the device from the side of the moisture-permeable hollow fiber membrane bundle 200, is transported through the air gap to the anode electrode tube 300 and enters the membrane electrode assembly 400;

[0068] S300. The anode electrode tube 300 and the cathode electrode tube 500 are energized, and water vapor is electrolyzed in the membrane electrode assembly 400;

[0069] S400. The oxygen generated by water vapor electrolysis passes through the anode catalyst layer 410 and returns to the gap between the anode electrode tube 300 and the moisture-permeable hollow fiber membrane bundle 200, and flows out along the pipe to the end;

[0070] S500. The hydrogen generated by water vapor electrolysis enters the gap between the cathode electrode tube 500 and the tube shell 600 through the cathode catalyst layer 430 and flows out along the pipe to the outlet at the end;

[0071] S600. The external hydrogen collection device collects the generated hydrogen to complete the preparation of hydrogen.

[0072] Example 2

[0073] The tubular PEM electrolysis seawater hydrogen production device in this embodiment is the same as that in Example 1, except that a hygroscopic medium 700 is added. The hygroscopic medium 700 is disposed between the fiber membrane bundle 200 and the anode electrode tube 300. The hygroscopic medium 700 is used to absorb water vapor that permeates the moisture-permeable hollow fiber membrane bundle and transfer it to the membrane electrode assembly 400. The hygroscopic medium can improve the moisture permeability and water vapor mass transfer efficiency of the membrane, and a variety of options are available, including but not limited to hydrogels and absorbent sponges.

[0074] The hygroscopic medium 700 in this embodiment utilizes a PAMPs / PAAM hydrogel. First, 4% N,N-methylenebisacrylamide and 0.6% α-ketoglutaric acid are added to 1 mol / L 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and cured under 365 nm ultraviolet light to form the resulting PAMPS hydrogel. 0.1% N,N-methylenebisacrylamide and α-ketoglutaric acid are added to 2 mol / L acrylamide (AAM). The PAMPS hydrogel is allowed to swell for 12 hours and then cured under 365 nm ultraviolet light to form the resulting PAMPs / PAAM hydrogel.

[0075] Reference Figure 10 This embodiment uses a seawater hydrogen production device using tubular PEM electrolysis with a moisture permeability height of 100mm and a moisture permeable hollow fiber membrane bundle positioning plate with a diameter of 20mm as an example. The moisture absorbing medium 700 is placed between the moisture permeable hollow fiber membrane bundle 200 and the anode electrode tube 300. The hot seawater temperature is 60°C. When fresh water is directly introduced without a moisture permeable membrane, the current density is 161mA / cm at a voltage of 2V. 2 If a flat breathable film is used to surround the inner support structure, the breathable area is 62.83cm 2 At 2V, the current density of a single electrolysis device is 36mA / cm 2 When the diameter of the moisture permeable hollow fiber membrane tube is 1mm and the tube hole spacing is 3mm (there are 37 moisture permeable hollow fiber membrane tubes, refer to Figure 11 In a), the moisture permeability area is 116.24 cm 2 The moisture permeability increased by 85% and the current density was 68mA / cm at 2V voltage. 2 When the diameter of the moisture permeable hollow fiber membrane tube is 1mm and the tube hole spacing is 2mm (there are 85 moisture permeable hollow fiber membrane tubes, refer to Figure 11 In b), the moisture permeability area is 267.04 cm 2 The moisture permeability increased by 325% and the current density was 146mA / cm at 2V voltage. 2 , close to the performance of fresh water electrolysis.

[0076] Example 3

[0077] The tubular PEM electrolysis seawater hydrogen production device in this embodiment is the same as that in Example 1, with a moisture permeable hollow fiber membrane bundle 200 having a diameter of 20 mm, a single tube having a diameter of 1 mm, and a tube hole spacing of 3 mm. An air gap and a hygroscopic medium 700 are provided between the fiber membrane bundle 200 and the anode electrode tube 300, wherein the hygroscopic medium is the PAMPs / PAAM hydrogel in Example 2. Hot seawater at 20°C, 40°C, 60°C, and 80°C is introduced respectively, and the electrolysis performance of the device after the hygroscopic medium is added is tested. Figure 12 As the temperature rises, electrolysis performance improves regardless of whether or not hygroscopic medium 700 is added. At lower seawater temperatures (20°C, 40°C), the addition of hygroscopic medium 700 to the device reduces electrolytic hydrogen production performance. However, at higher temperatures (60°C, 80°C), the addition of hygroscopic medium 700 improves performance. When operating at high temperatures, the addition of hygroscopic medium 700 to the tubular PEM electrolysis seawater hydrogen production device improves electrolytic hydrogen production capacity.

