JP6016401B2 - Hydrogen generator and hydrogen generation method - Google Patents

Description

  The present invention relates to a technical field such as a hydrogen generator for generating hydrogen.

  In the reaction vessel in which an oxygen-free atmosphere from which oxygen in the air has been removed is formed, the applicant applies a metal material that forms an oxide film on the surface or an oxide material that is formed from an oxide, and an alkali metal melt. An application has been filed regarding a technique for generating hydrogen from the surface of a metal material or an oxide material by heating salt and water (for example, Patent Documents 1 and 2).

International Application PCT / JP2011 / 66472 Japanese Patent Application No. 2011-261430

  However, in the technique of the above application, since the reaction for generating hydrogen is a special reaction, hydrogen is allowed to stay in the reaction vessel for a certain period of time under atmospheric pressure (atmospheric pressure when no pressure is reduced or increased). Otherwise, the reaction vessel may be damaged.

  The present invention has been made in view of such problems and the like, and a hydrogen generator and the like that does not damage the reaction container by avoiding maintaining the atmospheric pressure in the reaction container at or above atmospheric pressure. The issue is to provide.

  In order to solve the above-mentioned problem, the invention described in claim 1 is characterized in that a reaction agent containing an alkali metal and oxygen arranged in an oxygen-free reaction vessel from which oxygen in the air has been removed, An oxide material formed from a metal material or an oxide that forms an oxide film on the arranged surface, a heating means for heating water, an atmospheric pressure measuring means for measuring the atmospheric pressure in the reaction vessel, and the measurement A time measuring means for measuring a time during which the atmospheric pressure is equal to or higher than normal pressure, and when the measured time reaches a preset upper limit time, hydrogen is discharged from the reaction container, and the reaction container And a pressure control means for lowering the pressure inside the hydrogen generator.

  According to the present invention, when the time during which the atmospheric pressure in the reaction vessel is equal to or higher than the normal pressure reaches the preset upper limit time, hydrogen is discharged from the reaction vessel, so that the atmospheric pressure in the reaction vessel is constant. The state where the pressure is higher than the normal pressure does not continue for more than an hour, and the risk that the reaction vessel is damaged can be avoided.

  According to the second aspect of the present invention, there is provided a reactant containing an alkali metal and oxygen arranged in an oxygen-free reaction vessel from which oxygen in the air is removed, and an oxide on the surface arranged in the reaction vessel. Heating means for heating an oxide material formed from a metal material or an oxide forming a film, an atmospheric pressure measuring means for measuring the atmospheric pressure in the reaction vessel, and the measured atmospheric pressure up to a preset upper limit value And a pressure control means for discharging hydrogen from the reaction vessel and lowering the pressure in the reaction vessel when the pressure rises.

  According to this invention, when the atmospheric pressure in the reaction vessel rises to a preset upper limit value, hydrogen is discharged from the reaction vessel and the atmospheric pressure in the reaction vessel decreases, so the upper limit value is set appropriately. By doing so, it is possible to avoid the state where the atmospheric pressure in the reaction vessel is higher than the normal pressure for a certain time or more, and to avoid the risk of damaging the reaction vessel.

  A third aspect of the present invention is the hydrogen generator according to the second aspect, wherein the upper limit value is set to be equal to or less than a value indicating normal pressure. If the pressure inside the reaction vessel is higher than atmospheric pressure, the generated hydrogen may stay near the inner wall of the reaction vessel and damage the reaction vessel. According to the present invention, however, damage to the reaction vessel can be avoided. it can.

  Invention of Claim 4 is the hydrogen generator as described in any one of Claim 1 thru | or 3, Comprising: The water supply means which supplies the preset amount of water or water vapor | steam in the said reaction container Are further provided. According to the present invention, the water vapor supplied into the reaction vessel (or water vapor generated by heating water) contacts the inner wall of the reaction vessel and ionizes to release hydrogen, thereby increasing the amount of hydrogen generated. Can be made.

  Invention of Claim 5 is the hydrogen generator of Claim 4, Comprising: The said water supply means WHEREIN: The raise value per unit time of the measured atmospheric pressure fell below the preset lower limit value In some cases, water or water vapor is supplied. According to the present invention, when the amount of generated hydrogen is reduced (when the increase in atmospheric pressure in the reaction vessel is reduced), the time during which the amount of generated hydrogen is reduced because water or water vapor is supplied. Can be shortened.

