Hydrogen generation device for electrolyzing saline water to generate hydrogen gas

Abstract

Recently, hydrogen energy has been in demand for a green society. However, in hydrogen production by fossil fuel reforming, CO2 is emitted; in hydrogen production by by-product hydrogen, the production amount is small; in the water electrolysis method, the cost is high; and in the electrolysis of salt water, there are problems such as the generation of hydrochloric acid that has an adverse impact on the environment. 【Solution means】It includes a container for storing salt water, a positive electrode and a negative electrode for electrolysis, at least one of the positive electrode or the negative electrode, and a metal member arranged at a predetermined distance apart. The metal member is configured to react with hydrochloric acid generated by the electrolysis to produce hydrogen gas, enabling more hydrogen to be produced, making it possible to use abundant seawater as a raw material for hydrogen production, and also having the effect of removing hydrochloric acid, contributing to the development of a green energy society and a hydrogen society in the future.

Description

Technical Field

[0001] The present invention relates to hydrogen production by electrolyzing brine to produce hydrogen gas.

Background Art

[0002] These days, we have entered an era of decarbonization, and energy systems different from the conventional ones have been devised. Among them is hydrogen energy, and hydrogen stations and the like are becoming more widespread in society.

[0003] As an example of a hydrogen production method, there is fossil fuel reforming. This method is introduced in oil refineries and the like, but there is a problem of discharging CO2 in the production process. Also, as another hydrogen production method, there is by-product hydrogen, but there is a problem that the amount of by-product hydrogen is limited.

[0004] Furthermore, as another hydrogen production method, there is hydrogen production by electrolysis of water. However, since a large amount of electric power is used for hydrogen production, the production cost of hydrogen becomes high. In addition, these days, a solution of applying a magnetic field by a superconducting magnet to the area of electrolysis of an aqueous solution to increase the amount of hydrogen production has also begun to be provided. However, when using a superconducting magnet, there is a problem that the electric power cost and equipment cost further increase.

[0005] And when electrolyzing brine such as seawater, there is also a problem that hydrochloric acid generated accompanying hydrogen production affects the environment.

[0006] Furthermore, on the earth, water exists at about 71%, and about 97% of this water is seawater. There is also a problem that this abundant seawater has not been effectively utilized as a raw material for hydrogen production.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

[0008] In the above Patent Document 1, a hydrogen generation device is provided that uses an easily generated anode and supplies saline such as seawater without desalinating or purifying it for electrolysis, and does not produce harmful by-products such as chlorine. However, there is a problem that there is no method for generating more hydrogen.

[0009] The present invention is a hydrogen generation device that electrolyzes saline to generate hydrogen gas, a container for storing the above saline, a positive electrode and a negative electrode inserted into the saline stored in the container and energized for electrolysis, and in the saline, at least one of the positive electrode or the negative electrode and a metal member arranged at a predetermined distance apart are provided, The metal member is configured to react with hydrochloric acid generated by the electrolysis to generate hydrogen gas. By being a hydrogen generation device characterized by this, it becomes possible to generate more hydrogen. MEANS FOR SOLVING THE PROBLEMS

[0010] A hydrogen generation device that electrolyzes saline to generate hydrogen gas, a container for storing the above saline, a positive electrode and a negative electrode inserted into the saline stored in the container and energized for electrolysis, and in the saline, at least one of the positive electrode or the negative electrode and a metal member arranged at a predetermined distance apart are provided, The hydrogen generation device is characterized in that the metal member is configured to chemically react with hydrochloric acid generated by the electrolysis to generate hydrogen gas, whereby it is possible to generate more hydrogen.

Advantages of the Invention

[0011] A hydrogen generation device for electrolyzing brine to generate hydrogen gas, a container for storing the brine, a positive electrode and a negative electrode inserted into the brine stored in the container for conducting electricity and electrolyzing, in the brine, at least one of the positive electrode or the negative electrode and a metal member arranged at a predetermined distance apart are provided, The hydrogen generation device is characterized in that the metal member is configured to chemically react with hydrochloric acid generated by the electrolysis to generate hydrogen gas, whereby it is possible to generate more hydrogen.

[0012] For the above object, the present invention provides a container for storing brine, a positive electrode and a negative electrode inserted into the brine stored in the container for conducting electricity and electrolyzing, in the brine, at least one of the positive electrode or the negative electrode and a metal member arranged at a predetermined distance apart are provided, The hydrogen generation device is characterized in that the metal member is configured to chemically react with hydrochloric acid generated by the electrolysis to generate hydrogen gas, whereby it is possible to generate more hydrogen.

Brief Description of the Drawings

[0013]

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Mode for Carrying Out the Invention

[0014] Hereinafter, embodiments will be described with reference to the drawings.

[0015] In the description of the drawings, the same reference numerals are given to the same elements, and duplicate descriptions are omitted. Also, the drawings are for the purpose of understanding, and the actual dimensional ratios do not necessarily match the actual ones.

[0016] Also, there may be parts where the dimensional relationships and ratios are different between the drawings.

[0017] Furthermore, the following embodiments illustrate devices and methods for embodying the technical idea of the present invention, and the embodiments of the present invention do not specify the materials, shapes, structures, arrangements, etc. of the components as follows.

[0018] Here, FIG. 1 is a configuration diagram in one embodiment of the present invention.

