Hydrogen production apparatus and hydrogen production method

Abstract

To solve a problem that the generation ratio of hydrogen has been low and a large electric power has been used in conventional hydrogen production methods.SOLUTION: An acidic aqueous solution 227 is filled around a negative electrode 108. A blood or hemoglobin is filled around a positive electrode 107. A voltage is applied between the positive electrode 107 and the negative electrode 108 by means of an electrode voltage control circuit 114. Hydrogen is generated at the negative electrode 108 and collected by means of a gas collector 109. Electrons are emitted from the positive electrode 107, and thus the color changes as oxyhemoglobin is changed into methemoglobin. The change of color is measured by means of a color measuring device 234. When the change of color exceeds a specified value, the ratio of methemoglobin is determined to be high, and the hemoglobin is replaced.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a hydrogen production device and a hydrogen production method. [Background technology]

[0002] There is a method for producing hydrogen called "reforming," in which fossil fuels are burned to produce gas, and hydrogen is then extracted from that gas. However, this manufacturing process generates carbon dioxide.

[0003] There is a production method to produce hydrogen by "electrolysis," that is, by splitting water with electricity. Splitting water with electricity requires a large amount of electricity. Therefore, the power efficiency for the hydrogen produced is extremely poor.

[0004] In this specification and drawings, the configuration consisting of the negative electrode 108 and the aqueous solution 227 may be referred to as a negative electrode, and the configuration consisting of the positive electrode 107 and the solution 221 (blood, etc.) may be referred to as a positive electrode. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] WO2019 / 234992 [Patent Document 2] Patent Publication No. 2020-93950 Summary of the Invention [Problem to be solved by the invention]

[0006] The production method for generating hydrogen from organic gas methane requires heating to high temperatures. Heating generates carbon dioxide. As long as organic matter is used as the raw material, the generation of carbon dioxide is unavoidable.

[0007] In the production method of electrolyzing water and generating hydrogen using a catalyst, a large amount of electricity is required for the electrolysis of water because the theoretical potential window of water is 1.23 V. Therefore, if hydrogen is used as an energy source, more energy than this will be used to produce hydrogen. [Means for solving the problem]

[0008] The hydrogen generation device of the present invention comprises a negative electrode (cathode) having an acidic aqueous solution, a positive electrode (anode) having blood containing hemoglobin or a solution containing hemoglobin separated from red blood cells, a separator disposed between the negative electrode and the positive electrode, and a voltage application circuit that applies a voltage between the negative electrode and the positive electrode.

[0009] An acidic aqueous solution 227 is filled around the negative electrode 108, and blood or hemoglobin is filled around the positive electrode 107. A voltage is applied between the positive electrode 107 and the negative electrode 108 by an electrode voltage control circuit 114.

[0010] At the negative electrode 108, electrons are received and hydrogen ions are reduced to generate hydrogen. The hydrogen is collected by a gas collector 109. At the positive electrode (anode) 107, electrons are released and oxyhemoglobin is oxidized to methemoglobin. Oxygen is generated at the positive electrode (anode) 107. It is the heme complex ([Fe(II)]) that is oxidized by oxygen, and Fe(II) becomes Fe(III).

[0011] When blood or hemoglobin is exposed to the atmosphere, it is in the oxy-type, with oxygen adsorbed. When voltage is applied, the oxy-type blood or hemoglobin is oxidized and becomes methemoglobin.

[0012] Because oxyhemoglobin and methemoglobin have different absorption in the visible range, it is possible to confirm the change from oxyhemoglobin to methemoglobin by measuring the absorbance (Figure 11). The methemoglobin is discarded from the positive electrode and replaced (injected) with new blood or a hemoglobin solution into the positive electrode. In the above examples, methemoglobin was discarded, but the present invention is not limited to this.

[0013] Methemoglobin is collected and a voltage is applied to the collected methemoglobin to convert Fe(III) into a heme complex (Fe(II)). The E0 voltage is very small. In addition, it can be converted back into oxyhemoglobin (Hb(O2)) by bubbling oxygen or air into it and allowing it to bind to or adsorb oxygen. The converted oxyhemoglobin (Hb(O2)) can be injected into the positive electrode and used to generate hydrogen. Separator 119 separates the negative electrode (cathode) from the positive electrode (anode). Separator 119 allows hydrogen ions and water to pass through. Oxygenated blood or hemoglobin becomes methemoglobin when it is oxidized. Hemoglobin bound to oxygen is called oxyhemoglobin and has the bright red color of arterial blood. Methemoglobin cannot carry oxygen. It has a bluish chocolate brown color.

[0014] When oxyhemoglobin turns into methemoglobin, it changes color from the bright red of oxyhemoglobin to the bluish chocolate brown of methemoglobin.

[0015] Therefore, by monitoring (measuring) the absorbance or color, it is possible to quantitatively grasp the extent to which hemoglobin (oxyhemoglobin) has changed to methemoglobin. By quantitatively grasping the amount, it is possible to quantitatively control the hydrogen generation state. Effect of the Invention

[0016] The hydrogen generating device and method of the present invention can easily generate hydrogen with low power consumption, and can be provided as a low-cost hydrogen production device and method.

[0017] In the acidic aqueous solution at the negative electrode, hydrogen ions are reduced to generate hydrogen. The reduction potential depends on the pH. For example, at pH=0, it is close to 0 V. At pH=0.1, it is about -0.1 V, and at pH=2, it is about -0.2 V. The reduction potential is very small, so the power used to generate hydrogen is small.

[0018] At the positive electrode, the potential required to convert hemoglobin to methemoglobin is about +0.15 V, and the oxidation proceeds spontaneously. Therefore, the applied voltage for hydrogen generation is only the reduction potential of hydrogen and the overvoltage of the electrode.

[0019] Using blood and hemoglobin consumes less power than any other electrolysis method, is inexpensive, and is sustainable. The voltage for hydrogen generation depends almost entirely on the overvoltage of the electrodes, so a low voltage is sufficient.

[0020] When blood or hemoglobin is used for electrolysis at the positive electrode, the decomposition voltage for hydrogen generation is about the overvoltage of the electrode, realizing significant energy savings. Blood or hemoglobin can be used from pigs, cows, whales, etc. Since blood is discarded, the material cost is also low. [Brief description of the drawings]

[0021] [Figure 1] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Diagram 2] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Diagram 3] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Figure 4] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Diagram 5] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Figure 6] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Figure 7] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Figure 8] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Figure 9] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Figure 10] 1 is a configuration diagram of a hydrogen production device and an explanatory diagram of a hydrogen production method according to the present invention. FIG. [Figure 11] FIG. 1 is an explanatory diagram of a hydrogen production method according to the present invention. [Figure 12] FIG. 1 is an explanatory diagram of a hydrogen production method according to the present invention. [Figure 13] FIG. 1 is an explanatory diagram of a hydrogen production method according to the present invention. [Figure 14] FIG. 1 is an explanatory diagram of a vehicle having a hydrogen production device of the present invention. [Figure 15] FIG. 1 is an explanatory diagram of a hydrogen production method according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] When two electrodes are placed in water and a voltage higher than the potential window of water is applied, the water decomposes to generate hydrogen and oxygen. This is the electrolysis of water, and the reaction between the negative and positive electrodes is shown below. Hydrogen is produced at the negative electrode. H2O + e - -> 1 / 2H2+ OH - (1a) H + + e- -> 1 / 2H2(1a') At the positive electrode, H2O -> 1 / 2O2+ 2H + + e- (1b) 2OH - -> H2O + 1 / 2O2 + 2e - (1b') In aqueous solution, H + and OH - is in equilibrium with H + + OH - <--> H2O This equilibrium is the fastest reaction in aqueous solution and the reactions 1a vs. 1a' and 1b vs. 1b' cannot be distinguished.

[0023] In an acidic aqueous solution, 1a' and 1b are preferred. In an alkaline aqueous solution, 1a and 1b' are preferred. Considering the evolution of hydrogen, 1a' has a smaller reduction potential than 1a.

[0024] In other words, in an acidic aqueous solution, 1a' is preferred (1a' is the main reaction), so the reduction potential is low. On the other hand, in an alkaline aqueous solution, 1b' lowers the potential for oxygen production.

[0025] As a result, the cell voltage at which electrolysis occurs (theoretically, the applied voltage is 1.23 V) remains the same whether the solution is acidic or alkaline. However, the potential window of water varies depending on the electrolyte dissolved in it and the properties of the electrodes. Examples of acidic aqueous solutions include hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid aqueous solutions. In lead-acid batteries, it is possible to apply 2 V. The oxidation and reduction potentials of water change depending on the hydrogen ion concentration, but the potential window does not change.

[0026] In fact, this can be confirmed by CV measurements of 1 mol H2SO4 aqueous solution and 1 mol NaOH aqueous solution. In other words, there is no difference in the power consumption of electrolysis whether it is acidic or alkaline. The structure of normal water is in the weakest state of OH bonds, and the potential window is 1.23V. In the present invention, hydrogen is generated at the negative electrode 108. Therefore, the reduction potential of water is important. In other words, acidity is advantageous because the reduction potential of water is lower. Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

[0027] In the drawings for explaining the embodiments of the invention, elements having the same function or similar configuration are denoted by the same reference numerals, and descriptions thereof may be omitted. Also, the drawings may be enlarged, reduced, or omitted.

[0028] The embodiments of the present invention described in this specification and the drawings can be combined with each other. The embodiments described in this specification and the drawings include the embodiment, a similar embodiment, and a combination of the embodiment in part or in whole.

[0029] 1 is a diagram showing the principle of the hydrogen production device of the present invention and a diagram explaining the principle of the hydrogen production method. The negative electrode 108 reduces water (or hydrogen ions) to generate hydrogen (H2).

[0030] At the positive electrode (anode), electrons are released and oxyhemoglobin is oxidized to methemoglobin. The heme complex ([Fe(II)]) is oxidized, and Fe(II) becomes Fe(III). Oxygen is generated at the anode. The present invention oxidizes metal complexes. It can be oxidized at a lower voltage than water. The oxidation reaction is rapid and can be reversed.

[0031] Hydrogen generation by electrolysis occurs as HO or H + This occurs by the reduction of . In particular, in an acidic aqueous solution, the potential of (1a') is close to 0. Therefore, hydrogen gas can be produced at low voltage. The positive electrode 107 is at an oxidation reaction potential. A potential of 1.23 V is required to decompose water and generate oxygen. In reactions using Fe(II) complexes, [Fe II (CN)6] 4- -> [Fe III (CN)6] 3- + e - E0= -0.36V (2) The potential of the positive electrode 107 can be reduced. Fe(III) must be reduced to Fe(II) - without this reduction process hydrogen evolution will not continue.