  A sixth aspect of the present invention is the hydrogen generator according to the fourth aspect, wherein the water supply means supplies water or water vapor every preset time. According to the present invention, the time from when a set amount of water (or water vapor) is supplied until the hydrogen generation reaction becomes active and the reaction becomes dull is obtained in advance, and the time is set as the set time. The time during which the amount of generated hydrogen is reduced can be shortened.

  A seventh aspect of the present invention is the hydrogen generator according to any one of the fourth to sixth aspects, wherein the water supply means is configured to perform the set amount once every n times (n> 1). More water or water vapor is supplied. According to the present invention, the amount of water generated in the reaction vessel is increased more rapidly when the amount of water is supplied than in other times, thereby stimulating the hydrogen generation reaction and increasing the amount of hydrogen generated. .

  The invention according to claim 8 is the hydrogen generator according to any one of claims 1 to 7, wherein a cooling means for cooling the inside of the reaction vessel and the measured atmospheric pressure increase. And a cooling control means for operating the cooling means. According to this invention, the inside of the reaction vessel is temporarily cooled during the hydrogen generation reaction, the hydrogen generation reaction can be stimulated, and the amount of hydrogen generated can be increased.

  According to a ninth aspect of the present invention, there is provided a reactant containing an alkali metal and oxygen arranged in an oxygen-free reaction vessel from which oxygen in the air has been removed, and an oxide on the surface arranged in the reaction vessel. An oxide material formed from a metal material or oxide that forms a film, a heating step of heating water, an atmospheric pressure measurement step of measuring the atmospheric pressure in the reaction vessel, and the measured atmospheric pressure is equal to or higher than normal pressure A time measuring step for measuring a certain time, and an atmospheric pressure control for reducing the atmospheric pressure in the reaction vessel by discharging hydrogen from the reaction vessel when the measured time reaches a preset upper limit time A hydrogen generation method comprising the steps of:

  According to a tenth aspect of the present invention, there is provided a reactant containing an alkali metal and oxygen arranged in an oxygen-free reaction vessel from which oxygen in the air is removed, and an oxide on the surface arranged in the reaction vessel. A heating step of heating an oxide material formed from a metal material or an oxide that forms a film, an atmospheric pressure measurement step of measuring the atmospheric pressure in the reaction vessel, and the measured atmospheric pressure up to a preset upper limit value And a pressure control step of lowering the pressure inside the reaction vessel by discharging hydrogen from the reaction vessel when the pressure rises.

  According to the present invention, when the atmospheric pressure in the reaction vessel rises to a preset upper limit value, hydrogen is discharged from the reaction vessel and the atmospheric pressure in the reaction vessel decreases, so that the reaction vessel is damaged. The risk of endangering can be avoided.

1 is a diagram illustrating an example of a hydrogen generator M. FIG. 2 is a block diagram illustrating a configuration of a control device 1. FIG. 3 is a flowchart illustrating an example of a control process by a control unit 11. 4 is a diagram illustrating an example of a change in atmospheric pressure in a reaction vessel 2. FIG. 3 is a flowchart illustrating an example of a control process by a control unit 11. 4 is a diagram illustrating an example of a change in atmospheric pressure in a reaction vessel 2. FIG. 4 is a diagram illustrating an installation example of a water cooling jacket J installed in a reaction vessel 2. FIG. It is a figure which shows an example of the change of the atmospheric | air pressure in the reaction container 2, and temperature.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  As shown in FIG. 1, the hydrogen generator M in the present embodiment includes a hermetic reaction vessel 2, and the reaction vessel 2 can use a heating device 3 (mantle heater, planar heater, etc.) as heating means. The gas may be heated to at least 350 ° C. or higher. The heating device 3 preferably heats the reaction vessel 2 to a temperature of about 500 ° C. Further, a barometer B as a barometric pressure measuring means is provided in the reaction vessel 2.

  The reaction vessel 2 is provided with a hydrogen discharge pipe 22, and the hydrogen discharge pipe 22 is connected to a vacuum pump 25. Before the operation of the hydrogen generator M is started, a vacuum process is performed by the vacuum pump 25 in order to remove oxygen in the air in the reaction vessel 2. After the oxygen in the reaction vessel 2 is removed by the decompression process, the valve 24 is closed and an oxygen-free atmosphere is formed in the reaction vessel 2, and the operation is started with this state as an initial state. As the vacuum pump 25, for example, a dry pump is used, and it is preferable to perform a water-resistant treatment so as not to be inoperable by water vapor discharged together with hydrogen. Note that a suction fan may be used instead of the vacuum pump 25.