[0019] Next, FIG. 2 is a top view in one embodiment of the present invention.

[0020] In the electrolysis unit 1, there are a positive electrode 2, a negative electrode 3, and an aluminum plate 4 made of aluminum. Also, the electrolysis unit 1 contains brine 5, and the shape of the electrolysis unit is a rectangular parallelepiped.

[0021] Here, as an example of the brine 5, 100 cc of water at 20°C is used as a solvent, and 20 g of sodium chloride is used as a solute to generate brine 5, that is, an aqueous sodium chloride solution. The aluminum plate 4 is installed so as not to contact the positive electrode 2 and the negative electrode 3.

[0022] Also, here, for comparison, a case where the electrolysis unit 1 does not contain the aluminum plate 4 is also considered.

[0023] At this time, the electrolysis including the aluminum plate 4 is taken as sample 1, and the electrolysis without the aluminum plate 4 is taken as sample 2.

[0024] Furthermore, in the electrolysis, a platinum electrode is used as the electrode, and a voltage of 6V is applied.

[0025] Considering the electrolysis at that time, in the case of sample 1, the following changes occur in the aqueous sodium chloride solution.

[0026] Here, 2NaCl + 2H2O → 2NaOH + Cl2 + H2 As shown in , at the positive electrode 2 of the electrolysis unit 1, chloride ions are oxidized to generate chlorine gas, and at the negative electrode 3, water is reduced to generate hydrogen gas.

[0027] In addition, hydroxide ions are generated near the negative electrode 3. Since sodium ions are attracted to the vicinity of the negative electrode 3, the aqueous solution near the negative electrode 3 becomes an aqueous sodium hydroxide solution as the electrolysis progresses.

[0028] At this time, hydrogen gas can be generated at the negative electrode 3, but the chlorine gas generated at the positive electrode 2 reacts with water to produce hydrochloric acid and hypochlorous acid.

[0029] The hydrochloric acid generated here is an environmental problem, but it reacts with the aluminum plate 4, 2Al + 6HCl → 2AlCl3+ 3H2 as shown in , aluminum chloride and hydrogen are generated. By the reaction of aluminum and hydrochloric acid, more hydrogen can be generated, and furthermore, the hydrochloric acid, which is an environmental problem, can be removed.

[0030] In addition, aluminum reacts with water at room temperature to produce aluminum hydroxide and hydrogen. However, since aluminum is usually covered with aluminum oxide on its surface, the reaction with water does not occur as it is.

[0031] Here, when aluminum oxide is present on the surface of the aluminum plate, in the reaction with hydrochloric acid, Al2O3+ 6HCl → 2AlCl3+ 3H2O as shown in , aluminum chloride and water are generated.

[0032] In this experiment, the aluminum plate 4 is installed so as not to contact the positive electrode 2 and the negative electrode 3. However, in order to prevent a decrease in the efficiency of hydrogen generation due to the collision of gas bubbles generated from the electrodes and gas bubbles generated from the aluminum plate, it is desirable for the aluminum plate 4 to be at a distance of 5 mm or more from the positive electrode 2 and the negative electrode 3.

[0033] Furthermore, while the aluminum plate 4 may cause dissimilar metal contact corrosion by contacting the positive electrode 2 or the negative electrode 3, since the aluminum plate will dissolve in hydrochloric acid or the like, it is considered that dissimilar metal contact corrosion will not become a major problem. Also, although the aluminum plate 4 can be brought into contact with the positive electrode 2 or the negative electrode 3, it is necessary to consider that bubbles generated from the aluminum plate 4, the positive electrode 2, or the negative electrode 3 may collide with each other.

[0034] As described above, due to the reaction between hydrochloric acid and the aluminum plate, aluminum chloride and hydrogen will be generated. Therefore, in addition to the hydrogen generated by electrolysis, more hydrogen can be generated, and furthermore, hydrochloric acid can be removed.

[0035] Furthermore, hydroxide ions are generated near the negative electrode 3. Since sodium ions are attracted near the negative electrode 3, the aqueous solution near the negative electrode 3 will become an aqueous sodium hydroxide solution as electrolysis proceeds. Sodium hydroxide reacts with the aluminum plate 4, 2Al + 6H2O + 2NaOH → 2Na[Al(OH)4] + 3H2 and hydrogen is further generated as shown above. In this reaction case, chlorides related to hydrochloric acid are not generated.

[0036] Next, in the case of Sample 2 which is electrolysis without the aluminum plate 4, a platinum electrode is used as the electrode, and a voltage of 6V is applied to see what happens.

[0037] Considering the electrolysis at that time, in the case of Sample 2, the following changes occur in the aqueous sodium chloride solution.

[0038] Here, 2NaCl + 2H2O → 2NaOH + Cl2 + H2 As shown above, at the positive electrode 2 of the electrolysis section 1, chloride ions are oxidized to generate chlorine gas, and at the negative electrode 3, water is reduced to generate hydrogen gas.

[0039] In addition, although hydroxide ions are generated near the negative electrode 3, since sodium ions are attracted near the negative electrode 3, the aqueous solution near the negative electrode 3 becomes an aqueous sodium hydroxide solution as the electrolysis progresses.

[0040] At this time, although hydrogen gas is being generated at the negative electrode 3 here, the chlorine gas generated at the positive electrode 2 reacts with water to produce hydrochloric acid and hypochlorous acid.

