JP6165556B2 - Hydrogen production equipment - Google Patents

Description

  The present invention relates to an apparatus for generating hydrogen using water, a photocatalyst, and light.

Currently, hydrogen is used in a wide variety of fields including petroleum refining, chemical products, industrial products, and fuel cells. In particular, a fuel cell using hydrogen is expected as a clean energy source in which only water is generated in the reaction process. However, since hydrogen hardly exists in nature, it is artificially produced by methods such as steam reforming, partial reforming and catalytic reforming using fossil fuels, methods for separating hydrogen from coke oven gas, and electrolysis of water. Are manufactured. Since these hydrogen production methods involve combustion of fossil fuels and a large amount of CO ₂ emission, there is a problem that the environmental load is large.

On the other hand, as a hydrogen generation method with low fossil fuel combustion and CO ₂ emissions, as in Patent Document 1, water is brought into contact with the surface of the photocatalyst and the surface of the photocatalyst is irradiated with light having a wavelength and intensity necessary for the photocatalytic action. Thus, a method for decomposing water and generating hydrogen and oxygen has also been proposed.

JP 2009-262071 A

  The amount of hydrogen generated in a hydrogen generator using a photocatalyst depends on the surface area of the photocatalyst in addition to the wavelength and intensity of light and the efficiency of the photocatalyst. The larger the area of the photocatalyst that is in contact with water and irradiated with light, the more hydrogen is generated.

  Moreover, in order to irradiate the photocatalyst in contact with water with light from the light source, it is necessary to irradiate light through the water tank in which water and the photocatalyst are accommodated, but the light is reflected by the wall surface of the water tank, There is a problem that the amount of light reaching the water and the photocatalyst in the water tank decreases.

  The objective of this invention is providing the hydrogen production apparatus which can irradiate light effectively on the surface of the photocatalyst which has a complicated structure.

  In order to achieve the above object, the hydrogen production apparatus of the present invention accommodates a hydrogen generation tank, a photocatalyst tank for storing a photocatalyst and water, and a liquid light source by separating an internal space of the hydrogen generation tank. And a separation unit that separates the light source tank. The separation unit is made of a material that transmits light emitted from a liquid light source. An uneven shape is formed on at least one surface of the separation part, and the diameter of the unevenness is larger than the wavelength of light emitted from the liquid light source.

  In the present invention, since the uneven shape on the surface of the separation part prevents reflection of light from the light source, the light irradiated from the liquid light source can pass through the separation part with high efficiency. As a result, the surface of the photocatalyst in the hydrogen generation tank can be irradiated with a large amount of light, and the hydrogen generation efficiency can be improved.

The block diagram which shows the hydrogen production apparatus of this invention. (A)-(c) Sectional drawing of the isolation | separation part 5 of this invention. The block diagram which shows the hydrogen production apparatus of this invention. The notch sectional drawing of the hydrogen generator of 2nd Embodiment. (A)-(c) Sectional drawing which shows the manufacturing process of the unevenness | corrugation of the isolation | separation part 5, (d) and (e) The top view of the resist pattern 71. FIG.

  Hereinafter, a hydrogen production apparatus according to an embodiment of the present invention will be described in detail.

  As shown in FIG. 1, the hydrogen production apparatus of the present invention has a hydrogen generation tank 10, a photocatalyst tank 1 that contains the photocatalyst 20 and water 40 by separating the internal space of the hydrogen generation tank 10, and a liquid state And a separation unit 5 that separates the light source tank 2 that houses the light source 30. The separation unit 5 is made of a material that transmits light emitted from the liquid light source 30. The light emitted from the liquid light source 30 passes through the separation unit 5 and enters the photocatalyst tank 1, and the photocatalyst irradiated with the light decomposes water to generate hydrogen.

  An uneven shape is formed on at least one surface of the separating portion 5 as shown in FIGS. 2 (a) to 2 (c). The diameter of the unevenness 51 is larger than the wavelength of light emitted from the liquid light source 30.

  In this way, in the present invention, the unevenness 51 on the surface of the separation unit 5 prevents reflection of light emitted from the liquid light source 30 in each direction, so that the light emitted from the liquid light source is highly efficient. Can pass through the separator 5. Thereby, light can be irradiated to the surface of the photocatalyst 20 of the hydrogen generation tank 10 while suppressing light loss, and hydrogen generation efficiency can be improved.