  At least the inner wall of the reaction vessel 2 is made of a metal material that forms an oxide film on the surface. For example, a single metal that can be a plate-like structure such as iron (Fe), copper (Cu), aluminum (Al), chromium (Cr), titanium (Ti), nickel (Ni), or stainless steel (SUS304, 430) 316), nickel alloy (Inconel), titanium alloy (for aircraft), aluminum alloy (geralmine), copper alloy (brass, bronze, bronze), etc., and also iron with zinc (Zn), tin (Sn ) Plated tin, tin and the like. They form iron oxide (Fe2O3, Fe3O4), copper oxide (CuO), aluminum oxide (Al2O3), chromium oxide (Cr2O3), titanium oxide (TiO2), and nickel oxide (NiO) oxide films on their surfaces. .

  Also, stainless steel as an alloy is a passive film of chromium oxide, nickel alloy is nickel oxide (NiO) titanium alloy is titanium oxide (TiO2), aluminum alloy is aluminum oxide (Al2O3), copper alloy or copper oxide, and tin is oxidized Zinc (ZnO) and tin each form a film of tin oxide (SnO2).

  Further, the inner wall of the reaction vessel 2 formed of a metal material is an aqueous paint mainly composed of silicon oxide (SiO2) or iron oxide (Fe2O3), chromium oxide (Cr2O3), manganese oxide (MnO2), copper oxide ( When a paint in which CuO) and silicon oxide (SiO2) are evenly distributed is applied, the amount of hydrogen generation increases.

  The material of the reaction vessel 2 may be a ceramic material made of an oxide, such as aluminum oxide (Al 2 O 3) or zirconium oxide (ZrO 2), instead of a metal.

  When these materials are heated to 350 ° C. or higher, particularly around 500 ° C., hydrogen is generated from the inner wall of the reaction vessel 2. When hydrogen is generated, the atmospheric pressure in the reaction vessel 2 rises, and the reaction vessel 2 may be damaged if left under the influence of heat rays or the like due to a special reaction. Therefore, it is necessary to control the residence time of hydrogen in the reaction vessel 2.

  The reaction vessel 2 is provided with a water supply pipe 21 formed of the same material, and a set amount of water is supplied from a water supply device 4 as a water supply means. When water is supplied into the reaction vessel 2, the water immediately becomes water vapor at about 120 ° C., and the water vapor in the reaction vessel 2 contacts the inner wall of the reaction vessel 2 and is ionized to release hydrogen. A water storage tank (not shown) is provided in the water supply device 4, and water is extracted from the water storage tank and supplied into the reaction vessel 2 under the control of the control device 1. The water supply device 4 may supply water vapor generated by heating water into the reaction vessel 2.

  In the reaction vessel 2, a storage tray 7 for storing the reactant 8 is disposed so as to be freely accessible. The reactant 8 is most preferably sodium hydroxide (NaOH) or potassium hydroxide (KOH) that forms a molten salt at 300 ° C. or higher. As the solid reactant, potassium titanate (K2TiO3) and sodium titanate (Na2TiO3) are preferable. These reactants show great hydrophilicity. That is, the reactant 8 contains an alkali metal and oxygen. Innumerable fine particles invisible to the nano-order are scattered from the surface of the reactant 8, and the fine particles react with the inner wall of the reaction vessel 2 to generate hydrogen. Furthermore, water vapor and hydrophilic fine particles come into contact with each other to generate a remarkably large amount of hydrogen. Since the amount of fine particles scattered increases as the temperature in the reaction vessel 2 increases, it is important to manage the temperature so that the temperature in the reaction vessel 2 does not decrease.

  In the present embodiment, the reaction vessel 2 contributes to the hydrogen generation reaction, but the reaction vessel 2 is formed of a material other than the above-mentioned materials that do not contribute to the hydrogen generation reaction, such as carbon (C) or a concrete block. If it is, it is necessary to store the aforementioned metal material or ceramic material in the reaction vessel 2.

  A water tank 5 is provided downstream of the vacuum pump 25. Hydrogen generated in the reaction vessel 2 and unreacted water vapor pass through the vacuum pump 25 and flow into the water W in the water tank 5. The steam enters the water tank 5 and becomes water. On the other hand, the hydrogen is collected in the hydrogen tank 6 through the hydrogen collection tube 23 and through the flow meter F arranged further downstream thereof. The water W in the water tank 5 may be returned to the water storage tank of the water supply device 4.