[0041] Here, when comparing Sample 1 and Sample 2, in Sample 2, due to the presence of the aluminum plate 4, hydrogen can be generated and hydrochloric acid can be effectively removed, while in Sample 1, hydrochloric acid cannot be removed.

[0042] Also, when comparing Sample 1 and Sample 2, it was experimentally confirmed that in Sample 1 compared to Sample 2, in an environment of 20 °C, the amount of hydrogen generated can be more than 5% more.

[0043] Furthermore, at this time, in the electrolysis section, by installing a hydrogen storage tank at the upper part of the electrolysis section, it becomes possible to effectively store hydrogen.

[0044] Also at this time, it is also possible to install a plurality of aluminum plates on the positive electrode side, negative electrode side, or between the positive electrode and the negative electrode of the electrolysis section.

[0045] Furthermore, it is also possible to install a metal that dissolves in hydrochloric acid, sodium hydroxide, etc. other than the aluminum plate on the positive electrode side, negative electrode side, or between the positive electrode and the negative electrode of the electrolysis section, and it is also possible to install other metals that dissolve in hydrochloric acid and sodium hydroxide in addition to installing the aluminum plate.

[0046] Here, for example, if a zinc plate made of zinc is installed instead of the aluminum plate, the reaction between the zinc plate and hydrochloric acid is Zn + 2HCl → ZnCl2+ H2 As such, zinc chloride and hydrogen will be produced, and by the reaction of zinc and hydrochloric acid, more hydrogen can be produced, and furthermore, hydrochloric acid, which is an environmental problem, can be removed.

[0047] Also, the reaction of zinc and sodium hydroxide is Zn + 2NaOH + 2H2O → 2Na[Zn(OH)4] +H2 As such, sodium tetrahydroxozincate and hydrogen will be produced, and by the reaction of zinc and sodium hydroxide, more hydrogen can be produced.

[0048] Next, FIG. 3 is a configuration diagram in one embodiment of the present invention.

[0049] In FIG. 3, in the electrolysis unit 1, there are a positive electrode 2, a negative electrode 3, and an aluminum plate 4 made of aluminum. Further, the electrolysis unit 1 contains brine 5. Furthermore, outside the electrolysis unit 1, there is an ultraviolet irradiation device 6, and ultraviolet rays are irradiated from the ultraviolet irradiation device 6 through the electrolysis unit 1 onto the aluminum plate 4.

[0050] Considering the photoelectric effect here, the wavelength for extracting electrons from a substance as the work function is 330 nm or less in the case of aluminum.

[0051] This time, considering the aluminum plate 4, when extracting electrons from magnesium instead of aluminum, the energy is 420 nm or less, 310 nm or less for silver, 290 nm or less for lead, 275 nm or less for tin and zinc, and 270 nm or less for copper and iron.

[0052] Also, when irradiating the aluminum plate 4 with ultraviolet rays having a wavelength of 330 nm or less by the ultraviolet irradiation device 6 which is a light irradiation device from the outside of the electrolysis unit 1, in the portion where ultraviolet rays pass through in the electrolysis unit 1, the transmission of ultraviolet rays can be enhanced by applying ultraviolet transmission glass or the like.

[0053] At this time, the ultraviolet irradiation device 6 irradiates the aluminum plate 4 with the ultraviolet rays that have passed through the electrolysis unit, and electrons are generated in the aluminum plate 4 by the photoelectric effect to perform electrolysis. The electrolysis at this time is taken as sample 3.

[0054] Here, as an example of the brine 5, 100 cc of water at 20°C is used as the solvent, and 20 g of sodium chloride is used as the solute to produce brine, that is, an aqueous sodium chloride solution. As the brine 5, the aluminum plate 4 is installed so as not to contact the positive electrode 2 and the negative electrode 3.

[0055] Furthermore, in the electrolysis, a platinum electrode is used as the electrode, and a voltage of 6 V is applied.

[0056] At this time, hydrogen can be obtained from sample 3. However, compared with sample 1, it was confirmed by experiments that in sample 3 compared with sample 1, in an environment of 20°C, the amount of hydrogen generated can be more than 7% more. However, by changing the size of the portion of the aluminum plate irradiated with ultraviolet rays and the intensity of the ultraviolet rays, it is possible to increase the amount of hydrogen generated.

[0057] Next, FIG. 4 shows a top view showing the position of the aluminum plate of the present invention.

[0058] In FIG. 4, the aluminum plate 4 is installed inside the left side surface of the electrolysis unit 1, and the ultraviolet irradiation device 6 is installed outside the left side surface of the electrolysis unit 1, and has a function of irradiating the aluminum plate 4 with ultraviolet rays through the left side surface portion of the electrolysis unit 1.

[0059] Furthermore, at this time, by applying ultraviolet transmission glass or the like to the left side surface portion of the electrolysis unit 1 through which ultraviolet rays pass, the transmission of ultraviolet rays can be enhanced.

[0060] Furthermore, for the ultraviolet-transmitting glass, it is effective to suppress the mixing of impurities such as iron oxide to 0.01% or less and increase the ultraviolet transmittance. It can be applied to the entire surface of the electrolysis unit 1, or the entire left side surface through which ultraviolet rays pass, or specific parts of the left side surface through which ultraviolet rays pass.