  As for the shape of the said unevenness | corrugation 51, it is desirable to form in the at least one surface of the isolation | separation part 5 without a gap. By providing the unevenness 51 on at least one surface of the separation part 5 without a gap, a plane parallel to the main plane of the separation part 5 can be reduced. Thereby, the ratio that the light incident on the separation unit 5 from the liquid light source 30 at a random angle is totally reflected on the surface of the separation unit 5 can be reduced, and the rate of transmission through the separation unit 5 can be increased. The shape of the unevenness 51 is more preferable when it is composed only of a surface inclined to the main plane of the separating portion as shown in FIGS. 2 (a) and 2 (b), for example.

  As shown in FIG. 3, the separation unit 5 desirably forms a flow path for flowing the liquid light source 30. Thereby, since the liquid light source 30 can flow through the flow path formed by the separation unit 5, even when the liquid light source 30 having a short light emission lifetime is used, the photocatalyst 20 can always be irradiated with light. And the generation efficiency of hydrogen can be increased.

  As the liquid light source 30, a light source containing any one of a luminescent organism dispersed in a liquid, a phosphorescent material dispersed in a liquid, and a chemiluminescent solution can be used. As the luminescent organism, one containing at least one of luminescent bacteria and luminescent plankton can be used.

  The photocatalyst 20 can be disposed on the inner wall of the photocatalyst tank 1 of the hydrogen generation tank. As shown in FIG. 3, the photocatalyst 20 can be configured to be carried on an adherend 160 that is fixed to the inner wall of the photocatalyst tank 1 and has unevenness. Moreover, the surface area of the photocatalyst can be increased by forming irregularities on the inner wall of the photocatalyst tank 1. The unevenness of the inner wall of the photocatalyst tank 1 can be made particularly large by making the unevenness of the inner wall of the photocatalyst tank 1 into a pleated unevenness, for example, an unevenness of an intestine of an animal. The photocatalyst may include two types of photocatalyst for hydrogen generation and photocatalyst for oxygen generation.

  Further, as the photocatalyst 20, as shown in FIG. 1, a particulate material can be used and dispersed in the water 40.

  As shown in FIG. 3, the hydrogen generation tank 10 is generated inside an inlet 50 a that takes in the liquid light source 30 from the outside into the light source tank 2, and an outlet 50 b that flows out of the liquid light source 30 in the light source tank 2. It is possible to have a structure having a hydrogen outlet for taking out the hydrogen that has been discharged to the outside.

  In addition, as shown in FIG. 4, the hydrogen production apparatus may be configured to further include an adjustment tank 111 that adjusts the liquid light source 30 to a state capable of emitting light and flows into the inlet 50 a of the hydrogen generation tank 10. it can. When the liquid light source 30 is a luminescent organism dispersed in a liquid, the adjustment tank 111 may include a culture tank 102 for cultivating the luminescent organism.

  Since some liquid light sources 30 emit light upon receiving a stimulus, a stimulus is generated in the light source tank 2 by applying chemical, physical or electrical stimulation to the liquid light source 30 to emit light. Parts may be arranged. Specifically, a stirrer that stirs the liquid light source 30, a heating device that heats the liquid light source, a voltage application device that applies electrical stimulation, or the like can be disposed as the stimulus generator.

(First embodiment)
Hereinafter, an example of the hydrogen production apparatus of the first embodiment will be described more specifically with reference to FIG.

  The hydrogen production apparatus of FIG. 3 is provided with a flow path 50 through which a liquid light source (hereinafter referred to as a liquid light source) 30 flows as the light source tank 2 by disposing the separation unit 5 inside the hydrogen generation tank 10. ing. It is also possible to use a plate-like member as the separation part 5 and to form a channel 50 having a rectangular cross-section surrounded by the plate-like separation part 5. A circular flow path 50 can also be formed.

  The separation unit 5 is made of a material that is transparent to the light emitted from the liquid light source 30 and that is durable against the flow of the liquid light source 30 and the water 40. For example, highly light-transmitting resins such as acrylic resin, polycarbonate, and PET, and inorganic materials such as glass, sapphire, quartz, and diamond can be used.