[0032] The present invention uses oxyhemoglobin (Hb(O2)), the main component of blood, at the positive electrode. Note that hemoglobin in a state where oxygen is adsorbed is called oxyhemoglobin. In the hydrogen generation process, hydrogen is generated at the negative electrode by reaction (1a'), and the following reaction occurs at the positive electrode. Hb(O2) -> Hb +

[0033] Hb(O2) is oxyhemoglobin, Hb + is methemoglobin. Hb + In this case, the heme iron is oxidized to Fe(III). Methemoglobin does not have the function of adsorbing oxygen. Methemoglobin is sometimes referred to as Hb+ or MetHb.

[0034] Hemoglobin is contained in blood. The blood used can come from any mammal. A large amount of blood from cows and pigs is wasted. For example, cows have 50 kg of blood per head. All living creatures have hemoglobin, except for some seafood such as squid, rays, and sea squirts. Blood from whales, fish, etc. can also be used. In addition, the material is not limited to hemoglobin in blood, etc. Any material may be used as long as iron changes between trivalent and divalent forms and contains oxygen. Examples of metals other than iron include copper, chromium, and aluminum. Materials containing these metals (metal complexes, etc.) are used as the positive electrode solution.

[0035] The negative electrode solution 227 is an acidic aqueous solution having a pH of 1 to 3. Preferably, the solution is an acidic aqueous solution having a pH of 1 to 3. For example, 0.1 M (mol / dm 3 ) sulfuric acid or phosphoric acid aqueous solution is exemplified.

[0036] The positive electrode solution 221 is blood or an aqueous solution of hemoglobin separated from red blood cells. The separator 119 can be a cation exchange membrane that allows hydrogen ions to pass through, or a hydrophilic polymer membrane or glass filter that does not allow blood or hemoglobin to pass through. Other examples include cellophane film and polypropylene film with micropores. Hydrogen ions generated at the positive electrode (anode) pass through the separator 119 and move to the negative electrode (cathode). If a cation exchange membrane is used for the separator 119, the acid will not be consumed. All you need to do is add water during hydrogen production.

[0037] The negative electrode (cathode) is preferably kept acidic, at 0.1M (mol / dm 3 ) Sulfuric acid, nitric acid, or phosphoric acid aqueous solution (pH about 3) is also acceptable. The closer the pH is to a strong acid (pH = 1), the better the results. The hemoglobin aqueous solution at the positive electrode (anode) is neutral. It is also salt water. The negative electrode (cathode) can be any acid. For example, phosphoric acid can be used. If a cation exchange membrane is used for the separator 119, the acid will not be consumed. All you need to do is add water.

[0038] Examples of the negative electrode 108 include gold, platinum, chromium, vanadium, acid-resistant stainless steel, carbon, aluminum alloy, titanium alloy, and nickel alloy. Stainless steel is particularly acid-resistant and relatively inexpensive. Examples include S-TEN, COR-TEN, and MARILOY. Carbon-based electrodes are also exemplified. Examples of the positive electrode 107 include gold, platinum, silver, zinc, stainless steel, aluminum alloys, titanium alloys, nickel alloys, and mixtures of graphite and activated carbon.

[0039] In addition, metals such as fibrous titanium, stainless steel, nitinol alloy (nickel-titanium), platinum-iridium alloy, and platinum may be configured or formed into a cylindrical, polygonal, or rectangular mesh or honeycomb structure and used as the positive electrode 107. These are called studded electrodes.

[0040] When a permanent magnet or an electromagnetic magnet having magnetic force is used for the positive electrode 107, hemoglobin or oxyhemoglobin is attracted to the magnet, improving efficiency. In addition, in the case of an electromagnetic magnet, the state of hydrogen generation can be controlled by controlling the current passed through the electromagnetic magnet (such as the strength of the current).

[0041] When hydrogen is produced, water or an acidic aqueous solution is added to the negative electrode. Collected blood or hemoglobin separated from blood is added to the positive electrode. Blood can also be used as is. In addition, the acidic aqueous solution, hemoglobin, etc. that have deteriorated or completed the reaction are discharged as appropriate.

[0042] Any material used in the electrolysis of water may be used for the material of the negative electrode 108. However, if stainless steel is used for the negative electrode 108, hydrochloric acid cannot be used for the solution 227.

[0043] The reduction potential (hydrogen generation) at the negative electrode depends on the hydrogen ion concentration, and is about −0.1 V at pH 1. At the positive electrode 107, the oxidation potential can be considered to be almost 0 V.

[0044] Therefore, the potential for hydrogen generation depends on the overvoltage of the collecting electrode. Even if the overvoltage is set at 0.4 V, hydrogen generation is possible at 0.5 V or less. This is about 1 / 4 of the energy required for the potential electrolysis of water. Overvoltage also occurs in the electrolysis of water.

[0045] The salt concentration of blood is about 1%. At this concentration, red blood cells are stable. After red blood cells are separated using a centrifuge 208, when fresh water is added, the red blood cells burst and hemoglobin is eluted. Hemoglobin is obtained by centrifugation. It is preferable to perform bubbling after centrifugation to obtain more oxyhemoglobin.

[0046] It is efficient to separate hemoglobin from blood and use the hemoglobin as a hydrogen generator. When separating hemoglobin from blood using a centrifuge 208, or after separation, the hemoglobin can be changed or converted to oxyhemoglobin by bubbling oxygen or air into the hemoglobin. In this case, the oxygen adsorber 207 can be omitted. During bubbling, it is preferable to adjust the pH and temperature. Needless to say, bubbling can be performed by mixing with oxygen or the like and stirring, or by applying vibration or the like to mix the hemoglobin.

[0047] Hemoglobin is the main component of blood, which adsorbs oxygen and delivers it throughout the body. It can be said to be the foundation of life. Hemoglobin is contained in red blood cells. Even when hemoglobin is separated from red blood cells, it maintains its important function of adsorbing and releasing oxygen. In addition to humans, all mammals (including whales) use hemoglobin to transport oxygen.

[0048] Hemoglobin is composed of a heme complex and the protein globin. Looking at the details of oxygen adsorption by hemoglobin, an oxygen molecule is coordinated to the iron (II) heme complex. This bond is not simply electrostatic, but there is overlap between the orbitals, and the oxygen molecule is coordinated at an angle to the heme surface. It is amazing that covalently bonded oxygen molecules can repeatedly be adsorbed and desorbed in this way at such a high speed of less than one second, and it is unthinkable without the role of globin.

[0049] 1 g of hemoglobin contains 3.4 mg of iron. One molecule of oxygen binds to one iron. 1 kg of hemoglobin is 3.4 g, or 0.061 M (mol / dm 3 ) of iron is present.

[0050] This means that 1 kg of hemoglobin has a concentration of 0.061M (mol / dm 3 ) of oxygen will be present. It weighs 1.95g, and in gas form it is 1.4 (L liters).

[0051] In other words, 1 kg of hemoglobin contains 1.4 liters of oxygen. The solubility of oxygen in water is 8 mg / L at 25 degrees Celsius, so hemoglobin holds 390 times the amount of dissolved oxygen. Here, hemoglobin is abbreviated as Hb. Oxyhemoglobin that has adsorbed oxygen is Hb(O2). The reaction between Hb and oxygen is expressed by the following formula: Hb + O2<--> Hb(O2) Oxygenation (deoxygenation) Also, There is a reaction in which Fe(II) in Hb(O2) is oxidized to Fe(III). Hb(O2) -> Hb + Oxidation reaction E0= 0.15V The oxygenation and deoxygenation reactions are rapid, occurring within 1 second. The redox potential of the oxidation reaction is reported to be 0.15 V.

[0052] Hemoglobin is composed of an Fe(II) complex of heme and a protein called globin. When the Fe(II) heme complex is oxidized, it becomes methemoglobin (Fe(III) complex) MetHb + The important thing is that Hb(O2) and MetHb + The problem is that there is no electric potential at At the positive electrode (anode), electrons are released and oxyhemoglobin is oxidized to methemoglobin. Here, it is the heme complex ([Fe(II)]) that is oxidized, and Fe(II) becomes Fe(III). [Fe(II)] →[ Fe(III)] + + e - The redox potential of this reaction is +0.15 V and proceeds spontaneously to the right. Oxygen is produced during the oxidation of heme iron(II). [Fe(III)] + Since has a +1 charge, to maintain electrical neutrality, it is hydrolyzed, [Fe(III)] + + HO →[Fe(III)]OH + H + Hydrogen ions generated at the positive electrode (anode) pass through separator 119 and move to the negative electrode (cathode). The hydrogen production device and the hydrogen production method of the present invention will be described below. Figures 1 and 2 are explanatory diagrams of the hydrogen production device and the hydrogen production method of the present invention.

[0053] 1 and 2, a hydrogen production device (hydrogen production apparatus) 201 of the present invention includes a negative electrode 108 and a positive electrode 107. The positive electrode 107 utilizes an oxidation-reduction reaction of hemoglobin. There is no particular limitation on the material used for the collector of the positive electrode 107. Any material may be used as long as it is not corroded and can be used for electrolytic reduction. The negative electrode aqueous solution 227 is an acidic aqueous solution. The pH is preferably close to 1, but there is no practical problem if the pH is 3 or less.

[0054] A hemoglobin solution or blood itself is used as the positive electrode solution 221. Hemoglobin is used in the form of oxyhemoglobin. The separator 119 is a cation exchange membrane or a hydrophilic polymer membrane or glass filter that is impermeable to blood or hemoglobin.

[0055] An acidic aqueous solution is used for the negative electrode. The acidic aqueous solution may be an aqueous solution with a pH of 3 or less. When blood is used for the positive electrode, salt water is used. If a cation exchange membrane is used for the separator 119, chloride ions will not move to the negative electrode. This causes a change in the acid concentration of the aqueous solution 227. In the present invention, the aqueous solution 227 is stirred by operating the stirring fan 103.

[0056] Collecting electrodes such as the negative electrode 108 and the positive electrode 107 may be formed or configured from stainless steel, titanium, copper, zinc, nickel, aluminum, copper, stainless steel, alloys thereof, sintered alloys, wire mesh, foamed metal, ceramics, etc. Carbon electrodes are also acceptable.