[0061] Also, when the aluminum plate 4 is adsorbed inside the left side surface of the electrolysis unit 1, ultraviolet rays pass through the left side surface of the electrolysis unit 1 and irradiate the aluminum plate without passing through the brine. Regarding the electrons generated by the photoelectric effect on the aluminum surface irradiated with ultraviolet rays, it is possible to generate electrons from multiple aspects including the surface opposite to the aluminum surface irradiated with ultraviolet rays.

[0062] Here, an example where the aluminum plate 4 is installed inside the left side surface of the electrolysis unit 1 is described. However, it is also possible to install the aluminum plate 4 inside the right side surface, the front surface, the back surface, or the bottom surface of the electrolysis unit 1 and irradiate the aluminum plate 4 with the ultraviolet irradiation device. Also, when the shape of the electrolysis unit is not a rectangular parallelepiped and the shape seen from above is circular, it is also possible to install it inside the circular part of the electrolysis unit.

[0063] Also, in this example, aluminum is used. However, instead of aluminum, other metals such as magnesium, silver, lead, tin, zinc, copper, and iron can be used, and electrons can be generated by irradiating ultraviolet rays, X-rays, gamma rays, etc. corresponding to the photoelectric effect, thereby increasing the production of hydrogen.

[0064] Furthermore, in this example, brine is used. However, in electrolysis using liquids other than brine, it is also possible to increase the amount of hydrogen produced by generating electrons through the photoelectric effect.

[0065] Furthermore, ultraviolet rays can be classified into three types: ultraviolet A (UVA) with a wavelength of 315 nm to 400 nm, ultraviolet B (UVB) with a wavelength of 280 nm to 315 nm, and ultraviolet C (UVC) with a wavelength of 200 nm to 280 nm. However, when the object irradiated with ultraviolet rays is not aluminum but other metals, it is possible to select ultraviolet A, ultraviolet B, or ultraviolet C according to the characteristics of the photoelectric effect of the metal, or it is possible to select ultraviolet rays of a specific wavelength.

[0066] Furthermore, at this time, X-rays, gamma rays, etc., which are electromagnetic waves with wavelengths shorter than ultraviolet rays, can also be used. As a light irradiation device instead of the ultraviolet irradiation device, it is also possible to use an X-ray irradiation device or a gamma-ray irradiation device.

[0067] Furthermore, considering electrolysis outdoors, it is also possible to use sunlight including ultraviolet rays, X-rays, gamma rays, etc., and the heating effect due to the heat of sunlight can also be obtained additionally.

[0068] Also, in FIG. 3, the ultraviolet irradiation device 6 is provided outside the electrolysis unit 1, but the ultraviolet irradiation device 6 may also be provided inside the electrolysis unit 1.

[0069] Furthermore, one or more ultraviolet irradiation devices may be installed only outside the electrolysis unit 1, one or more may be installed only inside the electrolysis unit 1, or one or more may be installed both outside and inside the electrolysis unit 1.

[0070] At this time, when installing a plurality of ultraviolet irradiation devices, it is also possible to select each ultraviolet irradiation device with a different wavelength of the radiated ultraviolet rays, and it is also possible to select X-rays, gamma rays, etc., which are electromagnetic waves with wavelengths shorter than ultraviolet rays.

[0071] Here, the magnetic treatment of brine will be described. In this evaluation, 100 cc of water at 20°C without magnetic treatment is used as a solvent, and 20 g of sodium chloride is used as a solute to generate brine, that is, an aqueous sodium chloride solution, as a comparative sample.

[0072] On the other hand, regarding the case of generating salt water, i.e., an aqueous sodium chloride solution, using 100 cc of water at 20°C without magnetic treatment as a solvent and 20 g of sodium chloride as a solute, the means for performing magnetic treatment will be described with examples.

[0073] Figure 5 shows the neodymium magnet 7 used for magnetic treatment of salt water in this case. The physical dimensions are 50 mm and 10 mm respectively from the long side, and the thickness is 3 mm, and it is made of N40 material.

[0074] In addition, since the salt water will pass through the surface of this neodymium magnet 7, in order to prevent contamination of the surface of the neodymium magnet, it is also possible to prevent direct surface contamination of the neodymium magnet by covering the surface of the neodymium magnet with a thin film that allows magnetic flux to pass through easily.

[0075] As shown in Figure 6, four of these neodymium magnets 7 are arranged in the direction of attracting each other by magnetic force in the direction of the surface composed of the 10 - mm side and the 3 - mm side, and the four neodymium magnets are adsorbed by magnetic force.

[0076] At this time, if the upper surface of the neodymium magnet located at one end is the S - pole and the lower surface is the N - pole, then the adjacent neodymium magnet has the upper surface as the N - pole and the lower surface as the S - pole, the further adjacent neodymium magnet has the upper surface as the S - pole and the lower surface as the N - pole, and the neodymium magnet located at the other end of the further adjacent one has the upper surface as the N - pole and the lower surface as the S - pole.

[0077] Furthermore, prepare a plastic spacer for preventing adsorption between magnets as shown in Figure 7. The physical dimensions of this plastic spacer are 40 mm and 5 mm respectively from the long side, and the thickness is 1 mm.

[0078] Next, place two plastic spacers in FIG. 7 on the surfaces of the four adsorbed neodymium magnets in FIG. 6. At this time, the long sides of the two plastic spacers and the long sides of each of the four neodymium magnets are arranged at right angles. Further, place the two plastic spacers at both ends of the four neodymium magnets and mount them in a state to form a crossbeam, as shown in FIG. 8.