  A control device 1 that controls the hydrogen generator M is connected to a barometer B, a flow meter F, a heating device 3, a water supply device 4, a vacuum pump 25, and a valve 24. The control device 1 is composed of, for example, a personal computer or the like, and includes a control unit 11, a storage unit 12, an interface unit 13, a display unit 14, and an operation unit 15, which are examples of atmospheric pressure control means, as shown in FIG. Yes.

  The storage unit 12 includes, for example, a hard disk drive (HDD) and stores various programs such as an operating system and application programs. In particular, the storage unit 12 of the present embodiment stores application programs that execute various processes for controlling the hydrogen generator M. Note that the various programs may be acquired from other server devices or the like via a network, or may be recorded on a recording medium and read via an external drive device.

  The interface unit 13 serves as a window for data transmitted / received to / from other devices, devices, and measuring instruments. Specifically, the interface unit 13 includes the atmospheric pressure information indicating the atmospheric pressure in the reaction vessel 2 transmitted from the barometer B, and the hydrogen amount indicating the amount of hydrogen that has passed through the hydrogen collection tube 23 transmitted from the flow meter F. The information is converted into data that can be processed by the control unit 11. Further, the interface unit 13 performs data conversion when transmitting control information for controlling each of the heating device 3, the water supply device 4, the vacuum pump 25, and the valve 24. The valve 24 opens and closes the hydrogen discharge pipe 22 based on control information received from the control device 1. The valve 24 has a structure that can be manually opened and closed as necessary.

  The display unit 14 is configured by, for example, a liquid crystal display or the like, and an operation screen when the operator operates the hydrogen generator M or the control device 1, the temperature in the reaction vessel 2, the hydrogen that has passed through the hydrogen collection tube 23. A screen or the like for sequentially displaying the amount or the like is displayed. The operation unit 15 includes, for example, a keyboard, a mouse, and the like. The operation unit 15 receives an operation by the operator and transmits an operation signal indicating the operation content to the control unit 11.

  The control unit 11 includes a CPU (Central Processing Unit) having a calculation function, a ROM (Read Only Memory), a working RAM (Random Access Memory), an oscillation circuit (not shown), and the like. Based on the operation signal received from, processing corresponding to the operation content of the operator is performed.

  In the hydrogen generator M, hydrogen is generated regardless of whether the pressure in the reaction vessel 2 is normal or reduced, but all of the water injected into the reaction vessel 2 reacts instantaneously. Hydrogen is not generated. The generated hydrogen is preferably retained in the reaction vessel 2 for a certain period of time. However, if the hydrogen is retained for a long time at a pressure higher than normal pressure, the reaction vessel 2 is affected by heat rays during a special reaction. Since it breaks, it is necessary to control residence time appropriately. In particular, since a special reaction is likely to occur under reduced pressure, it is necessary to control the residence time more appropriately to reduce the influence on the reaction vessel 2.

  Therefore, the control unit 11 controls the vacuum pump 25 and the valve 24 so as to appropriately control the residence time of hydrogen in the reaction vessel 2 under reduced pressure. Here, a control process in which the control unit 11 controls the hydrogen generator M based on the atmospheric pressure information received from the barometer B will be described with reference to FIG. In the present embodiment, the control unit 11 continuously receives atmospheric pressure information. In addition, the normal pressure value at the place where the reaction vessel 2 is installed is stored in the storage unit 12 in advance.

  First, the control part 11 performs a pressure reduction process in order to make the inside of the reaction container 2 before the operation start of the hydrogen generator M into an initial state (step S11). Specifically, the depressurization process is performed until the atmospheric pressure in the reaction vessel 2 becomes about -0.5 atm to -1 atm. If it will be in an initial state, the control part 11 will start the heating with respect to the reaction container 2 to the heating apparatus 3 in order to start the driving | operation of the hydrogen generator M (step S12), and water for the set amount will be supplied to the water supply apparatus 4. Supply (step S13).

  Next, the control unit 11 refers to the atmospheric pressure information and determines whether or not the atmospheric pressure in the reaction vessel 2 exceeds the normal pressure (step S14). When the control unit 11 determines that the atmospheric pressure in the reaction vessel 2 does not exceed the normal pressure (step S14: NO), the control unit 11 proceeds to the process of step S18. On the other hand, when it is determined that the atmospheric pressure in the reaction vessel 2 exceeds the normal pressure (step S14: YES), the control unit 11 starts measuring time (step S15). The time can be measured using a system clock or the like.