[0078] The above is a specific description of the preferred implementation methods of the present application, but the invention is not limited to the embodiments. Those skilled in the art may make various equivalent modifications or substitutions without violating the spirit of the present application. These equivalent modifications or substitutions are all included in the scope defined by the claims of the present application.

Claims

1. A seawater hydrogen production device using tubular PEM electrolysis, characterized in that: include: An inner support structure, comprising an inner support tube and a stopper, wherein the side of the inner support tube is hollowed out to allow gas to pass through, and the stopper is mounted on the end of the inner support tube and has a plurality of stopper holes; A moisture-permeable hollow fiber membrane tube bundle, wherein the moisture-permeable hollow fiber membrane tube bundle is composed of a plurality of moisture-permeable hollow fiber membrane tubes and is disposed in the inner support tube, wherein the moisture-permeable hollow fiber membrane tubes pass through the limiting holes to complete fixation, and seawater passes through the interior of the moisture-permeable hollow fiber membrane tubes, and water vapor of the seawater can diffuse outward through the moisture-permeable hollow fiber membrane tubes; an anode electrode tube, the anode electrode tube being sleeved on the outer side of the inner support tube, and the side of the anode electrode tube being hollowed out to allow gas to pass through; A membrane electrode assembly, the membrane electrode assembly is tubular and is sleeved on the outside of the anode electrode tube, the membrane electrode assembly comprising an anode diffusion layer, an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer and a cathode diffusion layer attached in sequence from the inside out; a cathode electrode tube, the cathode electrode tube being sleeved on the outside of the membrane electrode assembly, the side of the cathode electrode tube being hollowed out to allow gas to pass through; a tube shell, wherein the tube shell is sleeved on the outer side of the cathode electrode tube, and a gap is left between the tube shell and the cathode electrode tube to allow gas to flow along the tube shell; The water vapor of seawater enters the device through the moisture-permeable hollow fiber membrane tube, and the water vapor is electrolyzed in the membrane electrode assembly. Hydrogen flows out from the side of the cathode electrode tube and flows along the tube shell to the air outlet to be collected.

2. The seawater hydrogen production device using tubular PEM electrolysis according to claim 1, characterized in that: The tubular PEM electrolysis seawater hydrogen production device also includes at least one of an air gap and a hygroscopic medium, wherein the air gap or the hygroscopic medium is arranged between the moisture permeable hollow fiber membrane bundle and the anode electrode tube, and the hygroscopic medium is used to absorb water vapor generated from the moisture permeable hollow fiber membrane bundle.

3. The seawater hydrogen production device using tubular PEM electrolysis according to claim 1, characterized in that: The end of the inner support tube and the side surface of the limiting member are both provided with threads, and the limiting member and the inner support tube are connected to each other through the threads.

4. The seawater hydrogen production device using tubular PEM electrolysis according to claim 1, characterized in that: The moisture permeable hollow fiber membrane tubes in the moisture permeable hollow fiber membrane tube bundle are distributed in an array.

5. The tubular PEM electrolysis seawater hydrogen production device according to any one of claims 1 to 4, characterized in that: The PEM electrolysis seawater hydrogen production device also includes a solar panel, a water pump and a voltage regulator. The water pump is used to drive seawater into the moisture-permeable hollow fiber membrane tube bundle. The voltage regulator is electrically connected to the anode electrode tube and the cathode electrode tube. The solar panel is electrically connected to the water pump and the voltage regulator to provide electrical energy.

6. The tubular PEM electrolysis seawater hydrogen production device according to any one of claims 1 to 4, characterized in that: The tubular PEM electrolysis seawater hydrogen production device further includes a connecting plate. There are multiple tubular PEM electrolysis seawater hydrogen production devices, and all are interconnected via the connecting plate.

7. A method for operating the seawater hydrogen production device using tubular PEM electrolysis according to any one of claims 1 to 6, characterized in that: include: Seawater enters the tubular PEM electrolysis seawater hydrogen production device, and its liquid water is isolated in the tube by the moisture permeable hollow fiber membrane tube, and water vapor passes through the moisture permeable hollow fiber membrane tube and enters the interior of the tubular PEM electrolysis seawater hydrogen production device; Water vapor flows from the side of the moisture-permeable hollow fiber membrane tube, passes through the anode electrode tube and enters the membrane electrode assembly; The anode electrode tube and the cathode electrode tube are energized respectively, and water vapor is electrolyzed in the membrane electrode assembly; Oxygen generated by water vapor electrolysis returns through the anode catalyst layer to the gap between the anode electrode tube and the fiber membrane tube bundle, and flows out along the pipeline to the end; The hydrogen generated by water vapor electrolysis enters the gap between the cathode electrode tube and the tube shell through the cathode catalyst layer, and flows out along the pipeline to the gas outlet; The external hydrogen collection device collects the generated hydrogen to complete the preparation of hydrogen.

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