[0079] Furthermore, prepare four adsorbed neodymium magnets in the same state as in FIG. 6.

[0080] Place four newly prepared neodymium magnets adsorbed on the surfaces of the two plastic spacers in FIG. 8 in the Z-axis direction where the adsorption is strongest with respect to the four adsorbed neodymium magnets at the bottom.

[0081] Also, mount them such that the long sides of the four neodymium magnets at the bottom are parallel to the long sides of the four neodymium magnets at the top.

[0082] At this time, the two plastic spacers are located at both ends of the four neodymium magnets at the bottom and the four neodymium magnets at the top. FIG. 9 shows an example of mounting eight neodymium magnets used for magnetic treatment of salt water in this state.

[0083] At this time, if one of the neodymium magnets located at one end of the four neodymium magnets on the lower side has an S pole on the upper surface and an N pole on the lower surface, the adjacent neodymium magnet has an N pole on the upper surface and an S pole on the lower surface, the further adjacent neodymium magnet has an S pole on the upper surface and an N pole on the lower surface, and the neodymium magnet located at the other end of the further adjacent one has an N pole on the upper surface and an S pole on the lower surface.

[0084] Among the four upper neodymium magnets, the neodymium magnet located at one end of the four upper neodymium magnets, which is opposite to the neodymium magnet located at one end of the four lower neodymium magnets, has an S pole on the upper surface and an N pole on the lower surface. The adjacent neodymium magnet has an N pole on the upper surface and an S pole on the lower surface. The further adjacent neodymium magnet has an S pole on the upper surface and an N pole on the lower surface. The neodymium magnet located at the other end of the further adjacent one has an N pole on the upper surface and an S pole on the lower surface.

[0085] Furthermore, in the same manner as described above, a state diagram with 16 neodymium magnets mounted is shown in FIG. 10. In the state where these 16 neodymium magnets are mounted, 6 plastic spacers are used, and there are 3 pairs of plastic spacers at the same height position in the Z direction. There are a total of 3 spaces 9 between the 3 pairs of plastic spacers and the neodymium magnets.

[0086] Here, an example of performing the magnetization treatment of saline will be described in further detail.

[0087] Here, in the 3 spaces 9 between the plastic spacers, considering an even flow rate of saline, 100 cc of water at 20 °C that has not been magnetically treated, which was described above, is used as a solvent, and 20 g of sodium chloride is used as a solute to generate saline, that is, an aqueous sodium chloride solution. This saline is passed through over 60 seconds, and the saline is collected.

[0088] The collected saline is passed through the 3 spaces 9 between the plastic spacers again in the same manner, considering an even flow rate of saline, over 60 seconds, and collected again.

[0089] By repeating this same method a total of 10 times, the magnetization treatment of saline can be carried out to obtain magnetically treated saline.

[0090] Also, by strengthening the magnetic force of the neodymium magnets or by methods such as increasing the amount of neodymium magnets, it is also possible to relax the conditions for the passage of saline.

[0091] For example, when passing salt water through the three spaces existing there by arranging 10 out of 16 neodymium magnets in the series direction as described in FIG. 10, it is also possible to relax the number of times of passing of the salt water, such as to 1 / 10.

[0092] Here, when magnetizing the salt water, consideration is given to achieving a uniform salt water flow rate in the three spaces 9, and the salt water is passed through over 60 seconds. This is for quantitative data collection. From the perspective of increasing the amount of hydrogen generated, it is not necessarily required to have a uniform salt water flow rate, nor is it necessarily required to pass the salt water through over 60 seconds, and the number of times does not necessarily have to be 10 times.

[0093] Salt water without magnetic treatment and salt water with magnetic treatment as described above were obtained. Electrolysis was respectively carried out using these salt waters, and the amounts of hydrogen generated were compared.

[0094] In the electrolysis, a platinum electrode was used as the electrode, and a voltage of 6V was applied.

[0095] As a result, it was experimentally confirmed that the amount of hydrogen generated by electrolysis using salt water with magnetic treatment was 10% or more more than the amount of hydrogen generated by electrolysis using salt water without magnetic treatment.

[0096] In addition, in another experimental method, a plurality of neodymium magnets were installed in the electrolysis section, and electrolysis was carried out using salt water without magnetic treatment. However, no obvious superiority was found in the amount of hydrogen generated by electrolysis when the neodymium magnets were installed in the electrolysis section compared to when they were not installed.

[0097] However, in this case, an experimental evaluation was carried out with neodymium magnets installed in the electrolysis section, and there remains a possibility that the amount of hydrogen generated can be increased by applying a stronger magnetic field.

[0098] On the other hand, there is also a method of increasing the amount of hydrogen generated by providing an extremely expensive superconducting magnet or the like in the electrolysis section. However, introducing a superconducting magnet has problems in that a large amount of electric power is required for magnetic force generation and the installation cost is also enormous.

[0099] Therefore, the hydrogen generation system that uses magnetically treated brine at a commercially available level of neodymium magnets, which has been described so far, can increase the amount of hydrogen generated and also has great cost advantages.

[0100] Next, FIG. 11 is a configuration diagram of an embodiment of the present invention.