  Next, the control unit 11 determines whether or not a preset upper limit time has been reached after starting time measurement in the process of step S15 (step S16). The upper limit time is set by experimentally acquiring the time obtained by subtracting the margin (margin) from the time that does not damage the reaction vessel 2 even if hydrogen is retained in the reaction vessel 2 under atmospheric pressure. I decided to. The control part 11 repeats the process of step S16 until it determines with measurement time having reached the upper limit time (step S16: NO), and when it determines with measurement time having reached the upper limit time (step S16: YES). In order to reduce the atmospheric pressure in the reaction vessel 2, a depressurization process is performed (step S17), and the process proceeds to step S14.

  On the other hand, if the control unit 11 determines in step S14 that the atmospheric pressure in the reaction vessel 2 does not exceed the normal pressure (step S14: NO), then the control unit 11 determines the increase in atmospheric pressure per unit time. It is calculated and determined whether or not the degree of increase in atmospheric pressure is below a predetermined set value (step S18). At this time, if the control unit 11 determines that the degree of increase in atmospheric pressure is not less than a predetermined set value (step S18: NO), the control unit 11 proceeds to the process of step S14. On the other hand, if it is determined that the degree of increase in atmospheric pressure is below a predetermined set value (step S18: YES), the controller 11 supplies water (or water vapor) for a set amount to the water supply device 4. Supply (step S19), the process proceeds to step S14.

  As described above, in the hydrogen generator M of the present embodiment, the heating device 3 includes the reactant 8 containing alkali metal and oxygen disposed in the oxygen-free reaction vessel 2 from which oxygen in the air has been removed. The metal material for forming an oxide film on the surface disposed in the reaction vessel 2 or the oxide material formed from the oxide and water are heated, and the barometer B measures the atmospheric pressure P in the reaction vessel 2 Then, the control unit 11 measures the time when the atmospheric pressure measured by the barometer B is equal to or higher than the normal pressure, and discharges hydrogen from the reaction container 2 when the measurement time reaches a preset upper limit time. The atmospheric pressure in the reaction vessel 2 is reduced. Therefore, according to the hydrogen generator M of the present embodiment, the state in which the atmospheric pressure in the reaction vessel 2 is higher than the normal pressure for the upper limit time (fixed time) does not continue, and the reaction vessel 2 may be damaged. Can be avoided.

  In the present embodiment, the degree of increase in atmospheric pressure per unit time is calculated, and water is newly supplied into the reaction vessel 2 when the degree of increase in atmospheric pressure is below a predetermined set value. However, instead of or in addition to this, the control unit 11 increases the heating temperature by the heating device 3 when the degree of increase in atmospheric pressure is lower than a predetermined set value, A warning message (or a warning message indicating that the amount of hydrogen generation is decreasing) indicating that the degree of increase is below a predetermined set value is displayed on the display unit 14 or a new reagent 8 is added. Or a message indicating the content of the instruction to supply (for example, “add a reactive agent”) may be displayed on the display unit 14.

  Next, a modification of the above embodiment will be described. In the above embodiment, when the time during which the atmospheric pressure in the reaction vessel 2 is equal to or higher than the normal pressure reaches a preset upper limit time, hydrogen is discharged from the reaction vessel 2 to lower the atmospheric pressure in the reaction vessel 2. However, in this modification, when the atmospheric pressure in the reaction vessel 2 reaches a preset upper limit value, hydrogen is discharged from the reaction vessel 2 to lower the atmospheric pressure in the reaction vessel 2. And The atmospheric pressure control of this modification will be described with reference to FIG. The pressure P0 in the reaction vessel 2 at the time T0 before the start of operation is a normal pressure. First, in order to set the inside of the reaction vessel 2 to an initial state, the control unit 11 opens the valve 24 and performs a pressure reduction process for operating the vacuum pump 25 to change the pressure P in the reaction vessel 2 to P1 (in this modification, − The pressure is reduced to 1 atm (P1 is preferably set to -0.5 to -1 atm) (T1 to T2).