  The surface of the separation part 5 is subjected to uneven processing. As shown in FIGS. 2 (a) to 2 (c), the shape of the irregularities 51 is finer on the surface of a semi-circular, V-shaped, rectangular, U-shaped, wavy, and large irregularities. The shape may be any shape such as a concavo-convex shape, but is preferably a shape that reduces the plane parallel to the main plane of the separation portion 5 as much as possible. Thereby, the ratio that the light incident on the separation unit 5 from the liquid light source 30 at a random angle is totally reflected on the surface of the separation unit 5 can be reduced, and the rate of transmission through the separation unit 5 can be increased. Therefore, it is desirable that the unevenness 51 is formed on at least one surface of the separation portion 5 without a gap, and the shape of the unevenness 51 is, for example, the main plane of the separation portion as shown in FIGS. It is more preferable when it consists only of surfaces that are inclined to each other.

  The diameter (pitch) of the unevenness 51 is preferably not less than 1 mm and not more than the wavelength of the light of the liquid light source 30, and more preferably not more than 10 μm. By setting the size as described above, when the luminescent organism is used as the liquid light source 30, the luminescent organism can be prevented from being caught between the irregularities 51. In addition, you may form an unevenness | corrugation in both surfaces by the side of the photocatalyst tank 1 and the light source tank 2 of the isolation | separation part 5. FIG.

  A photocatalyst tank 1 is formed on the outside of the separation unit 5 constituting the flow path 50. In the example of FIG. 3, a flow path 60 through which water 40 to be decomposed flows is formed as the photocatalyst tank 1. On the inner wall of the photocatalyst tank 1, an adherend 160 having an uneven structure is disposed, and the surface of the adherend 160 is covered with a layer of the photocatalyst 20. The adherend 160 has a pleated concavo-convex structure simulating the inner wall of the small intestine of a human body, and has a surface area 100 to 1000 times larger than that without the pleated concavo-convex structure. The flow path 50 meanders so as to sew between the adherends 160.

  Operation | movement of the hydrogen generator of this embodiment is demonstrated. While supplying the liquid light source 30 from the inlet 50a of the flow path 50 and discharging it from the outlet 50b, water to be decomposed is supplied from the inlet 60a of the flow path 60 and discharged from the outlet 60b. The liquid light source 30 approaches the surface of the adherend 160 having a complicated shape while flowing through the meandering flow path 50, and irradiates the photocatalyst 20 with light through the transparent separation unit 5.

  At this time, in this embodiment, since the unevenness is formed on at least one surface of the separation unit 5, the light emitted from the liquid light source 30 in all directions is difficult to be totally reflected on the surface of the separation unit 5. It can penetrate and reach the photocatalyst 20 with low loss.

  On the surface of the photocatalyst 20 irradiated with light from the liquid light source 30, water is decomposed by the action of the photocatalyst to generate hydrogen and oxygen. Since the amount of hydrogen produced is proportional to the surface area of the effective photocatalyst 20, it is possible to produce 100 to 1000 times more hydrogen in the present invention than when there is no unevenness. The generated hydrogen and oxygen are collected mainly from the outlet 60b, and hydrogen and oxygen are separated to obtain hydrogen. As shown in FIG. 4, it is also possible to arrange a hydrogen / oxygen separation filter 105 that separates hydrogen and oxygen.

  In the present embodiment, since the unevenness 51 is provided in the separation unit 5, the light emitted from the liquid light source can be incident on the photocatalyst tank 1 with high efficiency, and thus the amount of light reaching the photocatalyst 20 is large. Therefore, in the present invention, since the photocatalytic action can be exerted on the photocatalyst 20 having a large area with strong light, hydrogen can be generated with high efficiency.

  In the light source tank 2, a stimulus generating unit that emits light by applying a chemical, physical, or electrical stimulus to a liquid light source may be disposed. Specifically, a stirrer that stirs a liquid light source, a heating device that heats a liquid light source, a voltage application device that applies electrical stimulation, or the like can be disposed as a stimulus generator.

  Further, the shape of the adherend 160 in the hydrogen generation tank 10 is not limited to the shape shown in FIG. 3, and it is also possible to use a mesh shape or a cylindrical shape.