[0101] Here, when hydrogen is generated, in the electrolysis section 1, it is also possible to make the bottom surface 10 of the electrolysis section inclined with a gradient and utilize gravity to facilitate the collection of precipitates due to electrolysis.

[0102] At this time, since aluminum chloride and the like have a solubility in water that is determined depending on the temperature, precipitated substances that cannot be dissolved can be collected. When the gradient is 50° or more, the effect of collecting precipitates becomes greater.

[0103] Next, FIG. 12 is a configuration diagram of an embodiment having a filter section of the present invention, and it has a filter section in the front stage of the electrolysis section.

[0104] In the present invention, when electrolyzing brine such as seawater, a method of increasing hydrogen generation by adding an aluminum plate is provided. However, since seawater contains various impurities, filtration is required when actually using seawater.

[0105] On the other hand, since seawater is highly corrosive and may contain various organisms, it is necessary to select a filtration device that can cope with a severe environment.

[0106] As a filtration device capable of coping with such a situation, an auto strainer for seawater, sand filtration, a disk filter, etc. can be applied.

[0107] By providing a filter unit having such a filtration function in front of the electrolysis unit, various impurities can be effectively removed from seawater, etc. by filtration of the filter unit before performing electrolysis of brine.

[0108] Next, FIG. 13 is a configuration diagram in one embodiment having an ion exchange membrane of the present invention.

[0109] The electrolysis unit 1 has an ion exchange membrane 12 in a form that partitions the liquid on the positive electrode side and the liquid on the negative electrode side, and shows a case where the aluminum plate 4 is installed on the positive electrode side.

[0110] If, by chance, this ion exchange membrane 12 is a cation exchange membrane, the space between the positive electrode 2 and the negative electrode 3 will be partitioned by a cation exchange membrane that only allows cations to pass through, and cations such as sodium ions can be moved, and anions can be prevented from moving.

[0111] Also, if, by chance, this ion exchange membrane 12 is an anion exchange membrane, the space between the positive electrode 2 and the negative electrode 3 will be partitioned by an anion exchange membrane that only allows anions to pass through, and anions can be moved, and cations can also be prevented from moving.

[0112] At this time, consider the case where the space between the positive electrode and the negative electrode is partitioned by a cation exchange membrane that only allows cations to pass through, and the aluminum plate 4 is installed on the positive electrode side, and an aqueous sodium chloride solution is added to the positive electrode side and a diluted aqueous sodium hydroxide solution is added to the negative electrode side.

[0113] In this case, during electrolysis, hydroxide ions are generated near the negative electrode 3. Since sodium ions are attracted to the vicinity of the negative electrode 3, the aqueous solution near the negative electrode 3 becomes an aqueous sodium hydroxide solution as electrolysis progresses.

[0114] Furthermore, by means of the cation exchange membrane installed in the electrolysis section, cations such as sodium ions can be moved from the positive electrode side to the negative electrode side, combine with the hydroxide ions generated near the negative electrode 3, and it becomes possible to further generate sodium hydroxide.

[0115] Also at this time, if there are cations such as aluminum ions on the positive electrode side, cations such as aluminum ions may move from the positive electrode side to the negative electrode side through the cation exchange membrane and react with sodium hydroxide. In this case, Al 3+ + 3NaOH → 3Na + + Al(OH)3 aluminum hydroxide will be produced as follows.

[0116] Furthermore, when an excessive amount of sodium hydroxide is added to the negative electrode side of the electrolysis section, the precipitate of aluminum hydroxide dissolves to form a colorless aqueous solution, generating tetrahydroxoaluminate ions. However, aluminum hydroxide will not dissolve if an excessive amount of sodium hydroxide is not added.

[0117] Thus, when a cation exchange membrane is provided in the electrolysis section, the effect of being able to further generate sodium hydroxide can also be obtained.

[0118] Also, in this example, the aluminum plate 4 is installed on the positive electrode side, but it is also possible to install the aluminum plate 4 on the negative electrode side, and furthermore, it is also possible to install the aluminum plate 4 on both the positive electrode side and the negative electrode side.

[0119] Furthermore, although an example with one cation exchange membrane installed is described here, it is also possible to install both a cation exchange membrane and an anion exchange membrane simultaneously in the electrolysis section.

[0120] Next, FIG. 14 is a configuration diagram of one embodiment having a warming treatment section of the present invention, and a warming treatment section is provided in the front stage of the electrolysis section.

[0121] Here, an example of the warming treatment will be described.

[0122] In the experiment, the hydrogen generation situation due to the difference in temperature in brine was confirmed. Here, an example will be described in which the hydrogen generation amount by electrolysis was experimentally evaluated when the brine was at 20°C, 30°C, and 40°C.

[0123] In the electrolysis, a platinum electrode was used as the electrode, and a voltage of 6V was applied.

[0124] As a result, it was confirmed that the amount of hydrogen generated by electrolysis was about 50% more when the brine was at 30°C compared to the amount of hydrogen generated by electrolysis using normal-temperature brine at 20°C.

[0125] Also, it was confirmed that the amount of hydrogen generated by electrolysis was about 80% more when the brine was at 40°C compared to the amount of hydrogen generated by electrolysis using normal-temperature brine at 20°C.

[0126] From the above, by heating the brine, it becomes possible to increase the amount of hydrogen generated by electrolysis.

[0127] Regarding the heating temperature, although the experimental results at 20°C, 30°C, and 40°C are shown here, heating to other temperatures such as a higher temperature is also possible in terms of the mechanism.