  When the initial state is reached, the control unit 11 starts the operation of the hydrogen generator M. Specifically, the control unit 11 causes the heating device 3 to start heating the reaction vessel 2 and causes the water supply device 4 to supply a predetermined amount of water. When the reaction vessel 2 is heated, hydrogen is generated and the pressure P in the reaction vessel 2 begins to rise gradually (T3 to T4). When the pressure P reaches P0, the control unit 11 performs a pressure reduction process, that is, opens the valve 24 and operates the vacuum pump 25 to discharge hydrogen and water vapor, thereby reducing the pressure P in the reaction vessel 2 to P1. (T4 to T5). When the atmospheric pressure P in the reaction vessel 2 drops to P1, the control unit 11 closes the valve 24 and stops the vacuum pump 25 to stop the pressure reduction process.

  Thus, the control part 11 performs a pressure reduction process whenever the atmospheric pressure P in the reaction container 2 reaches P0 due to the generation of hydrogen, and reduces the atmospheric pressure P to P1 (T5 to T7). On the other hand, when the increase degree of the atmospheric pressure P per unit time falls below a predetermined set value (T7 to T8), the control unit 11 causes the water supply device 4 to newly supply a set amount of water. (T8). However, it is assumed that the reactant 8 in the storage tray 7 is sufficiently left, and the reactant 8 needs to be added when the remaining amount of the reactant 8 is small. Thereafter, the control unit 11 performs a decompression process and a water supply process according to the atmospheric pressure P in the reaction vessel 2. That is, the control unit 11 controls the atmospheric pressure P in the reaction vessel 2 within the range of P0 to P1, and when the increase degree of the atmospheric pressure P per unit time falls below a predetermined set value (inside the reaction vessel 2). When the amount of water vapor decreases, water is supplied. Although the upper limit value of the atmospheric pressure P is P0 (normal pressure) here, the upper limit value may be set to a value lower than the normal pressure.

  Next, a control process in which the control unit 11 controls the hydrogen generator M based on the atmospheric pressure information received from the barometer B will be described with reference to FIG. Note that the control unit 11 continuously receives atmospheric pressure information.

  First, the control part 11 performs a pressure reduction process in order to make the inside of the reaction container 2 before the operation start of the hydrogen generator M into an initial state (step S31). If it will be in an initial state, the control part 11 will start the heating with respect to the reaction container 2 to the heating apparatus 3 in order to start the driving | operation of the hydrogen generator M (step S32), and will supply water for the set amount to the water supply apparatus 4. Supply (step S33).

  Next, the control unit 11 refers to the atmospheric pressure information and determines whether or not the atmospheric pressure P in the reaction vessel 2 has reached P0 (normal pressure) (step S34). At this time, when it is determined that the pressure P in the reaction vessel 2 has reached P0 (normal pressure) (step S34: YES), the control unit 11 reduces the pressure P in the reaction vessel 2 to P1. Therefore, a decompression process is performed (step S35), and the process proceeds to step S34. On the other hand, when it is determined that the pressure P in the reaction vessel 2 has not reached P0 (normal pressure) (step S34: NO), the control unit 11 then calculates the degree of increase in the pressure P per unit time. Then, it is determined whether or not the degree of increase in the atmospheric pressure P is below a predetermined set value (step S36). At this time, if the control unit 11 determines that the degree of increase in the atmospheric pressure P is not below a predetermined set value (step S36: NO), the control unit 11 proceeds to the process of step S34. On the other hand, when the controller 11 determines that the degree of increase in the atmospheric pressure P is below a predetermined set value (step S36: YES), the controller 11 supplies the water supply device 4 with a set amount of water (or water vapor). (Step S37), and the process proceeds to Step S34.

  As described above, the hydrogen generator M of the present modified example includes the reactant 8 containing alkali metal and oxygen disposed in the oxygen-free reaction vessel 2 from which the heating device 3 has removed oxygen in the air. The metal material forming an oxide film on the surface disposed in the reaction vessel 2 or the oxide material formed from the oxide is heated, and the barometer B measures the atmospheric pressure P in the reaction vessel 2 and controls it. When the pressure P measured by the barometer B rises to P0 in FIG. 4 (an example of “preset upper limit value”), the unit 11 discharges hydrogen from the reaction vessel 2 and the reaction vessel 2 Reduce the pressure inside. Therefore, according to the hydrogen generator M of this modification, when the atmospheric pressure P in the reaction vessel 2 rises to P0, hydrogen is discharged from the reaction vessel 2 and the atmospheric pressure P in the reaction vessel 2 decreases. Therefore, by appropriately setting P0, it is possible to avoid the state where the atmospheric pressure P in the reaction vessel 2 is higher than the normal pressure for a certain time or more, and to avoid the risk of damaging the reaction vessel 2. be able to.