<< Liquid light source 30 >>
As the liquid light source, a light source that does not require electric power for light output is used. For example, a light emitting organism mixed (dispersed) in a liquid, a powdered phosphorescent material mixed (dispersed) in a liquid, and Any of the chemiluminescent solutions can be used. As the liquid light source 30, a light source that emits light having a wavelength that causes the photocatalyst 20 to produce a photocatalytic action is used. The wavelength necessary for the action of the photocatalyst 20 depends on the material of the photocatalyst, but generally, the shorter the wavelength, the higher the efficiency. Therefore, the emission wavelength of the liquid light source emits light below visible light, more preferably below 500 nm. It is desirable to have a peak.

  In addition, since the photocatalyst 20 has a light intensity necessary for exhibiting a photocatalytic action depending on its type, the liquid light source can store light so that it can emit light having an intensity necessary for decomposing water by the photocatalyst. Adjust the type, concentration and amount of materials, luminescent organisms and chemiluminescent solutions.

  In general, the relationship between the light intensity and the amount of hydrogen produced by the reaction of the photocatalyst is proportional in the range where the light intensity is weak, but when the light intensity increases, the hydrogen produced by the reaction of the photocatalyst. Is proportional to the (1/2) th power of the light intensity. Therefore, when the light intensity is increased to some extent, it is more effective to increase the surface area of the photocatalyst than to increase the light intensity. The amount of hydrogen produced is proportional to the surface area of the photocatalyst. The present invention is superior to the case of using a fixed light source in that a liquid light source is used to increase (control) the intensity of the light source and to increase the surface area of the photocatalyst.

<Luminescent organisms>
When the liquid light source 30 is a mixture of luminescent organisms in a liquid, luminescent bacteria and luminescent plankton can be used as the luminescent organisms. Since the diameter of the luminescent bacteria is as small as 1 to 2 μm and the diameter of the luminescent plankton is as small as 40 μm to 1 mm, when both are mixed with the liquid and used as the liquid light source 30, the liquid is excellent in fluidity. Moreover, since it can be cultured easily if there is appropriate nutrition at room temperature, it is easy to handle. There is also an advantage that it is easy to use because of low toxicity to the human body.

  Specifically, the luminescent bacteria are known luminescence that exhibits strong luminescence and wavelength, such as Photobacterium phosphoreum of the genus Photobacterium that emits blue with an emission wavelength of 475 nm and Vibrio fischeri Y-1 of the genus Vibrio that emits yellow with an emission wavelength of 535 nm. One or more of bacteria (about 19 types) can be used. In addition to these known luminescent bacteria, it is also possible to use novel luminescent bacteria or luminescent bacteria that have been genetically modified. For example, it is possible to use a protein that is recombined by genetic recombination or the like in a protein (lumazine protein (Lump) in photobacterium phosphoreum, YFP protein in Vibrio fischeri Y-1).

  As a specific example of luminescent plankton, Jacochu can be used for animals and quail beetles can be used for plants. Jakouchu is a transparent unicellular organism in the shape of a peach about 1 mm in diameter.

  In the case of using luminescent plankton, the emission intensity can be increased by increasing the concentration (density) of luminescent plankton in the liquid light source 30, so that the amount of hydrogen produced increases. On the other hand, since the luminescent bacteria have a characteristic that they do not emit light unless the density of the bacteria is more than a certain level, it is desirable to set the concentration (density) to 5% by weight or more. However, if the concentration becomes too high, the viscosity of the liquid light source 30 increases and the fluidity decreases, so the concentration is desirably 90% by weight or less.

  In addition to the concentration (density), the emission intensity depends on chemical, physical and electrical stimuli such as salt concentration, oxygen concentration, temperature, and agitation of the liquid light source 30, and the emission intensity is increased by these stimuli. Therefore, it is possible to stimulate the luminescent organism.

  The solvent (liquid) for mixing (dispersing) the luminous bacteria and plankton is selected according to the luminous bacteria and plankton. For example, when the luminescent bacteria and plankton are marine, saline is used as a solvent, and when they are fresh water, water is used. When cultivating luminescent bacteria using saline, it is preferable to set the salinity concentration to 3-5%, which is a general concentration of seawater. Since the emission intensity changes, the salt concentration is set so that the necessary emission intensity can be obtained.