[0057] In addition, the surface may be plated with platinum, gold, silver, tin, zinc, tungsten, titanium, copper, or nickel, or an alloy of these may be formed or disposed. It is preferable to periodically replace the aqueous solution 227 by allowing it to flow in and out.

[0058] The aqueous solution 227 is composed of a pump (not shown) for discharging the aqueous solution 227 from a container (not shown) storing the aqueous solution 227, a pump (not shown) for causing the aqueous solution 227 to flow into the container 102, and the like.

[0059] The stirring fan 103 is operated to make the concentration of the aqueous solution 227 in the container 102 uniform. At the positive electrode, a stirring fan (not shown) is also used to stir the solution 221. A pH meter 111 is installed or disposed in the container 102 or the like to measure the pH of the solution 221 and the aqueous solution 227. It is preferable to inject acid at appropriate times to adjust the pH. Water is injected into the aqueous solution 227 at appropriate times in accordance with the state of hydrogen generation.

[0060] In the embodiment of the present invention, the positive electrode 107, the negative electrode 108, etc. are expressed as electrodes, but are not limited to this. It goes without saying that any configuration, shape, or structure may be used as long as it can input and output electrons or charges.

[0061] In this specification and drawings, the configuration consisting of the negative electrode 108 and the aqueous solution 227 may be referred to as a negative electrode, and the configuration consisting of the positive electrode 107 and the solution 221 may be referred to as a positive electrode. The reaction rate can be set or adjusted by moving the position of the negative electrode 108 in the direction A or B and adjusting the distance from the positive electrode 107.

[0062] The same applies to the position of the positive electrode 107. The reaction rate can be set or adjusted by moving the position of the positive electrode 107 in the direction C or D to adjust the distance from the negative electrode 108. Also, the voltage generated by the variable DC power supply 112 to be applied between the negative electrode 108 and the positive electrode 107 is adjusted. Note that the variable DC power supply 112 is not limited to being variable. It goes without saying that it may be one that outputs or controls a fixed value of voltage or current.

[0063] In addition, at least one of the positive electrode 107 and the negative electrode 108 is rotated. By vibrating the positive electrode 107 and the negative electrode 108, it is possible to prevent or suppress adhesion of hydrogen and oxygen to the electrode surfaces. It is also possible to improve the recovery or generation of hydrogen and oxygen.

[0064] The above matters can be similarly applied to other embodiments. Note that the embodiments described in this specification and the drawings can be applied in whole or in part to other embodiments. It goes without saying that the embodiments can be combined.

[0065] One example of separator 119 is a cation exchange membrane, but separator 119 may be any material as long as it has a configuration or physical properties that prevent hemoglobin from dissolving from the positive electrode into the negative electrode.

[0066] The electrode voltage control circuit 114 is composed of a variable DC power supply 112, a switch circuit 115, and an ammeter 512. The voltage generated by the variable DC power supply 112 is not limited to DC. For example, it may be pulsed or the like. In addition, it is not limited to voltage control. It goes without saying that it may be one that controls current. The switch circuit 115 is not limited to only on / off control. It may be any circuit that can disconnect or connect a current or voltage, or control a current or voltage.

[0067] The control circuit 101 controls the variable DC power supply 112 and the switch circuit 115 of the electrode voltage control circuit 114. It also acquires the current value of the ammeter 512. It also obtains absorbance data and chromaticity data measured or acquired by the color measurement instrument 234, and uses these data to control the hydrogen generation device and the hydrogen generation method.

[0068] Hydrogen gas is generated at the negative electrode 108, and the generated hydrogen gas is collected in a gas reservoir 120 via a pipe 110 where the hydrogen gas is collected by a gas collector 109. A gas flow meter 411 is formed or disposed in the pipe 110, and measures the amount of hydrogen gas generated. The voltage of a variable DC power supply 112 and the like are controlled according to the amount of hydrogen gas generated and changes in the amount of hydrogen gas generated. Oxygen is generated at the positive electrode 107. It is preferable to provide a gas collector for collecting oxygen.

[0069] At the positive electrode 107, oxyhemoglobin Hb (O2) gives electrons to the positive electrode 107 to become methemoglobin (MetHb), and oxygen is generated at the positive electrode 107. The amount of oxygen generated is greater than the amount of hydrogen generated. Oxygen is used as an oxidizing agent.

[0070] At the negative electrode, hydrogen ions are reduced in an acidic aqueous solution to generate hydrogen. The reduction potential depends on the pH, and at pH=0, it is close to 0V. At pH=0.1, it is about -0.1V, and at pH=2, it is about -0.2V.

[0071] Methemoglobin (MetHb) does not have the function of adsorbing oxygen. As methemoglobin is produced, oxyhemoglobin releases oxygen, and oxygen is generated from the positive electrode 107. However, this is only the release of the oxygen that the oxyhemoglobin possesses, and is not the result of direct electrolysis.

[0072] At the positive electrode 107, the potential of hemoglobin → methemoglobin is about +0.15 V, and oxidation proceeds spontaneously. In other words, the voltage applied for hydrogen generation is only the reduction potential of hydrogen and the overvoltage of the electrode. Therefore, only a small amount of power is required for hydrogen generation. The reaction between Hb and oxygen is expressed by the following equation: Hb + O2<--> Hb(O2) Oxygenation (deoxygenation) Also, There is a reaction in which Fe(II) in Hb(O2) is oxidized to Fe(III). Hb(O2) -> Hb + Oxidation reaction E0= 0.15V

[0073] Hemoglobin is a complex protein with a tetrameric structure consisting of four subunits composed of iron-containing pigment (heme) and protein (globin) contained in the red blood cells of vertebrates. The iron in the central part of the heme binds to one oxygen molecule. In other words, one hemoglobin can bind to and transport four oxygen molecules.

[0074] Hemoglobin binds 1.36 mL of oxygen per gram. Hemoglobin bound to oxygen is called oxyhemoglobin (oxygenated hemoglobin) and has the bright red color of arterial blood.

[0075] Hemoglobin that is not bound to oxygen is called deoxyhemoglobin (deoxygenated hemoglobin) and has the dark red color that is the color of venous blood.

[0076] Methemoglobin (MetHb) is a compound formed by removing the divalent iron ion (Fe 2+ ) is oxidized to trivalent iron ions (Fe 3+ As a result, the heme binds less oxygen and the hemoglobin loses its ability to transport oxygen.

[0077] Methemoglobin (MeHb) is a type of hemoglobin in which the divalent (ferro) iron ion coordinated to normal hemoglobin is trivalent (ferric). Methemoglobin (MetHb) cannot carry oxygen.

[0078] Hemoglobin changes color to bright red or dark red depending on the state of oxygen binding. Also, the divalent iron ion (Fe 2+ ) is oxidized to trivalent iron ions (Fe 3+ ), the color changes to a bluish shade of chocolate brown. The state of hemoglobin can therefore be determined or measured by its color or by its infrared or red light transmission (absorbance). At the cathode, the hydrogen ions are reduced by receiving electrons to generate hydrogen. H + + e - -> 1 / 2H2 At the anode, oxyhemoglobin is oxidized to methemoglobin by releasing electrons. Here, it is the heme complex ([Fe(II)]) that is oxidized, and Fe(II) becomes Fe(III). [Fe(II)] -> [Fe(III)] + + e - The redox potential of this reaction is +0.15V, and the reaction proceeds spontaneously to the right (half-life is 1.5 days). Oxygen is produced during the oxidation of heme iron(II). [Fe(III)] + Since has a +1 charge, to maintain electrical neutrality, it is hydrolyzed, [Fe(III)] + + HO -> [Fe(III)]OH + H + The hydrogen ions generated at the positive electrode pass through the separator 109 and move to the negative electrode.

[0079] The hydrogen production device of the present invention monitors the state of binding with oxygen by measuring or grasping the chromaticity of blood or hemoglobin in chromaticity coordinates, as illustrated in Figure 12. Blood and hemoglobin have absorption in the visible region, which can be distinguished from the absorption of methemoglobin (MetHb).

[0080] Therefore, as shown in Figure 11, the composition state of hemoglobin and methemoglobin can be quantitatively measured or observed by measuring the absorption coefficient (absorbance). By measuring or observing, the state of hydrogen generation can be monitored, observed, and controlled.

[0081] As shown in FIG. 1, a variable DC power supply 112 is connected between the terminal electrode 202b and the terminal electrode 202a of the negative electrode 108. The variable DC power supply 112 is configured to be able to generate any voltage in the range of 0V to 10V. In particular, the voltage between 0V and 1V can be set with high accuracy. Also, the magnitude and direction of the current to be passed can be varied. Also, the current to be passed can be limited to a predetermined current. The voltage value is controlled by the control circuit 101.

[0082] When the switch circuit 115 is turned on, a current flows between the negative electrode 108 and the positive electrode 107, and hydrogen gas is generated. If necessary, the voltage value of the variable DC power supply 112 is adjusted or changed.

[0083] Hydrogen (H2) generated at the negative electrode 108 is collected by a gas collector 109 and stored in a gas reservoir 120 via a pipe 110. A current or voltage is applied between the negative electrode 108 and the positive electrode 107 to produce hydrogen.

[0084] In the process in which oxyhemoglobin (HbO2) is oxidized to methemoglobin (MetHb) at the positive electrode 107, oxygen is released because methemoglobin (MetHb) has no oxygen adsorption function.

[0085] Oxyhemoglobin (HbO2) and methemoglobin (MetHb) have different colors. Therefore, when oxyhemoglobin changes to methemoglobin (MetHb), it can be determined by its color. As shown in FIG. 11, by measuring the absorption intensity (absorbance) of a specific wavelength with a color measuring device 234, the composition, generation, and conversion ratio of oxyhemoglobin (HbO2) and methemoglobin can be determined. It goes without saying that the chromaticity may also be measured with the color measuring device 234, as described in FIG. 12.

[0086] The absorbance or chromaticity measured by the color measuring instrument 234 may be of either a reflection type (measuring reflected light from a target substance, etc.) or a transmission type (measuring light transmitted through a target substance, etc.). Methemoglobin (MetHb) does not have the function of adsorbing oxygen. As methemoglobin (MetHb) is produced, oxygen is generated from the positive electrode 107.