  In this modification, P0 is set as the pressure for starting the decompression process in order to operate the hydrogen generator M in a state where the pressure P in the reaction vessel 2 is equal to or lower than P0 (normal pressure). This is because if the pressure in the reaction vessel 2 is equal to or higher than normal pressure, the generated hydrogen may stay in the vicinity of the inner wall of the reaction vessel 2 to prevent the reaction or damage the reaction vessel 2. is there. Therefore, when operated in a reduced pressure environment as in this modification, the generated hydrogen is removed from the inner wall, the reaction is activated, a larger amount of hydrogen can be collected, and the reaction vessel 2 is not damaged. In addition, during operation of the hydrogen generator M, the vacuum pump 25 can be operated so that the atmospheric pressure in the reaction vessel 2 is always equal to or lower than the atmospheric pressure (for example, -1 atm). In addition, the operating cost can be reduced by operating the vacuum pump 25 only when the atmospheric pressure in the reaction vessel 2 rises to a certain value.

  Furthermore, in the hydrogen generator M of this modification, the water supply device 4 supplies a preset amount of water or water vapor into the reaction vessel 2. Therefore, according to the hydrogen generator M of this modification, the water vapor (or water vapor generated by heating water) supplied into the reaction vessel 2 contacts the inner wall of the reaction vessel 2 and is ionized to release hydrogen. As a result, the amount of hydrogen generated can be increased.

  Furthermore, the hydrogen generator M of the present modified example uses water or water vapor when the water supply device 4 has a rise value per unit time of the atmospheric pressure measured by the barometer B below a preset lower limit value. Supply. Therefore, according to the hydrogen generator M of the present modification, water or water vapor is supplied when the amount of hydrogen generated decreases (when the increase in the atmospheric pressure in the reaction vessel 2 decreases). It is possible to shorten the time during which the amount of generation is reduced.

  In this modification, as described above, in order to operate the hydrogen generator M in a reduced pressure environment, P0 is set as the upper limit value of the atmospheric pressure for starting the reduced pressure process. However, the upper limit of the atmospheric pressure for starting the reduced pressure process is set. The value may be set to a value (for example, −0.1 atm or the like) indicating an atmospheric pressure lower than normal pressure other than P0.

  On the other hand, hydrogen is generated even when the atmospheric pressure in the reaction vessel 2 is atmospheric pressure or higher. Therefore, as shown in FIG. 6, the operation of the hydrogen generator M is started in a state where the pressure P in the reaction vessel 2 is P0 (normal pressure), and when the pressure P in the reaction vessel 2 reaches P2, the reaction vessel It is good also as a structure which performs a pressure reduction process until the atmospheric pressure P in 2 becomes P0 (normal pressure). At this time, it is preferable to set P2 (atmospheric pressure at which the decompression process is started) to a value obtained by subtracting a margin (margin value) from a value damaged by the atmospheric pressure (internal pressure) in the reaction vessel 2. Thereby, the hydrogen generator M can be safely operated without damaging the reaction vessel 2 due to the internal pressure.

  Further, as shown in FIG. 7, a water cooling jacket J as a cooling means is wound around the outer periphery of the reaction vessel 2, and when the control unit 11 as the cooling control means generates hydrogen in the reaction vessel 2, Water may be supplied to the jacket J and the reaction vessel 2 may be cooled. In this case, the control unit 11 does not constantly cool the reaction vessel 2 but, as shown in FIG. 8, the period during which hydrogen is generated (for example, T3 to T4, T5 to T6, T7 to T9 in FIG. 8). The temperature T in the reaction vessel 2 is lowered for a part of the period). As a result, the inside of the reaction vessel 2 is temporarily cooled during the hydrogen generation reaction, the hydrogen generation reaction can be stimulated, and the amount of hydrogen generated can be increased.

  Furthermore, in this modified example, when the degree of increase in atmospheric pressure falls below a predetermined set value (step S36: NO in FIG. 5), water (or water vapor) is supplied by a set amount. Without performing the process of S36, the hydrogen generation reaction is activated after supplying a predetermined amount of water (or water vapor), and the time until the reaction becomes dull is obtained in advance. Water (or water vapor) may be supplied in a set amount (that is, water (or water vapor) may be supplied periodically). In addition, when water (or water vapor) is supplied in the process of step S37 in FIG. 5 or when water (or water vapor) is supplied at regular intervals, the set amount is once every predetermined number of times (for example, 5 times). More water (or water vapor) may be supplied. Specifically, twice the set amount of water may be supplied every predetermined number of times (for example, the fifth, tenth, fifteenth,...). At the time when a large amount of water is supplied, the amount of water vapor in the reaction vessel 2 increases more rapidly than at other times, thereby stimulating the hydrogen generation reaction and increasing the amount of hydrogen generated.

