JP2009215148A - Hydrogen gas storage method and storage device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique where, to a space generated by bringing water and an alkali metal or an alkaline-earth metal or magnesium into chemical reaction, so as to reduce the content of water, high pressure hydrogen gas is produced in accordance with the ratio of the generated hydrogen gas to be occupied, and the hydrogen gas having high pressure is occluded into a hydrogen storage vessel containing a hydrogen storage alloy. <P>SOLUTION: When an alkali metal or an alkaline-earth metal or magnesium and water at a prescribed temperature are reacted, so as to produce hydrogen gas, by performing the reaction in a reaction tank 30A filled with water and any inert gas including nitrogen gas and sealed, in accordance with the ratio occupied by the hydrogen gas generated by the reaction to the total of the initial space occupied by any inert gas including nitrogen gas in the reaction tank 30A and the space by the reduction in the content of the water by the reaction in the reaction tank 30A, high pressure hydrogen gas is produced, and the high pressure hydrogen gas is occluded into the hydrogen storage alloy. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrogen gas storage method and storage device, and more specifically, from a state completely filled with any one of water and an inert gas including nitrogen gas, sometimes water. Chemical reaction between water and any of alkali metal, alkaline earth metal, or magnesium, taking into account the space occupied by any of the inert gases including nitrogen gas, as necessary High-pressure hydrogen gas is produced according to the proportion of hydrogen gas generated by the reaction in the space generated by reducing the amount of water, and the generated high-pressure hydrogen gas is stored in a hydrogen storage container containing a hydrogen storage alloy. It describes the technology that has been made to occlude.

  Conventionally, as a technique related to a hydrogen gas storage method and storage device, there are a high pressure cylinder, a liquefied one, a hydrogen storage alloy, and the like.

  In that case, the high-pressure cylinder was stored at a pressure of 20 MPa or 35 MPa as an example, and the volumetric hydrogen density showed a small value.

  Moreover, regarding the liquefied one, the volumetric hydrogen density showed a small value, but was larger than that obtained by the high pressure cylinder.

  On the other hand, as for the pressure of the hydrogen occlusion alloy, it is not necessary to set the operating pressure at the time of occlusion to a high pressure, but a certain pressure is required even if it is 1 MPa or less.

  However, the conventional hydrogen gas storage method and storage apparatus have the following problems.

  First, for the high pressure cylinder, an apparatus for pressurizing to a pressure of 20 MPa or 35 MPa was required. And the occupation section and the installation area required a part larger than that of the hydrogen storage alloy.

  Moreover, regarding the liquefied thing, the big apparatus was required in order to liquefy. And the occupation section and the installation area required a part larger than that of the hydrogen storage alloy.

  On the other hand, for the hydrogen storage alloy, some pressure was required to store hydrogen in the hydrogen storage alloy, although it was 1 MPa or less.

  In the present invention, when hydrogen gas is produced by reacting water at a predetermined temperature with either alkali metal, alkaline earth metal, or magnesium, the reaction is completely performed by either water or an inert gas containing nitrogen gas. By performing the reaction in the reaction tank 30A that is filled, sealed, and completely shut off from the outside, depending on the reaction in the reaction tank 30A and the space occupied by the inert gas including the initial nitrogen gas in the reaction tank 30A. It is characterized by creating high-pressure hydrogen gas according to the proportion of hydrogen gas generated by reacting against the sum of space due to water loss, and storing the high-pressure hydrogen gas in a hydrogen storage alloy, Nitrogen gas is produced from compressed air by a membrane separation method or a PSA method. First, the reaction tank 30A is completely filled. Injecting water, then draining and filling with nitrogen gas, and finally starting the reaction after sending either alkali metal or alkaline earth metal or magnesium Furthermore, when hydrogen gas is produced by reacting either alkali metal, alkaline earth metal, or magnesium with water at a predetermined temperature, the reaction is completely filled with water and sealed and completely shut off from the outside. By performing the reaction in the reaction tank 30B, high-pressure hydrogen gas is produced according to the proportion of the hydrogen gas generated by the reaction with respect to the space resulting from the reduction of water by the reaction in the reaction tank 30B. It is characterized in that the gas is stored in a hydrogen storage alloy, and further, water is first injected and then alkali metal or alkaline earth metal is injected. Alternatively, after feeding either magnesium, the reaction is started from a state where there is no space in the reaction tank 30B. Furthermore, water can be heated or cooled as necessary. By solving this problem, the above-mentioned problems have been solved.