[0087] FIG. 2 is an explanatory diagram of the hydrogen production device and hydrogen production method of the present invention. The blood used can be obtained in large quantities from cows, pigs, and chickens, which are used as meat. The blood is collected in a blood collection container 220. The blood is poured into or mixed with a blood adjustment container 209. A blood preservation solution 204 is contained in a preservation solution container 203. The preservation solution container 203 is made of polyvinyl chloride, for example.

[0088] The blood preservation solution 204 contains 2.20 w / v% sodium citrate hydrate and 0.80 w / v% citric acid hydrate. The blood preservation solution 204 is injected into a blood adjustment container 209. The blood preservation solution 204 is used at a ratio of 204 (mL) per 100 (mL) of blood volume. However, if the storage period is short, no preservation solution is necessary and storage at room temperature is possible. For long-term storage, refrigeration is preferable. In the blood adjustment container 209, the blood preservation solution 204 and the blood are stirred and mixed by the stirrer 103 to become adjusted blood 206.

[0089] The conditioned blood 206 is sent to a centrifuge 208. The centrifuge 208 is provided with a plurality of separation chambers 210 (separation chamber 210a, separation chamber 210b, separation chamber 210c, separation chamber 210d). The conditioned blood 206 is injected into the separation chambers 210 sequentially. A rotating shaft 231 is disposed at the center position of the centrifuge 208, and the separation chambers 210 rotate around the rotating shaft 231. In the process of separating hemoglobin from blood, if the blood is used as is, the following steps can be omitted.

[0090] When blood is centrifuged, red blood cells can be separated. When fresh water is added to the separated red blood cells, the red blood cells are ruptured by osmotic pressure, and hemoglobin is eluted. Hemoglobin can be obtained by separating the shells of the red blood cells by centrifugation. Before spinning, the whole blood is mixed. Once the centrifugation process begins, the blood separates into layers of air, plasma, and red blood cells in the separation chamber 210.

[0091] Next, the speed slows down and the slider (not shown) starts to move, and the separation process is started by applying pressure. After that, the sensor detects the interface between the air and the plasma, and the clamp (not shown) switches and the plasma is transferred to the plasma bag. After the plasma has been pushed out and the sensor detects the red blood cells, the clamp closes. To ensure the fluidity of the red blood cell component, the viscosity is adjusted by adding blood preservation solution 204, saline, etc. If necessary, the red blood cell component is sent to the oxygen adsorber 207. In the oxygen adsorber 207, hemoglobin adsorbs oxygen and becomes oxyhemoglobin (HbO2).

[0092] Red blood cell components contain hemoglobin. The hemoglobin undergoes oxygen concentration, pH, and temperature adjustment in the oxygen adsorber 207. When the temperature of hemoglobin decreases and the oxygen gas concentration increases, the oxygen dissociation curve shifts to the left, and hemoglobin becomes more likely to bind to oxygen.

[0093] Blood or hemoglobin is introduced and placed in the oxygen adsorption device 207. Oxygen or air is bubbled through the oxygen adsorption device 207. By bubbling, hemoglobin binds to or absorbs oxygen, becoming oxyhemoglobin. During bubbling, the pH is increased. By increasing the temperature, the conversion and change to oxyhemoglobin is improved.

[0094] The binding of hemoglobin to oxygen is affected by changes in the higher-order structure of hemoglobin. In other words, when one molecule of oxygen binds to hemoglobin, the structure of the other hemes that are not bound to oxygen changes to a state in which they can more easily bind to oxygen. Therefore, the binding of oxygen is accelerated. Hemoglobin that binds to oxygen turns bright red, making it easy to measure or understand the oxygen binding state.

[0095] Hemoglobin turns bright red when bound to oxygen, so oxygen saturation (the percentage of hemoglobin bound to oxygen) can be measured, obtained, or observed by measuring absorbance or color.

[0096] Figure 13 shows the absorbance curves that show which light is absorbed more by oxyhemoglobin (HbO2) bound to oxygen and by hemoglobin (Hb) that has released oxygen. The color of the light is represented by the wavelength on the horizontal axis. Wavelength w1 is red light, and wavelength w2 is infrared light.

[0097] The two graphs (solid line, dotted line) show which wavelengths HbO2 and Hb absorb well and which wavelengths they do not absorb well. The lower the line, the less that wavelength is absorbed (the more it passes through).

[0098] Hemoglobin bound to oxygen is bright red because it does not absorb much red light and allows it to pass through. Hemoglobin that has released oxygen is dark because it absorbs light well.

[0099] When red light (R) is applied to blood, if there is more hemoglobin and oxygen bound to it, more light passes through and the sensor receives more light. Infrared light (IR) passes through blood with or without hemoglobin and oxygen bound to it.

[0100] If HbO2 increases and Hb decreases, the sensor receives more red light (R) and less infrared light (IR). Inversely, the sensor receives less red light and less infrared light. In other words, if you know the ratio of R / IR received by the sensor, you can find the ratio of HbO2 to Hb, i.e., oxygen saturation.

[0101] The relationship between the ratio of the variable components of the transmitted light amount of red light (R) and infrared light (IR) and the SpO2 value varies depending on the LED wavelengths of R and IR used. The relation between the two is called the calibration constant.

[0102] In the color measurement instrument 234 of the present invention, the LED of the light source can be changed. Therefore, by selecting the emission wavelength of the LED, the wavelength w1 and the wavelength w2 can be set arbitrarily. In the oxygen adsorber 207, the ratio, amount and oxygen saturation of oxyhemoglobin are quantified by the method described with reference to FIG.

[0103] 13 shows a color measuring device 234 that measures or observes oxygen saturation based on the relationship between the ratio of the fluctuation components of the amount of transmitted light of red light (R) and infrared light (IR) and the SpO2 value. In other words, the amount and ratio of oxyhemoglobin that has adsorbed oxygen are measured, observed, or obtained. As shown in FIG. 13, infrared light IR (wavelength w2) passes through blood with little difference whether hemoglobin is bound to oxygen or not.

[0104] If HbO2 increases and Hb decreases, the amount of red light (R wavelength w1) received by the light receiving sensor (not shown) increases, and the amount of infrared light (IR) does not change much. If HbO2 decreases and Hb increases, the amount of infrared light (IR wavelength w2) does not change much. In other words, if the ratio of R / IR received by the sensor is known, the ratio of HbO2 to Hb, i.e., oxygen saturation, can be determined.

[0105] The %SpO2 is calculated from the R / IR ratio using a calibration constant. The relationship between the ratio of the variable components of the transmitted light amount of red light (R) and infrared light (IR) and the SpO2 value varies depending on the wavelength of the LED used to emit the R and IR light. The calibration constant is calculated from the relationship between the two. The calibration constant is determined by experimentally determining the correlation with the SaO2 value.

[0106] In the color measuring device 234 of the present invention, the LED of the light source can be changed. Therefore, the wavelengths w1 and w2 can be set arbitrarily. In addition, light of a specific wavelength (R, IR) may be transmitted from a light source such as white light through a color filter and irradiated onto blood, hemoglobin, etc. The above embodiment is an explanation of an embodiment of the R / IR color measuring instrument 234. The color measuring instrument 234 of the present invention is not limited to this.

[0107] Fig. 12 is an explanatory diagram of a color measuring device 234 in another embodiment. Fig. 12 shows an xy chromaticity diagram. However, it is not necessary to be limited to xy chromaticity in expressing the change in chromaticity. It may be uv chromaticity or u'v' chromaticity.

[0108] The chromaticity is determined by preparing three physical filters (combined with a sensor) and measuring the reflected (or transmitted) light from the sample. At this time, the transmission characteristics of the physical filters are adjusted so that the response characteristics of each sensor are the response characteristics (or linear characteristics therefrom).

[0109] When hemoglobin in blood binds with oxygen, it is bright red, for example, as shown by the a coordinate in Figure 12. Hemoglobin in a state where oxygen has dissociated is dark red, as shown by the b coordinate in Figure 12. The difference between the a coordinate and the b coordinate is shown as △xy. Therefore, by observing or measuring the a coordinate and the b coordinate to obtain △xy, it is possible to determine that hemoglobin has bound oxygen when △xy is equal to or exceeds a predetermined value. The proportion of hemoglobin that has bound with oxygen and become oxyhemoglobin can also be obtained.

[0110] As described above, the color measuring device 234 used in the hydrogen generation device of the present invention has a light emitting source (not shown), and light from the light emitting source passes through or is reflected by the blood or hemoglobin on the positive electrode, etc., and the light is received by a light receiving sensor.

[0111] Blood or hemoglobin absorbs, transmits, or reflects light of specific wavelengths depending on the state of oxygen binding or absorption. Also, the chromaticity of the transmitted (or reflected) light changes depending on the absorption state or distribution ratio of the light of the wavelength.

[0112] The color measurement device 234 measures or obtains changes in R / IR, chromaticity, etc., due to light of a specific wavelength or distribution, thereby obtaining information such as the oxygen binding state of blood or hemoglobin.

[0113] Based on the measurement data from the color measuring device 234, the discharge, discharge ratio, and discharge rate of blood or hemoglobin from the oxygen adsorption device 207, or the injection, injection ratio, and injection rate of blood or hemoglobin to the oxygen adsorption device 207 are changed, set, and implemented, and the hydrogen generation device is controlled.

[0114] The data of the color measurement device 234 is set by measuring, observing or acquiring a reference blood or hemoglobin in advance and setting a calibration value or a reference value. The calibration value or the reference value is used to perform calibration of R / IR, XY chromaticity, etc.

[0115] A color measuring device 234 is disposed or attached to the oxygen adsorber 207. In the oxygen adsorber 207, hemoglobin adsorbs oxygen and becomes oxyhemoglobin. Alternatively, the ratio of hemoglobin that has adsorbed oxygen is increased. When a predetermined oxygen saturation level and oxygen adsorption ratio are reached, the oxygen adsorber 207 discharges blood and the like from the oxygen adsorber 207.

[0116] The blood combined with oxygen is sent to pump 403 and injected into the positive electrode via injection tube 222a. The injection timing and injection speed are adjusted or set by the timing of opening and closing the solenoid valve 405, the opening and closing time, the opening and closing angle of the valve, etc. The flow rate per unit time can be controlled by adjusting the opening and closing angle of the valve.