<Phosphorescent material>
As an example of the phosphorescent material, zinc sulfide (ZnS-based) or strontium aluminate (SrAl ₂ O ₄ -based) can be used. As these average particle diameters, those of 0.1 to 30 μm can be used. In this case, the afterglow time is about 30 minutes to 2 hours.

  As a specific example, a sulfide phosphor can be used as a phosphorescent material. Specifically, one or more of CaS: Bi (purple blue light emission), CaSrS: Bi (blue light emission), ZnS: Cu (green light emission), ZnCdS: Cu (yellow to orange light emission), and the like are used. it can.

As the phosphorescent material, a compound represented by MAl ₂ O ₄ or MAl _x O _y (where M is selected from the group consisting of Ca, Sr, and Ba) can also be used. If necessary, the compound can be doped with an element. Specifically, among SrAl ₂ O ₄ : Eu, Dy (emission wavelength 520 nm), Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy (emission wavelength 490 nm), CaAl ₂ O ₄ : Eu, Nd (emission wavelength 440 nm) One or more of these can be used.

  The liquid light source 30 is obtained by making these phosphorescent materials into particles having a particle diameter of 0.1 μm to several mm and mixing them with a solvent. The phosphorescent material is used after being sufficiently irradiated with light in advance and stored.

  In order to obtain a liquid light source, the solvent in which the phosphorescent material is dispersed is not particularly limited as long as it has fluidity such as water and oil. In addition, an additive such as a surfactant may be added to prevent the photocatalyst and the powdery phosphorescent material from adhering to each other.

<Chemiluminescence solution>
When a chemiluminescent solution is used, if it is a liquid itself, it does not have to be mixed with a solvent separately. Moreover, it is also possible to use what mixed (dispersed) the following substances in the solvent or dissolved in the solvent as the chemiluminescent solution. For example, green-emitting fluorescent substance 9,10-bis (phenylethynyl) anthracene (C ₆ H ₅ : C) ₂ C ₁₄ H ₈ , orange-emitting fluorescent substance rubrene (5,6,11,12-tetraphenylnaphthacene) C _{One or more of 42} H ₂₈ , blue-emitting fluorescent material perylene C ₂₀ H ₂₂ , luminol, lophine, lucigenin, and oxalate can be used. The solvent for mixing (dispersing) the above substances may be any fluid such as water or oil. In addition, a solvent in which the substance is dissolved is selected and used as the solvent to be dissolved. For example, a basic aqueous solution can be used.

<< Photocatalyst >>
Any type of photocatalyst can be used as long as it can decompose water into hydrogen and oxygen.
However, when using a luminescent organism as a liquid light source, considering that the survival of the luminescent organism is often difficult when the wavelength is shortened to the ultraviolet region, and that the emission wavelength of the luminescent organism is often about 400 to 700 nm, What produces a photocatalytic action by visible light is desirable. In that case, a visible light-responsive artificial photosynthesis type photocatalyst having a two-step excitation mechanism is desirable. In the two-stage photoexcitation (Z-scheme) type water splitting system, the water splitting is divided into a hydrogen generating system and an oxygen generating system, and an iodate / iodide (IO ³⁻ / I ⁻ ) is an electron carrier between them. It is connected by reversible ion pairs such as Fe ions. Accordingly, since the energy of light necessary for each system is reduced, it is possible to use long-wavelength visible light with small energy.

Specifically, ZrO ₂ / TaON (hydrogen generating photocatalyst) and WO ₃ (oxygen generating catalyst) each holding Pt nanoparticles can be used as the photocatalyst 20. Another example of a combination of a hydrogen generating photocatalyst and an oxygen generating photocatalyst is shown below. (Indicated by “photocatalyst for hydrogen generation”-“photocatalyst for oxygen generation”) Pt / SrTiO ₃ : Cr—Ta / WO ₃ , Pt / TaON-WO ₃ , Pt / StTiO ₃ : Rh—BiVO ₄ , Pt / StTiO 3 ₃ : Rh—WO ₃ , Ru / StTiO ₃ : Rh—BiVO ₄ , Ru / StTiO ₃ : any one of Rh—WO ₃ , Cr—Rh / GaN: ZnO, and BaTaO ₂ N—WO ₃ Two or more can be used as the photocatalyst 20.