M Hydrogen generator 1 Control device 11 Control unit 12 Storage unit 13 Interface unit 14 Display unit 15 Operation unit 2 Reaction vessel 3 Heating device 4 Water supply device 5 Water tank 6 Hydrogen tank 7 Storage tray 8 Reactant 21 Water supply pipe 22 Hydrogen Discharge pipe 23 Hydrogen collection pipe 24 Valve 25 Vacuum pump F Flow meter B Barometer

Claims (9)

A reactive agent containing an alkali metal and oxygen arranged in an oxygen-free reaction vessel from which oxygen in the air has been removed, and a metal material or oxide that forms an oxide film on the surface arranged in the reaction vessel An oxide material formed from, a heating means for heating water,
Pressure measuring means for measuring the pressure in the reaction vessel;
Time measuring means for measuring a time during which the measured atmospheric pressure is equal to or higher than normal pressure;
When the measured time reaches a preset upper limit time, atmospheric pressure control means for discharging hydrogen from the reaction vessel and reducing the atmospheric pressure in the reaction vessel;
Cooling means for cooling the inside of the reaction vessel;
Cooling control means for operating the cooling means when the measured atmospheric pressure is rising;
A hydrogen generator characterized by comprising: A reactive agent containing an alkali metal and oxygen arranged in an oxygen-free reaction vessel from which oxygen in the air has been removed, and a metal material or oxide that forms an oxide film on the surface arranged in the reaction vessel Heating means for heating the oxide material formed from
Pressure measuring means for measuring the pressure in the reaction vessel;
An atmospheric pressure control means for discharging hydrogen from the reaction vessel when the measured atmospheric pressure rises to a preset upper limit value, and reducing the atmospheric pressure in the reaction vessel;
Cooling means for cooling the inside of the reaction vessel;
Cooling control means for operating the cooling means when the measured atmospheric pressure is rising;
A hydrogen generator characterized by comprising: The hydrogen generator according to claim 2,
The upper limit value is set to be equal to or lower than a value indicating normal pressure. The hydrogen generator according to any one of claims 1 to 3,
Water supply means for supplying a preset amount of water or water vapor into the reaction vessel;
A hydrogen generator, further comprising: The hydrogen generator according to claim 4, wherein
The water supply means supplies water or water vapor when the rise value per unit time of the measured atmospheric pressure falls below a preset lower limit value. The hydrogen generator according to claim 4, wherein
The hydrogen generator is characterized in that the water supply means supplies water or water vapor every preset time set in advance. The hydrogen generator according to any one of claims 4 to 6,
The hydrogen generator is characterized in that the water supply means supplies more water or water vapor than the set amount once every n times (n> 1). A reactive agent containing an alkali metal and oxygen arranged in an oxygen-free reaction vessel from which oxygen in the air has been removed, and a metal material or oxide that forms an oxide film on the surface arranged in the reaction vessel An oxide material formed from a heating step of heating water;
  A pressure measuring step for measuring the pressure in the reaction vessel;
  A time measuring step of measuring a time during which the measured atmospheric pressure is equal to or higher than normal pressure;
  When the measured time reaches a preset upper limit time, hydrogen is discharged from the reaction vessel to reduce the atmospheric pressure in the reaction vessel; and
  A cooling step for cooling the inside of the reaction vessel;
  A cooling control step of operating the cooling step when the measured atmospheric pressure is rising;
  A hydrogen generation method comprising: A reactive agent containing an alkali metal and oxygen arranged in an oxygen-free reaction vessel from which oxygen in the air has been removed, and a metal material or oxide that forms an oxide film on the surface arranged in the reaction vessel A heating step of heating the oxide material formed from
  A pressure measuring step for measuring the pressure in the reaction vessel;
  An atmospheric pressure control step of reducing the atmospheric pressure in the reaction vessel by discharging hydrogen from the reaction vessel when the measured atmospheric pressure rises to a preset upper limit;
  A cooling step for cooling the inside of the reaction vessel;
  A cooling control step of operating the cooling step when the measured atmospheric pressure is rising;
  A hydrogen generation method comprising:

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