[0117] The solenoid valve 405 is not limited to an electromagnetic switch. It may be a mechanical valve that is manually opened and closed, or may be a valve that automatically opens and closes in response to a change in pressure. The solenoid valve 405 may be in any form as long as it can allow liquid or the like to flow out by opening it and can hold or suppress the movement of liquid or the like by closing it. The valve may be capable of not only opening and closing, but also increasing or decreasing the flow rate. All of these are within the scope of the technical concept of the present invention.

[0118] At the negative electrode, the pH is measured with a pH meter 111. When using sulfuric acid or phosphoric acid, the SO4 2- or PO4 3- Or HPO4 2- Since hydrogen does not pass through the ion exchange membrane, it remains at the negative electrode. Therefore, the pH of the negative electrode solution does not change significantly due to hydrogen generation. Therefore, it is preferable to use an aqueous solution of sulfuric acid or phosphoric acid.

[0119] As hydrogen gas is produced, the aqueous solution 227 decreases, so water or other substances must be added or replenished as necessary. When using a polymer membrane or glass filter, pH fluctuations are unavoidable. In that case, add acid.

[0120] If blood is kept at a neutral pH (7 to 8) at room temperature, most of the oxygen will be adsorbed (oxyhemoglobin) and it can be used as is in the positive electrode solution.

[0121] When the pH reaches a certain level or higher, the aqueous solution 227 is replaced or the aqueous solution 227 is injected from the aqueous solution container 116 into the negative electrode. The aqueous solution container 116 is not limited to a container. Anything that can hold a certain amount of aqueous solution may be used. For example, it may be in the form of a sponge.

[0122] Color measuring instrument 234 will be described below with reference to Figures 11 and 12. Color measuring instrument 234 has at least one of the functions, mechanisms, and structures of a function for measuring or observing the extinction coefficient and absorbance described in Figure 11, and a function for measuring or observing chromaticity described in Figure 12.

[0123] When hemoglobin in blood binds with oxygen, it turns a bright red color. The degree of redness can be used to detect or measure oxygen saturation (the proportion of hemoglobin bound to oxygen, or the proportion of oxyhemoglobin).

[0124] Methemoglobin (MetHb) is a form of hemoglobin in which the divalent (ferro) iron ion is replaced by a trivalent (ferro) iron ion. Methemoglobin cannot carry oxygen and is a chocolate brown with a bluish tint. Oxyhemoglobin, which is hemoglobin bound to oxygen, is the bright red color of arterial blood.

[0125] If oxyhemoglobin is oxidized to produce methemoglobin at the positive electrode, the color will change from the bright red of oxyhemoglobin to the bluish chocolate brown color of methemoglobin.

[0126] Therefore, by monitoring (measuring) the absorbance or chromaticity at a specific wavelength, it is possible to quantitatively determine the extent to which hemoglobin (oxyhemoglobin) has changed to methemoglobin.

[0127] In Figure 11, like Figure 13, the vertical axis shows the absorbance and absorption coefficient curves indicating which light is absorbed more by oxyhemoglobin (HbO2) bound to oxygen and methemoglobin (MetHb). The dotted line shows methemoglobin (MetHb), and the solid line shows hemoglobin bound to oxygen (HbO2) (oxyhemoglobin). The horizontal axis shows the wavelength (nm).

[0128] Hemoglobin bound to oxygen, called oxyhemoglobin (HbO2), is the bright red color of arterial blood. Methemoglobin (MetHb) is a "chocolate brown with a bluish tint."

[0129] When oxyhemoglobin (HbO2) is oxidized to produce methemoglobin (MetHb), the color changes from the bright red of oxyhemoglobin to the bluish chocolate brown color of methemoglobin.

[0130] Therefore, by monitoring, measuring, and acquiring absorbance or color at a specific wavelength, it is possible to quantitatively determine the extent to which hemoglobin (oxyhemoglobin) has changed to methemoglobin, or to grasp the ratio, etc. Understanding the change to methemoglobin is useful for determining the amount of hydrogen gas generated, the positive electrode blood, and the timing of replacement of hemoglobin.

[0131] Wavelength w1 is a red wavelength, and wavelength w2 is an infrared wavelength. Wavelength w1 is selected within the red wavelength range, at which there is a difference in absorbance between oxyhemoglobin (HbO2) and methemoglobin (MetHb). For ease of explanation, let w1 = 670 nm as an example. Wavelength w2 is selected within the infrared wavelength range, at which there is a difference in absorbance between oxyhemoglobin (HbO2) and methemoglobin (MetHb). For ease of explanation, let w1 = 920 nm as an example.

[0132] The wavelength w1 is selected from the range of red wavelengths in which the difference in absorbance between oxyhemoglobin (HbO2) and methemoglobin (MetHb) is large. The wavelength w1 is preferably in the range of 600 nm to 720 nm. More preferably, the wavelength w1 is in the range of 620 nm to 700 nm.

[0133] The wavelength w2 is selected from the infrared wavelength range in which the difference in absorbance between oxyhemoglobin (HbO2) and methemoglobin (MetHb) is large. The wavelength w2 is preferably in the range of 800 nm or more and 980 nm or less. More preferably, the wavelength w2 is in the range of 880 nm or more and 960 nm or less.

[0134] In the wavelength range from 760 nm to 840 nm, the difference t between oxyhemoglobin (HbO2) and methemoglobin (MetHb) is small. For example, let t be the difference at a wavelength of 800 nm. By obtaining the values ​​of s1 with respect to t and s2 with respect to t, the amount of change or the rate of change in oxyhemoglobin (HbO2) and methemoglobin (MetHb) can be quantified.

[0135] By measuring the values ​​of absorbance c1, absorbance a1, absorbance b1, absorbance c2, absorbance a2, and absorbance b2, the amount or rate of change in oxyhemoglobin (HbO2) and methemoglobin (MetHb) can be quantified.

[0136] By measuring at least one of the values ​​of absorbance a1 relative to absorbance c1, the value of absorbance b1 relative to absorbance c1, the value of absorbance a2 relative to absorbance c2, and the value of absorbance b2 relative to absorbance c2, the amount or rate of change in oxyhemoglobin (HbO2) and methemoglobin (MetHb) can be quantified.

[0137] Hemoglobin bound to oxygen (oxyhemoglobin (HbO2)) is bright red. This is because it transmits only red light without absorbing much of it. In other words, it has low absorbance of red wavelengths of light. On the other hand, methemoglobin (MetHb) is a chocolate brown with a bluish tint. It easily absorbs red wavelengths of light.

[0138] At the positive electrode (anode) 107, electrons are released and oxyhemoglobin is oxidized to methemoglobin. The heme complex ([Fe(II)]) is oxidized, and Fe(II) becomes Fe(III). Depending on the rate at which oxyhemoglobin is converted to methemoglobin, the color changes to chocolate brown with a bluish tint.

[0139] When oxyhemoglobin is oxidized and changes to methemoglobin, the absorbance difference s1 and the absorbance difference s2 become larger. The initially measured values ​​of absorbance a1 and absorbance b1 of oxyhemoglobin are used as reference values, and as it changes to methemoglobin, they approach the values ​​of absorbance a2 and absorbance b2. The amount of change in hydrogen gas can be measured or obtained from the values ​​of absorbance a1 to absorbance a2 and absorbance b1 to absorbance b2.

[0140] In the vicinity of a wavelength of 800 nm, the difference in absorbance between oxyhemoglobin and methemoglobin is small (the value of t is small). Therefore, it is preferable to calibrate absorbance a1, absorbance a2, absorbance b1, and absorbance b2 based on the values ​​of absorbance c1 and absorbance c2 at a wavelength of 800 nm, etc.

[0141] In the color measuring instrument 234 of the present invention, the LED of the light source can be changed. Therefore, the wavelengths of light emitted by the LED can be arbitrarily set to wavelengths w1 and w2. Also, the light from the light source emitting wavelengths from red to infrared can be configured to extract specific red light or specific infrared light through a color filter so that absorbance and the like can be measured. The above items are similar to those in the measurement of XY chromaticity. Also, light generated by an organic EL element, light generated by a high-pressure mercury lamp, etc. can be used instead of the LED.

[0142] The above embodiment is an explanation of an embodiment of the color measuring device 234 by R / IR. The color measuring device 234 of the present invention is not limited to this. FIG. 12 is an explanatory diagram of the color measuring device 234 in another embodiment. FIG. 12 shows an xy chromaticity diagram. However, it is not necessary to be limited to xy chromaticity in expressing the change in chromaticity. It may be uv chromaticity or u'v' chromaticity.

[0143] The chromaticity is determined by preparing three physical filters (combined with a sensor) and measuring the reflected (or transmitted) light from the sample. In this case, the transmission characteristics of the physical filters are adjusted so that the response characteristics of each sensor are the response characteristics (or linear characteristics therefrom). When hemoglobin in blood binds with oxygen, it is bright red, as shown by the a coordinate in Figure 12.

[0144] Methemoglobin, which is the oxidized form of oxyhemoglobin, turns a bluish color like chocolate brown, and is shown as coordinate c in Figure 12(b), for example. The difference between coordinate a and coordinate c is shown as △xy. Therefore, by monitoring or measuring coordinate a and coordinate c to obtain △xy, it can be determined that a considerable or specified amount of methemoglobin has been reached when △xy exceeds a certain value.

[0145] The voltage or current applied between the positive electrode 107 and the negative electrode 108 is controlled by the electrode voltage control circuit 114, and the amount of hydrogen generated is measured and controlled by the gas flow meter 411.

[0146] The aqueous solution container 116 is disposed at the negative electrode. The aqueous solution container 116 and the negative electrode are connected by an injection pipe 222b, and new aqueous solution is injected into the negative electrode through the injection pipe 222b. Alternatively, the pH is measured by a pH meter 111 at the negative electrode, and when the pH reaches a certain level or higher, the aqueous solution 227 is replaced, or the aqueous solution 227 is injected from the aqueous solution container 116 into the negative electrode. Deteriorated aqueous solution 227 is discharged from a discharge pipe 223b. Hydrogen (H2) generated at the negative electrode 108 is collected by a gas collector 109 and transferred through a pipe 110 to a gas reservoir 120.

[0147] The stirring fan 103 is rotated in a direction to spray up the aqueous solution 227. Also, by rotating it in the direction of the gas collector 109, the efficiency of collecting the generated hydrogen can be increased. Instead of the stirring fan 103, a pump that generates a water flow may be used.

[0148] Hydrogen embrittlement may occur in the gas collector 109 and the piping 110. Hydrogen affects metals, reducing their toughness and making them more susceptible to brittle fracture. Hydrogen embrittlement is more severe in steels with higher strength, and is particularly likely to occur in metals with high tensile strength.