  As a method for arranging the photocatalyst 20 on the adherend 160, a method of mixing the particulate photocatalyst 20 with a binder such as a resin or an inorganic material, applying or dripping it onto the surface of the adherend 160, and then solidifying the photocatalyst 20 or EB A method of forming a film on the surface of the adherend by vapor deposition such as vapor deposition or sputtering can be used. As shown in FIG. 1, the photocatalyst 20 can be dispersed in water 40 as particles.

<< Roughness forming method of separation part 5 >>
A method for forming irregularities on the surface of the separation portion 5 will be described. Here, as an example, as the separating portion 5, a sapphire substrate having a C-plane main plane is used to form the unevenness 51.

  First, as shown in FIG. 5A, a resist pattern 71 is formed on the C surface of the sapphire substrate 70 using a known photolithography technique or the like. The resist pattern 71 has a plurality of openings 72 as shown in FIG. 5D and FIG. The arrangement of the openings 72 may be random or periodic. The shape of the opening 72 can be a circle or a polygon. The size of the opening 72 is preferably such that the diameter (pitch) of the unevenness after the unevenness processing is equal to or greater than the wavelength of the light of the liquid light source 30 and the plane of the surface of the sapphire substrate 70 is as small as possible. For example, when the shape of the opening 72 is a circle, φ3 μm and a pitch of about 4.5 μm are preferable. The resist pattern 71 is used as a protective mask during the reactive ion etching process in the step of FIG. 5B, but is not limited to a resist material, and a hard mask such as a metal can also be used.

Next, as shown in FIG. 5B, reactive ion etching (RIE) is performed on the upper surface of the sapphire substrate 70 to etch the sapphire substrate 70 in the opening 72, thereby forming a recess 73. As the etching gas, for example, BCl ₃ , Cl ₂ , Ar, or the like can be used. At this time, the shape of the recess 73 can be changed depending on the etching conditions. For example, the side walls of the recesses can be inclined surfaces 74 of 15 to 60 degrees with respect to the a-axis of the sapphire substrate. In addition, when the resist 71 having a narrow distance (pitch) between the adjacent openings 72 is used, the upper surface of the sapphire substrate is formed only by the inclined surface 74, and there is no plane (C plane) region. It is also possible to form the unevenness 51.

Specifically, a mixed gas of BCl ₃ and Ar is used as an etching gas, supplied into the chamber at a flow rate ratio of 1: 1, the pressure is adjusted so that the degree of vacuum is 0.6 Pa, and the RF condition is When RIE is performed with Ant power 450W and Bias power 550W and an etching time of 600 sec, a recess 73 having a depth of about 1 μm and a side wall inclination angle of about 30 degrees with respect to the a-axis can be formed.

  Finally, as shown in FIG. 5C, the resist pattern 71 is removed. As a removal method, a commercially available resist stripping solution can be used. Furthermore, when a slight resist residue adheres to the concavo-convex processed portion, it is preferable to completely remove it with a mixed solution of sulfuric acid and hydrogen peroxide solution.

  By performing the steps of FIGS. 5A to 5C on the other surface of the sapphire substrate, it is possible to perform uneven processing on both surfaces of the sapphire substrate.

  Note that, here, the sapphire substrate is processed by RIE as the separation portion 5, but the present invention is not limited to this method. It is possible to perform a desired concavo-convex process using other etching methods (wet etching, dry etching, etc.), sand blasting, and other processing methods such as laser processing.

(Second Embodiment)
As shown in FIG. 4, the hydrogen production apparatus of the first embodiment has a configuration in which, in addition to the hydrogen generation tank 10, an adjustment tank 111 that adjusts the liquid light source to a state capable of emitting light and flows into the inflow port. It is possible to For example, the adjustment tank 111 includes the control tank 101. When the liquid light source 30 is a light source using a luminescent organism, the control tank 101 adjusts the temperature or salt concentration of the liquid light source, an oxygen supply unit that supplies oxygen to the liquid light source, and It is possible to include at least one stimulus generating unit that emits light by applying a chemical, physical, or electrical stimulus to a liquid light source. Further, when the liquid light source is a liquid using a phosphorescent material, the control tank 101 includes a light irradiation unit that irradiates the liquid light source with light and stores the light before supplying the hydrogen generation tank. To do. In the case of a chemiluminescent solution, a stimulus generating unit that starts chemical luminescence by applying chemical, physical, or electrical stimulation to a liquid light source can be disposed in the control device.