[0128] Furthermore, as the warming treatment, heating by a heater or the like is possible. Also, when using seawater as the salt water, a configuration of warming treatment by sunlight during the day existing in nature is also possible. When heating by sunlight, the electricity cost of a heater or the like is not required, and an inexpensive system can be constructed.

[0129] Thus, by providing a warming treatment unit having a heating function by a heater, sunlight, or the like in the stage before the electrolysis unit or inside the electrolysis unit, it becomes possible to heat the salt water before or during the electrolysis of the salt water, without emitting carbon dioxide, and to produce more hydrogen.

[0130] Next, the usefulness and precautions of liquid stirring will be described.

[0131] In the electrolysis unit, as an example, an automatic stirrer such as a propeller type is provided, and stirring is performed by the automatic stirrer to equalize the concentration and temperature of the salt water. Then, by electrolyzing the stirred salt water, it becomes possible to produce more hydrogen without emitting carbon dioxide.

[0132] However, in the electrolysis unit, by providing a stirring unit having a stirring function for the salt water, it becomes possible to produce more hydrogen without emitting carbon dioxide. However, since there is a possibility that precipitates such as aluminum chloride may diffuse, care is required when applying.

[0133] Next, FIG. 15 is a configuration diagram of an embodiment having an aluminum plate supply unit of the present invention, and an aluminum plate supply unit 14 is provided on the right side surface of the electrolysis unit.

[0134] At this time, the aluminum plate supply unit 14 has a function of not leaking the liquid inside the electrolysis unit to the outside of the electrolysis unit, and further has a function of supplying the aluminum plate 4 to the electrolysis unit 1.

[0135] Considering that the salt water is electrolyzed at this time, 2NaCl + 2H2O → 2NaOH + Cl2+ H2 As shown in , at the positive electrode 2 of the electrolysis unit 1, chloride ions are oxidized to generate chlorine gas, and at the negative electrode 3, water is reduced to generate hydrogen gas.

[0136] In addition, hydroxide ions are generated near the negative electrode 3. Since sodium ions are attracted to the vicinity of the negative electrode 3, the aqueous solution near the negative electrode 3 becomes an aqueous sodium hydroxide solution as the electrolysis progresses.

[0137] At this time, hydrogen gas is being generated at the negative electrode 3. The chlorine gas generated at the positive electrode 2 reacts with water to produce hydrochloric acid and hypochlorous acid.

[0138] The hydrochloric acid generated here reacts with the aluminum plate 4, 2Al + 6HCl → 2AlCl3+ 3H2 and aluminum chloride and hydrogen are produced as shown in . Thus, it becomes possible to generate more hydrogen, and furthermore, hydrochloric acid can be removed.

[0139] Here, by supplying the necessary amount of the aluminum plate that can remove the amount of hydrochloric acid generated from the aluminum plate supply unit 14 to the electrolysis unit 1, the generated hydrochloric acid can be effectively removed.

[0140] In addition to hydrochloric acid, it is also possible to adjust the necessary amount for the reaction of the aluminum plate supplied from the aluminum plate supply unit 14 in consideration of reacting the substances generated by electrolysis with the aluminum plate through calculation.

[0141] Here, an example in which the aluminum plate supply unit 14 is installed on the right side surface of the electrolysis unit is described. However, the aluminum plate supply unit 14 can also be installed on the left side surface, the front surface, the back surface, etc. of the electrolysis unit 1. Also, even when the shape of the electrolysis unit is not a rectangular parallelepiped and the upper surface shape is circular, it is possible to install the aluminum plate supply unit.

[0142] Furthermore, in the supply of the aluminum plate, the aluminum plate can be supplied by horizontal supply, supply from the lower diagonal direction, supply from the upper diagonal direction, supply from the right diagonal direction, or supply from the left diagonal direction, etc.

[0143] Also, although an aluminum plate is being supplied here, circular rod-shaped aluminum, elliptical rod-shaped aluminum, aluminum foil, etc. can also be supplied.

[0144] Furthermore, in order to increase the surface area of the aluminum plate and make the reaction with hydrochloric acid, etc. more active, it is also effective to provide unevenness, etc. on the surface of the aluminum plate.

[0145] Furthermore, at this time, the aluminum plate supply part 14 is in one place, but supply from two or more locations is also possible.

[0146] And in this case, an aluminum plate is being supplied from the aluminum plate supply part, but supply with a metal other than the aluminum plate can also be substituted, and in addition to the aluminum plate, supply of a metal other than the aluminum plate is also possible.

[0147] Next, Fig. 16 is a configuration diagram of one embodiment having the aluminum plate supply part of the present invention. The aluminum plate supply part 14 is provided on the left side surface of the front of the electrolysis part, and an ultraviolet irradiation device 6 is provided outside the left side surface.

[0148] At this time, the aluminum plate supply part 14 has a function of not leaking the liquid inside the electrolysis part to the outside of the electrolysis part, and furthermore has a function of supplying the aluminum plate 4 to the electrolysis part 1.

[0149] Also, the ultraviolet irradiation device 6 has a function of irradiating ultraviolet rays through the left side surface of the electrolysis part 1 toward the left side surface of the aluminum plate 4 supplied from the aluminum plate supply part 14 to the electrolysis part 1.