[0149] The gas reservoir 120, the gas collector 109, and the piping 110 are subjected to a baking process. The baking is performed for the purpose of releasing the absorbed hydrogen to prevent brittle fracture. The specific method varies depending on the metal material and the type and processing performed on it, but heating is performed at 190°C to 220°C for 2 hours to 24 hours. It is preferable to deposit or coat glass or an inorganic material on the inner surfaces (eg, the portions in contact with hydrogen) of the gas reservoir 120, the gas collector 109, and the pipe 110.

[0150] The negative electrode 108 reduces water (or hydrogen ions) to generate hydrogen (H2). The positive electrode 107 does something completely different from the decomposition of water. It does not generate oxygen (O2), but oxidizes metal ions. It can be oxidized at a lower voltage than water. The oxidation reaction is rapid.

[0151] Hydrogen (H2) generated at the negative electrode 108 is collected by a gas collector 109 and is collected in a gas reservoir 120 through a pipe 110. A hydrogen gas dryer (not shown) is disposed at the input of the gas reservoir 120.

[0152] A hydrogen gas dryer (not shown) is a device that removes moisture contained in hydrogen gas. An example of the adsorption type is one in which moisture is absorbed into an adsorbent to remove moisture. Some types use a heater to regenerate the adsorbent, while others do not. For the heating type, the main circuit is made up of a regeneration tower heater replacement valve, a regeneration path valve, etc. to match the heater.

[0153] An electrode voltage control circuit 114 is connected between the negative electrode 108 and the positive electrode 107. In the electrode voltage control circuit 114, an ammeter 512, a switch circuit 115, and a variable DC power supply 112 are disposed or installed.

[0154] The variable DC power supply 112 is configured to be able to generate any voltage in the range of 0V to 20V. The variable DC power supply 112 is configured to be able to control the output current to a constant current. Also, it is configured to be able to reverse the current direction and change the voltage polarity. It is preferable that the output voltage be changed based on the generation state of hydrogen being generated.

[0155] If the amount of hydrogen generated becomes abnormally low or high compared to a predetermined value, an alarm is issued since there is a possibility that an abnormality has occurred in the hydrogen generating device, and the hydrogen generating device is also stopped.

[0156] The variable DC power supply 112 is configured to be able to vary the applied current or voltage in response to the amount of hydrogen generated. The variable DC power supply 112 can change the direction of current flow. By changing the direction, the positive electrode 107 and the negative electrode 108 can be essentially swapped. The variation of the voltage or current is controlled by the control circuit 101.

[0157] The positive electrode 107 can be reduced by changing the direction of current flow or the polarity of the applied voltage from the variable DC power supply 112. Also, methemoglobin can be converted to oxyhemoglobin.

[0158] An ammeter 512 is disposed in the path through which the current flows. The ammeter 512 measures the current flowing in the path, and the measured current value and current change are sent to the control circuit 101. The control circuit 101 controls the on (closed) and off (open) of the switch circuit 115 based on the current value etc., and changes or controls the output value of the variable DC power supply 112. Hydrogen is generated by applying a potential. The state of hydrogen production (hydrogen generation) is grasped by the current value measured by the gas flow meter 411 or the ammeter 512.

[0159] When the switch circuit 115 is turned on, a current flows between the negative electrode 108 and the positive electrode 107, and hydrogen is generated. It is preferable to change the voltage applied between the positive electrode 107 and the negative electrode 108 in accordance with the amount of hydrogen produced. The voltage or current of the variable DC power supply 112 is adjusted so that the amount of hydrogen produced per unit time falls within a predetermined range.

[0160] When a voltage is applied between the negative electrode 108 and the positive electrode 107, hydrogen is generated at the negative electrode. If sulfuric acid or phosphoric acid is used as the acid and a cation exchange membrane is used as the separator, there is no large change in the pH of the negative electrode.

[0161] The hydrogen collected in the gas storage tank 120 is mixed with other gases such as nitrogen gas. Therefore, hydrogen purification is performed. Although not shown in Figures 1 and 2, the present invention has a hydrogen purifier (not shown). The hydrogen purifier (not shown) uses a membrane separation method.

[0162] Membrane separation, one of the hydrogen purification technologies, is a technology that uses pressure differences to remove impurities during hydrogen production and use, and obtain highly pure hydrogen. Among the separation membranes, polymer separation membrane modules have little performance degradation due to water vapor and are lightweight. Polymer separation membrane modules contain hydrogen-compatible materials and are equipped with separation membranes with highly controlled pore structures.

[0163] The negative electrode 108 is vibrated by an ultrasonic generating element used in an ultrasonic cleaning device. The hydrogen gas generated at and attached to the negative electrode 108 is dispersed from the negative electrode 108, so that it can be efficiently collected by the gas collector 109.

[0164] The above items are preferably also applied to the positive electrode 107. It goes without saying that the above items can also be applied to other embodiments, for example, the cylindrical embodiment in Fig. 3, etc., and the embodiments in Figs. 7, 8, 9, 10, etc.

[0165] By setting the stirring fan 103 in a blowing direction (from the bottom to the top of the paper), the hydrogen generated on and attached to the negative electrode 108 can be dispersed from the negative electrode 108, and the hydrogen can be efficiently collected by the gas collector 109.

[0166] The amount of hydrogen collected by the gas collector 109 is measured by a gas amount measuring device (gas flow meter 411). The current supplied by the variable DC power supply 112 varies depending on the amount of hydrogen measured by the gas amount measuring device (gas flow meter 411).

[0167] When the amount of hydrogen per unit time is greater than a predetermined value, the amount of current flowing through the negative electrode 108 is reduced. When the amount of hydrogen per unit time is less than a predetermined value, the amount of current is increased. The current value (voltage value) may be varied in response to the current (voltage) application time, rather than in response to the measured amount of hydrogen produced.

[0168] The separator 119 is, for example, a cation exchange membrane. The positive electrode 107 and the negative electrode 108 are separated by the separator 119. When the switch circuit 115 is turned on (closed), the hydrogen production reaction proceeds.

[0169] The amount or rate of change in hemoglobin bound to oxygen at the positive electrode is quantitatively determined by measuring, monitoring, and acquiring the data using the color measuring device 234 described in Figures 11, 12, and 13. The blood or hemoglobin immediately after being injected into the positive electrode is measured using the color measuring device 234 and used as a reference value. It is also calibrated.

[0170] The change of oxyhemoglobin to methemoglobin through oxidation can be observed or measured by a change in color according to the rate of oxidation. The state of change is measured or monitored by a color measuring device 234.

[0171] When the R / IR ratio or chromaticity changes to a predetermined value or exceeds a predetermined value, it is determined that the conversion to methemoglobin has been completed or ended, and the methemoglobin is discharged from the discharge pipe 223 a to the collector 224 . After the methemoglobin has been discharged, the solenoid valve 405 is opened and new oxyhemoglobin, blood or hemoglobin is introduced into the positive electrode via the injection tube 222a.

[0172] The blood (in which the heme iron has been oxidized to Fe(III)) or methemoglobin discharged into the collector 224 is dried by hot air from a dryer 226 to become blood powder 225. The blood powder 225 consisting of the dried blood or hemoglobin is a good protein and can be used as livestock feed or a pharmaceutical material.

[0173] 3, 4, 5, 6, and 10 show embodiments in which the hydrogen production device (hydrogen production apparatus) 201 of the present invention is configured or formed in a cylindrical shape, a linear shape, etc. In the following, for ease of explanation, the hydrogen production device will be described as having a cylindrical shape.

[0174] 3, 4, 5, 6, 7, 8, 9, and 10, each diagram (a) is a partial diagram and an explanatory diagram that typically illustrates a cross section of the hydrogen production device (hydrogen production apparatus) 201. Each diagram (b) is a cross section taken along line AA' in each diagram (a).

[0175] 3, 4, 5, 6, 7, 8, 9, and 10 are parts of FIG. 1 and FIG. 2. Or they can be combined with FIG. 1 and FIG. 2. Or they can be combined in whole or in part. Contents explained in FIG. 1, FIG. 2, etc. are applied to contents not explained or shown in FIG. 3, 4, 5, 6, 7, 8, 9, and FIG. 10.

[0176] Blood (or hemoglobin) 221 is injected, filled, or placed in the cylindrical positive electrode 107. As described with reference to Figs. 1 and 2, etc., at the positive electrode, it is preferable to bubble, stir, mix, etc. oxygen or air into the blood or hemoglobin, thereby promoting the conversion of hemoglobin to oxyhemoglobin. It goes without saying that the above matters, contents, and embodiments can also be applied to the embodiments of FIGS. 4, 5, 6, 7, 8, 9, 10, and 14.

[0177] In the embodiments of Figs. 7, 8, 9 and 10, similarly to the other embodiments, it is preferable to provide a temperature regulator / setter capable of setting or varying the temperature of the aqueous solution 221 and the aqueous solution 227.

[0178] The positive electrode 107 is made of a conductive material or a metal material. For example, it is in the shape of a sponge, a coil, or a net-like tube. Blood and hemoglobin (oxyhemoglobin) move through the net-like or mesh-like holes.

[0179] Examples of materials for forming the positive electrode 107 include gold, platinum, stainless steel, titanium, aluminum alloy, Nitinol alloy (nickel-titanium: TiNi), iridium alloy, and a mixture of graphite and activated carbon. In particular, it is preferable to use a TiNi-based shape memory alloy.

[0180] The shape and structure of the positive electrode 107 are cylindrical, polygonal, or rectangular mesh-shaped metals such as titanium, stainless steel, nitinol alloy (nickel-titanium: TiNi), platinum-iridium alloy, platinum, etc., made of the above-mentioned metals in the form of fibers. These are sometimes called stencil electrodes 107.

[0181] A separator 119 is formed or disposed on the outer periphery of the positive electrode 107. The separator 119 may be a cation exchange membrane, or a hydrophilic polymer membrane or glass filter that does not allow blood or hemoglobin to pass through. Another example is a fluorine-based cation exchange membrane made from a sulfonic acid polymer.

[0182] 3(a), a cylindrical container 102 is disposed at the outermost periphery. The container is made of a resin material such as polyethylene resin, polypropylene resin, etc. A negative electrode 108 is formed or configured on the inner periphery of the container 102.