  When the liquid light source is a luminescent organism dispersed in a liquid, the adjustment tank 111 preferably includes a culture tank 102 for cultivating the luminescent organism. Thereby, since a luminescent organism can be cultured, the quantity which supplies a luminescent organism from the outside can be reduced or made zero.

  It is also preferable to further include a circulation mechanism for returning the liquid light source 30 that has flowed out from the outlet of the hydrogen generation tank 10 to the adjustment tank 111. The light source 30 can be reused by adjusting the liquid light source 30 that no longer emits light in the hydrogen generation tank 10 to return to the adjustment tank 111 to emit light again. The circulation mechanism emits almost no light when the liquid light source in the flow path of the hydrogen generation tank detects no light emission or when a predetermined time elapses after flowing into the flow path. It can be determined that the process has been completed and returned to the adjustment tank.

  The above-described culture tank 102 can be connected to a microbial decomposition tank that microbially decomposes the waste water. The microbial decomposition tank supplies the culture tank 102 with at least one of organic substances and gas generated by microbial decomposition. Thereby, the nutrient required for culture | cultivation can be supplied to a culture tank.

1: Photocatalyst tank, 2: Light source tank, 5: Separation unit, 10: Hydrogen generation tank, 20: Photocatalyst, 30: Liquid light source, 40: Water, 50: Flow path of liquid light source, 60: Flow of water to be decomposed Road, 101: Control tank, 102: Culture tank, 105: Hydrogen / oxygen separation filter

Claims (13)

A hydrogen generation tank, a photocatalyst tank for storing a photocatalyst and water by separating an internal space of the hydrogen generation tank, and a separation unit that separates into a light source tank for storing a liquid light source;
The separation portion is made of a material that transmits light emitted from the liquid light source. At least one surface of the separation portion is formed with an uneven shape, and the diameter of the unevenness is determined by the liquid light source. A hydrogen production apparatus characterized by being larger than the wavelength of emitted light.   The hydrogen production apparatus according to claim 1, wherein the uneven shape is formed on at least one surface of the separation portion without a gap.   3. The hydrogen production apparatus according to claim 1, wherein the concavo-convex shape includes only a surface inclined to the main plane of the separation portion.   The hydrogen production apparatus according to claim 1, wherein the separation unit constitutes a flow path through which the liquid light source flows.   5. The hydrogen production apparatus according to claim 1, wherein the liquid light source is any one of a luminescent organism dispersed in a liquid, a phosphorescent material dispersed in a liquid, and a chemiluminescent solution. A hydrogen production apparatus comprising:   The hydrogen production apparatus according to any one of claims 1 to 5, wherein the photocatalyst is disposed on an inner wall of the photocatalyst tank of the hydrogen generation tank.   The hydrogen production apparatus according to claim 6, wherein the photocatalyst is supported on an adherend having irregularities formed and fixed to the inner wall.   The hydrogen production apparatus according to any one of claims 1 to 5, wherein the photocatalyst is a particle and is dispersed in the water.   9. The hydrogen production apparatus according to claim 1, wherein the hydrogen generation tank includes an inflow port for taking the liquid light source into the light source tank from outside, and the liquid light source of the light source tank. A hydrogen production apparatus, characterized by having an outflow port through which gas flows out and a hydrogen extraction port through which hydrogen generated inside is extracted.   The hydrogen production apparatus according to claim 9, further comprising an adjustment tank that adjusts the liquid light source to a state capable of emitting light and allows the liquid light source to flow into the inflow port.   The hydrogen production apparatus according to claim 10, wherein the liquid light source is a luminescent organism dispersed in a liquid, and the adjustment tank includes a culture tank for culturing the luminescent organism. apparatus.   6. The hydrogen production apparatus according to claim 5, wherein the luminous organism includes at least one of luminous bacteria and luminous plankton.   The hydrogen production apparatus according to any one of claims 1 to 12, wherein the photocatalyst includes two types of hydrogen production photocatalyst and oxygen production photocatalyst.

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