[0150] Considering the photoelectric effect here, the wavelength for extracting electrons from a substance as the work function is 330 nm or less in the case of aluminum.

[0151] This time, the aluminum plate 4 is considered. However, when extracting electrons from magnesium instead of aluminum, the energy is 420 nm or less, for silver it is 310 nm or less, for lead it is 290 nm or less, for tin and zinc it is 275 nm or less, and for copper and iron it is 270 nm or less.

[0152] Also, when irradiating the aluminum plate 4 with ultraviolet light having a wavelength of 330 nm or less from the ultraviolet light irradiation device 6 from the outside of the electrolysis unit 1, in the portion where the ultraviolet light passes through in the electrolysis unit 1, the transmission of ultraviolet light can be enhanced by applying ultraviolet-transmitting glass or the like.

[0153] At this time, the ultraviolet light transmitted through the left side surface of the electrolysis unit 1 by the ultraviolet light irradiation device 6 is irradiated onto the aluminum plate 4, and electrons can be generated in the aluminum plate 4 by the photoelectric effect to perform electrolysis.

[0154] Furthermore, at this time, the ultraviolet light irradiation device 6 has been described with an example in which ultraviolet light is irradiated through the left side surface of the electrolysis unit 1 toward the left side surface of the aluminum plate 4 supplied from the aluminum plate supply unit 14 to the electrolysis unit 1. However, by irradiating the ultraviolet light toward a portion of the left side surface of the aluminum plate 4 that does not enter the electrolysis unit 1, electrons are generated from various parts of the aluminum plate by the photoelectric effect, which is effective for electrolysis.

[0155] As described above, in the hydrogen generation device of the present invention that electrolyzes salt water to generate hydrogen gas, a container for storing salt water, a positive electrode and a negative electrode inserted into the salt water stored in the container and energized to perform electrolysis, and in the salt water, at least one of the positive electrode or the negative electrode and a metal member disposed at a predetermined distance apart from each other are provided. The hydrogen generation device is characterized in that the metal member is configured to chemically react with hydrochloric acid generated by the electrolysis to generate hydrogen gas. By this, it becomes possible to generate more hydrogen, it is also possible to use abundant seawater as a raw material for hydrogen generation, and it also has the effect of removing hydrochloric acid, which is a technology that can contribute to the development of a future green energy society and hydrogen society.

Industrial Applicability

[0156] In the hydrogen generation device of the present invention that electrolyzes salt water to generate hydrogen gas, it becomes possible to generate more hydrogen, it is also possible to use abundant seawater as a raw material for hydrogen generation, and it also has the effect of removing hydrochloric acid, which is a technology that can contribute to the development of a future green energy society and hydrogen society.

Explanation of Reference Numerals

[0157] 1 ··· Electrolysis section 2 ··· Positive electrode 3 ··· Negative electrode 4 ··· Aluminum plate 5 ··· Salt water 6 ··· Ultraviolet irradiation device 7 ··· Neodymium magnet 8 ··· Plastic spacer 9 ··· Three spaces 10 ··· Bottom surface of the electrolysis section 11 ··· Filter section 12 ··· Ion exchange membrane 13 ··· Warm water treatment section 14 ··· Aluminum plate supply section

Claims

1. A hydrogen generation device for electrolyzing brine to generate hydrogen gas, comprising: a container for storing the brine; a positive electrode and a negative electrode inserted into the brine stored in the container for electrolyzing by passing an electric current; in the brine, at least one of the positive electrode or the negative electrode and a metal member disposed at a predetermined distance apart from the electrode; The hydrogen generation device, wherein the metal member is configured to react with hydrochloric acid generated by the electrolysis to generate hydrogen gas.

2. The metal member generates a metal chloride by the chemical reaction with the hydrochloric acid, The hydrogen generation device according to claim 1, wherein the metal member is configured to be continuously supplied into the brine from the outside of the container to supplement the metal member that has disappeared by the chemical reaction.

3. The hydrogen generation device further comprises a light irradiation device for irradiating light on the surface of the metal member in the container to emit electrons from the surface of the metal member, When the positive electrode and the negative electrode are energized for electrolysis, the light irradiation device is configured to irradiate light on the surface of the metal member, The hydrogen generation device according to claim 1, wherein the wavelength of the light emitted from the light irradiation device corresponds to a wavelength having energy equal to or higher than the work function required to emit electrons from the surface of the metal member.

4. The metal member has a plate-like or rod-like shape, The surface of the metal member is in close contact with the inner wall surface of the container, and the back surface facing the surface is disposed so as to be exposed in the brine, The hydrogen generation device according to claim 3, wherein the surface of the metal member is irradiated with light.

5. The metal member is movably attached while being in close contact with the inner wall surface of the container, The hydrogen generation device according to claim 4, wherein the metal member is configured to be continuously supplied into the brine from the outside of the container to supplement the metal member that has disappeared by the chemical reaction.

6. A hydrogen generation method for electrolyzing brine to generate hydrogen gas, comprising: a container for storing the brine; a positive electrode and a negative electrode inserted into the brine stored in the container for electrolyzing by passing an electric current; The brine is provided with at least one of the positive electrode or the negative electrode, and a metal member disposed at a predetermined distance from the electrode. The metal member is configured to react chemically with hydrochloric acid generated by the electrolysis to produce hydrogen gas. A method for producing hydrogen, characterized by this.

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