[0183] Although the container 102, the positive electrode 107, and the negative electrode 108 are described as being cylindrical, the present invention is not limited thereto. Needless to say, they may be of other shapes, forms, and structures, such as square, rectangular, polygonal, honeycomb, linear, and pipe shapes. In addition, the positive electrode 107 and the negative electrode 108 may be formed or configured of a metal mesh, a porous metal plate, or porous carbon. Examples of porous metal plates include expanded metal, punching metal, porous metal foil, and porous carbon.

[0184] The positive electrode 107 and the negative electrode 108 are not limited to being concentric. For example, a plurality of cylindrical positive electrodes 107 may be configured or arranged within the negative electrode 108. Also, a plurality of cylindrical negative electrodes 108 may be configured or arranged within the positive electrode 107.

[0185] It goes without saying that the positive electrode 107 and the negative electrode 108 may be configured or formed as a honeycomb structure. It goes without saying that the honeycomb structure is not limited to a hexagon, and may be a triangle or a rectangle.

[0186] It goes without saying that the above matters are also applicable to other embodiments in the present specification and drawings, and that a part or all of the above can be combined with other embodiments.

[0187] Examples of the negative electrode 108 include gold, platinum, silver, acid-resistant stainless steel, aluminum alloy, titanium alloy, nickel alloy, and carbon. Stainless steel is particularly acid-resistant and relatively inexpensive. For example, S-TEN, COR-TEN, and MARILOY are examples. An electrode voltage control circuit 114 is connected to the negative electrode 108 and the positive electrode 107.

[0188] An aqueous solution 227 is filled between the negative electrode 108 and the separator 119. Blood (hemoglobin) 221 is controlled by an electromagnetic valve 405 and filled into the positive electrode 107 via an injection tube 222a, as shown in FIGS.

[0189] Hydrogen gas is generated at the negative electrode 108, and the hydrogen is collected by a gas collector 109. At the positive electrode 107, the heme iron at the active site of blood or hemoglobin (both of which have adsorbed oxygen) is oxidized from divalent to trivalent. The state of change is observed by a color measuring device 234.

[0190] The color changes as oxyhemoglobin changes to methemoglobin. The color change is measured and monitored by a color measuring device 234. When the measured or monitored value reaches a predetermined reference value, the blood or hemoglobin is discharged into a collector 224, and new blood or hemoglobin (oxyhemoglobin) 221 is introduced into the positive electrode.

[0191] At the positive electrode 107, the amount of oxygen generated increases or decreases depending on the state of change to methemoglobin. By monitoring or observing the increase or decrease in the amount of oxygen generated, the amount of hydrogen generated can be estimated. By monitoring or observing the increase or decrease in the amount of hydrogen generated, the amount of oxygen generated can be estimated. Therefore, by monitoring, observing, and acquiring the amount of oxygen generated, the rate of oxygen generation, and the increase or decrease in the amount of oxygen generated, the hydrogen generation state can be predicted and controlled by the controller 101, and good hydrogen generation control can be realized. Furthermore, by monitoring, observing, and acquiring the amount of hydrogen generated, the rate of hydrogen generation, and the increase or decrease in the amount of hydrogen generated, the oxygen generation state can be predicted and controlled by the controller 101, and good oxygen generation control can be realized.

[0192] If the pore size of the positive electrode 107 is smaller than the size of hemoglobin, hemoglobin (oxyhemoglobin) cannot pass through the positive electrode 107. Since hemoglobin (oxyhemoglobin) does not move from the positive electrode 107 to the aqueous solution 227, the separator 119 is not necessary.

[0193] Blood or hemoglobin (oxyhemoglobin) 221 is oxidized at the cylindrical positive electrode 107. Hydrogen is continuously produced by the oxidation at the positive electrode and the reduction reaction at the negative electrode.

[0194] 3 has a configuration in which the separator 119 is disposed or formed on the outer periphery of the positive electrode 107. In the embodiment of FIG.

[0195] 5 shows a configuration having a cylindrical pipe-shaped positive electrode 107 in the center. The cylindrical pipe-shaped metal part becomes the positive electrode 107. Blood or hemoglobin (oxyhemoglobin) 221 is placed or injected between the positive electrode 107 and the separator 119. An aqueous solution 227 is placed or injected between the negative electrode 108 and the separator 119. At the positive electrode 107, the oxyhemoglobin 221 receives electrons and generates oxygen. The other configurations are the same as those in Figs. 3 and 4, so a description thereof will be omitted. In the above embodiment, the negative electrode 108 is disposed on the outer periphery, and the positive electrode 107 is disposed on the inner periphery. However, the present invention is not limited to this. FIG. 6 shows a configuration or structure in which the positional relationship between the negative electrode 108 and the positive electrode 107 in FIG. 5 is reversed.

[0196] It has a cylindrical pipe-shaped negative electrode 108 in the center. The cylindrical pipe-shaped metal part serves as the negative electrode 108. An aqueous solution 227 is placed or injected between the negative electrode 108 and the separator 119. Blood or hemoglobin 221 is placed or injected between the positive electrode 107 and the separator 119. Other configurations are similar to those in Figs. 3, 4, and 5, and therefore will not be described. 3, 4, 5, and 6, the positive electrode 107 and the negative electrode 108 are described as being cylindrical, but the present invention is not limited to this.

[0197] 7, like Figs. 1 and 2, for example, the container 102 is rectangular or cubic in shape. Plate-shaped negative electrodes 108 and positive electrodes 107 are formed or arranged in the container 102. The multiple positive electrodes 107 are connected to a common electrode voltage control circuit 114. The multiple negative electrodes 108 are connected to a common electrode voltage control circuit 114.

[0198] 7, blood or hemoglobin (oxyhemoglobin) 221 is placed or injected on both sides of the positive electrode 107. A separator 119 is placed between the positive electrode 107 and the negative electrode 108. Other configurations and the like have been described in FIG. 1, FIG. 2, etc., and therefore will not be described here.

[0199] In the embodiments of Figs. 3, 4, 5, 6, and 10, the positive electrode 107 and the negative electrode 108 are described as being cylindrical. Fig. 8 shows a configuration in which two planar negative electrodes 108 are arranged in parallel, and an aqueous solution 227 is filled between the two planar negative electrodes 108. A separator 119 and a positive electrode 107 (not shown) are arranged in the aqueous solution 227 in a curved tube shape. Blood or hemoglobin (oxyhemoglobin) 221 (not shown) is injected or flows in the separator 119. Hydrogen is generated at the negative electrode, and the hydrogen is collected by a gas collector 109.

[0200] It is preferable to mix or bubble oxygen and air at the positive electrode. This can improve the production of oxyhemoglobin. In this case, the oxygen adsorber 207 can be omitted. When mixing or bubbling with oxygen or air, it is preferable to adjust the pH and temperature. Needless to say, bubbling may be performed by mixing with oxygen, etc. and stirring, or by applying vibration, etc. to mix. Applying vibration can cause oxygen or hydrogen attached to the positive electrode 107 and negative electrode 108 to be released, improving the efficiency of generating hydrogen, etc.

[0201] Blood or hemoglobin (oxyhemoglobin) 221 in separator 119 is discharged by opening solenoid valve 405b, and is injected into separator 119 by opening solenoid valve 405a. Blood or hemoglobin (oxyhemoglobin) 221 is retained in separator 119 by closing solenoid valve 405b.

[0202] When hemoglobin binds to oxygen, it turns into oxyhemoglobin, which is the bright red color of arterial blood. When hemoglobin does not bind to oxygen, it turns into the dark red color of venous blood.

[0203] 11 and 12, the present invention measures or observes the oxygen binding state of hemoglobin 221 with a color measuring device 234 and controls the discharge of methemoglobin 221 and the injection of oxyhemoglobin 221. The composition and ratio of oxyhemoglobin and methemoglobin are detected and controlled from absorbance.

[0204] Fig. 9 is an explanatory diagram of the injection and discharge of blood or hemoglobin 221. In order to observe multiple locations of blood or hemoglobin (oxyhemoglobin) 221, color measuring instruments 234 are installed or positioned at multiple locations. Note that the positive electrode 107 is omitted from Fig. 9.

[0205] Blood, hemoglobin, and methemoglobin 221 are prone to uneven oxygen binding depending on the part. For example, as shown in Fig. 9(a), the measurement values ​​of color meter 234b, which measures the color, etc., of blood, hemoglobin, and methemoglobin 221 injected first, and color meter 234a, which measures the color, etc. of blood, hemoglobin, and methemoglobin 221 injected later, often differ. By using multiple color meters 234, the oxygen binding state of hemoglobin 221 or the oxidation state of methemoglobin can be quantitatively measured or observed.

[0206] An aqueous solution 227 flows from an injection tube 222b between the separator 119 and the negative electrode 108. Blood or hemoglobin (oxyhemoglobin) 221 is injected, discharged, or held in the separator 119 by an electromagnetic valve (switch) 405a and an electromagnetic valve (switch) 405b.

[0207] 9(a), solenoid valve (switch) 405a is opened and solenoid valve (switch) 405b is closed. Blood or hemoglobin 221 flows into separator 119 from the direction of the arrow.

[0208] 9(b), when the separator 119 is filled with blood or hemoglobin (oxyhemoglobin) 221, the solenoid valve (switch) 405a is closed. Immediately after the solenoid valve (switch) 405a and the solenoid valve (switch) 405b are closed, the color measuring device 234a and the color measuring device 234b measure or obtain initial values. The measured value is at least one of the R / IR ratio and the chromaticity (XY, etc.).

[0209] Next, the electrode voltage control circuit 114 applies a voltage or current between the positive electrode 107 (not shown) and the negative electrode 108. Hydrogen is generated at the negative electrode. At the positive electrode 107, oxyhemoglobin is oxidized to become methemoglobin.

[0210] The state or percentage of oxygen binding can be quantified using at least one of the R / IR ratio and chromaticity (XY, etc.) measured or acquired by the color measuring device 234a and the color measuring device 234b. The rate of change can also be acquired. The state or percentage of oxygen binding is quantified by comparing with the reference value measured in FIG. 9(b). The initial value of blood or hemoglobin is detected by absorbance, and after current is passed, the composition ratio of oxyhemoglobin and the oxidation product methemoglobin is detected.

[0211] When the binding state or binding ratio with oxygen measured by the color measuring device 234a, 234b reaches a predetermined value or exceeds a predetermined value, the solenoid valve (opening / closing device) 405b is opened, as shown in Figure 9 (c), and the blood or hemoglobin 221 is discharged from the discharge pipe 223a to the collector 224. The blood or hemoglobin (heme iron is in an oxidized state) 221 discharged into a collector 224 is dried and collected as blood powder 225.

[0212] Next, as shown in Fig. 9(d), the solenoid valve (switch) 405a is opened, and the blood preservation liquid 204 is injected into the positive electrode 107 (positive electrode). However, the reason for injecting the blood preservation liquid 204 is to prevent the remaining blood in the positive electrode 107 (positive electrode) from coagulating and to wash it. Therefore, the liquid to be injected is not limited to the blood preservation liquid 204, and may be water, salt water, or the like. Also, water with citric acid dissolved therein may be used.

[0213] The inside of the positive electrode 107 (positive electrode) is washed by alternately opening and closing the solenoid valve (switch) 405a and the solenoid valve (switch) 405b and injecting and discharging the blood preservation solution 204, etc. After washing, blood or hemoglobin (oxyhemoglobin) 221 is injected into the positive electrode 107 (positive electrode) as described in FIG. 9(a).

[0214] 8 and 9 show an embodiment in which a plurality of color measuring devices 234 are possessed or installed. As shown in Figs. 8 and 9, by arranging a plurality of color measuring devices 234 at the inlet, outlet, or injection side or discharge side of the aqueous solution 221 (aqueous solution 227), it is possible to measure and observe the change in the aqueous solution 221 (aqueous solution 227) and the state at each part. Therefore, it is possible to efficiently and satisfactorily control the generation state of gas such as hydrogen (oxygen). In addition, it is preferable that the color change is carried out based on or taking into consideration the temperature output by a temperature measuring device (not shown).

[0215] The above points are not limited to the aqueous solution 221 being blood, etc. It goes without saying that the above points can also be applied to embodiments that use aqueous solutions that change color, etc.

[0216] In the embodiment of FIG. 2, hemoglobin is separated from blood by the centrifuge 208, and oxygen is adsorbed to the separated hemoglobin by the oxygen adsorber 207, but the present invention is not limited to this.

[0217] FIG. 10 is a structural diagram and an explanatory diagram of a hydrogen generating device of the present invention, which has a cylindrical structure as shown in FIG. 3(b) and is configured so that the inside or outside can be rotated, and has a centrifugal separation function added.

[0218] Blood 221 and the like are injected between separator 119 and positive electrode 107. Rotation in the direction of arrow A or arrow B generates centrifugal force. The centrifugal force separates blood 221 into plasma and blood cell components containing red blood cells (hemoglobin). A convex portion is formed or arranged on rotating shaft 231, which promotes separation of plasma from blood cell components containing red blood cells (oxyhemoglobin). The centrifugal force causes blood cell components containing red blood cells (oxyhemoglobin) to gather near the separator 119 .

[0219] At the positive electrode (anode) 107, electrons are released, and oxyhemoglobin is oxidized to methemoglobin. The heme complex ([Fe(II)]) is oxidized, and Fe(II) becomes Fe(III). The other configurations are the same as those in Figs. 3 and 4, and therefore will not be described.

[0220] The hemoglobin etc. at the positive electrode is stirred by the convex part of the rotating shaft 231. Oxygen or air may be mixed or bubbled during stirring. The generation of oxyhemoglobin can be improved by bubbling etc. In this case, the oxygen adsorber 207 can be omitted. When mixing or bubbling with oxygen or air, it is preferable to adjust the pH and temperature. Needless to say, bubbling etc. may be performed by mixing with oxygen etc. and stirring etc., or by applying vibration etc. to mix. Applying vibration can cause oxygen or hydrogen attached to the positive electrode 107 and the negative electrode 108 to be released, improving the generation efficiency of hydrogen etc. The above points also apply to the negative electrode, and needless to say, they can also be applied to the embodiments of Figs.

[0221] In the embodiment of the present invention, blood and hemoglobin 221 extracted from mammals are used, but the present invention is not limited to this. For example, artificial red blood cells (Hb-V) in the form of Hb solution encapsulated in liposomes, hemoglobin vesicles as an artificial red blood cell preparation, and artificial oxygen carriers made of hemoglobin nanoparticles may be used.

[0222] In addition, mollusks such as squid and octopus, and arthropods such as crayfish and spiders have "hemocyanin" instead of hemoglobin. Hemocyanin is a huge protein with a molecular weight of several million, and the key to oxygen transport is the two copper ions in the active center.

[0223] Copper ions can be in two states: monovalent and divalent. When oxygen is not bound to them, they act as monovalent copper ions, and when oxygen molecules come, they change to divalent copper ions and can donate electrons to the oxygen. Therefore, hemocyanin can be used as the positive electrode material 221 in the hydrogen generation device and hydrogen generation method of the present invention. By performing electrolysis with different acid concentrations at the cathode and anode, the power required to generate hydrogen can be reduced, resulting in energy savings. In FIG. 15, at pH=0 (e.g., 1 mol sulfuric acid), H + The reduction potential of is close to 0 V, and at pH=11, OH - The oxidation potential of is approximately 0.6V.

[0224] When a hydrogen ion permeable cation exchange membrane is used for the separator 119, and an aqueous solution of sulfuric acid is used for the cathode and an aqueous solution of ammonium hydroxide (NH4OH) is used for the anode, NH4 + does not permeate the separator 119. Therefore, the alkali concentration at the anode does not change due to electrolysis. The pH of 1 mol of NH4OH is 11.6. When electrolyzing 1 mol of sulfuric acid aqueous solution at the cathode, the applied voltage is about 0.6 V, which is about half the rate of electrolysis of water.

[0225] If the ionic radius of the alkali is large, it will not pass through the hydrogen ion permeable cation exchange membrane 119. For example, there are KOH, Mg(OH)2, Ca(OH)2, Ba(OH)2, or organic ions such as tetraethylammonium ion and tetramethylammonium ion. At the cathode, hydrogen is produced. H2O + e - → 1 / 2H2+ OH - (1a) H + + e- → 1 / 2H2(1a') At the anode, oxygen is produced. H2O → 1 / 2O2 + 2H + + e- (1b) 2OH - → H2O + 1 / 2O2 + 2e - (1b') From the above, it is possible to achieve energy savings by performing electrolysis with different acid concentrations at the cathode and anode.

[0226] It goes without saying that the above embodiment can be applied to other embodiments described in this specification and the drawings, and that it can be combined in part or in whole with other embodiments.

[0227] In another embodiment, a hydrogen ion permeable cation exchange membrane is used for the separator 119. An acid solution such as an aqueous sulfuric acid solution is used for the cathode as described in the previous embodiment. An aqueous ammonium hydroxide (NH4OH) solution is added to the blood or hemoglobin 221 of the anode and mixed to perform electrolysis. NH4 + does not permeate the separator 119. Therefore, the alkali concentration at the anode does not change due to electrolysis. The voltage required for electrolysis can be reduced. The alkaline solution may be KOH, Mg(OH)2, Ca(OH)2, Ba(OH)2, or an organic ion, such as tetraethylammonium ion or tetramethylammonium.

[0228] The negative electrode aqueous solution 227 is made acidic, and the positive electrode aqueous solution 221, etc. are made acidic. To make the positive electrode aqueous solution 221, etc. acidic, the above-mentioned acid solution is added or mixed. By using the proton-permeable cation exchange membrane 119, hydrogen can be generated efficiently. Also, the positive electrode aqueous solution 221 may be made an acidic aqueous solution without using hemoglobin, etc., in the positive electrode.

[0229] When oxygen ions and hydroxyl groups are generated at the negative electrode, metal powder such as zinc, iron, copper, chromium, aluminum, magnesium, lead, etc. is added to the negative electrode to bond with the metal and generate metal oxides and metal hydroxides. The generation of metal oxides, oxides, and metal hydroxides improves the efficiency of hydrogen generation. The material added to the negative electrode is not limited to metals. In the case where an internal hydrogen leak occurs in the hydrogen production device of the present invention, gas production in the hydrogen production device is stopped, and a warning and an audio alarm are generated to issue a warning.

[0230] If a leak occurs external to the generator or persists for more than 20 minutes, shut down the hydrogen production equipment to prevent accumulation of hydrogen gas in the lab environment or in any equipment being supplied. The present invention will shut down the system if the internal pressure exceeds 120 psi. It also has an external output signal that can be connected to an external device.

[0231] 14 is an explanatory diagram of a vehicle (car, train, bicycle, bus, truck, etc.) having the hydrogen generation device of the present invention. In the vehicle, blood or the like is stored as fuel in a blood adjustment container 209, hydrogen is generated by the hydrogen generation device installed inside, and the vehicle runs on the generated hydrogen.

[0232] 14 is illustrated and described as a "vehicle", but the present invention is not limited to this. For example, it goes without saying that the present invention can also be applied to generators (devices equipped with the hydrogen generation device of the present invention and generating electricity using generated hydrogen), ships, fuel cells, aircraft, forklifts, iron-making equipment, etc. [Industrial Applicability]

[0233] According to the present invention, hydrogen can be easily generated with low power. In addition, since the present invention uses blood from livestock, etc., which would have been discarded in the past, the present invention can provide a low-cost hydrogen production device and method. [Explanation of symbols]

[0234] 101 Control circuit 102 Container 103 Stirring fan 107 Positive electrode 108 Negative electrode 109 Gas collector 110 Piping 111 pH Meter 112 Variable DC power supply 114 Electrode voltage control circuit 115 Switch Circuit 116 Aqueous solution container 119 Separator 120 Gas Reservoir 201 Hydrogen production equipment (hydrogen production device) 202 Terminal electrode 203 Preservation liquid container 204 Blood preservation solution 205 Preservation solution injection tube 206 Adjusted blood 207 Oxygen Adsorber 208 Centrifuge 210 Separation room 220 Blood collection container 221 Blood / Hemoglobin 222 Injection tube 223 Discharge pipe 224 Collector 225 Blood Powder 226 Dryer 227 Aqueous solution (water) 231 Rotational Axis 234 Color Measuring Instrument 403 Pump 405 Solenoid valves / switches 411 Gas flow meter 512 Ammeter

Claims

[Claim 1] a negative electrode having an acidic aqueous solution; a positive electrode having hemoglobin; a separator disposed between the negative electrode and the positive electrode; A hydrogen generating device comprising: a voltage application circuit that applies a voltage between the negative electrode and the positive electrode.

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