  Further, the present invention provides a sealed reaction tank 30A that generates hydrogen gas by reacting either alkali metal, alkaline earth metal, or magnesium with water at a predetermined temperature, and contains nitrogen gas in a sealed reaction tank 30A that is completely shut off from the outside. An inert gas supply device 10 that can supply any of the active gases is connected, and a water supply device 40A that can supply water is connected, and any one of alkali metal, alkaline earth metal, and magnesium falls. From the state in which the solid particle storage device 20 stored as possible is connected and the reaction tank 30A is completely filled with either an inert gas containing water and nitrogen gas, the initial nitrogen gas in the reaction tank 30A is used. The space occupied by any of the inert gas containing water and the sum of the space due to the reduction of water due to the reaction in the reaction tank 30A Then, the hydrogen gas generated by the reaction is converted into high-pressure hydrogen gas, and the high-pressure hydrogen gas is stored in the hydrogen storage container 70 containing the hydrogen storage alloy from the upper part of the reaction tank 30A. Further, water can be fed into a sealed and completely shut off reaction tank 30B that generates hydrogen gas by reacting water of a predetermined temperature with either alkali metal, alkaline earth metal or magnesium. A water supply device 40B that can be connected, a solid particle storage device 20 that stores either alkali metal, alkaline earth metal, or magnesium so that it can fall is connected, and the reaction tank 30B is completely filled with water To react to the space due to the reduction of water by the reaction in the reaction tank 30B. According to the ratio of the hydrogen gas generated by this, high-pressure hydrogen gas is used, and the high-pressure hydrogen gas is stored in the hydrogen storage container 70 containing the hydrogen storage alloy from the upper part of the reaction tank 30B. A heating / cooling means 50 for heating or cooling water to a required temperature is disposed in the water supply devices 40A, 40B or the reaction tanks 30A, 30B or in the vicinity thereof, and further, the reaction tank 30A, 30B is formed with a residual fluid discharge port 303 that allows the internal fluid to be discharged from the upper part, and a waste removal outlet 302 that allows the internal waste and liquid to be discharged from the lower part. In order for the reaction tanks 30A and 30B to be more completely shut off from the outside, an inert gas supply is provided between the reaction tanks 30A and 30B and the inert gas supply device 10. High-pressure hydrogen between the on-off valve 201 and the solid particle storage device 20, the solid particle charging on-off valve 204, the water supply on-off valve 210 between the water supply devices 40 </ b> A and 40 </ b> B, and the hydrogen storage container 70. A residual fluid discharge on-off valve 206 is disposed between the gas on-off valve 208 and the residual fluid discharge port 303, and a waste trap discharge opening / closing valve 207 is disposed between the gas shut-off valve 302 and the waste trap outlet 302. The hydrogen storage container 70 can be heated and cooled from the outside, and a pressure reducing valve 211 for reducing the pressure of the high pressure hydrogen gas is provided between the high pressure hydrogen gas on-off valve 208 and the hydrogen storage container 70. The above-described problem has been solved by the feature of the provision.

  As is clear from the above description, the present invention can provide the following effects.

  First, when hydrogen gas is produced by reacting water at a predetermined temperature with either alkali metal, alkaline earth metal, or magnesium, the reaction is performed by any of inert gas including water and nitrogen gas. By performing the reaction in a reaction tank that is completely filled, sealed, and completely isolated from the outside, water is generated by the reaction of the space occupied by any of the inert gases including nitrogen gas in the reaction tank and the reaction in the reaction tank. The inert gas containing nitrogen gas is created by creating high-pressure hydrogen gas according to the proportion of the hydrogen gas generated by the reaction against the sum of the space due to the reduction in the amount of hydrogen, and storing the high-pressure hydrogen gas in the hydrogen storage alloy. Although it is a mixed gas with any of the gases, it is not necessary to go through a device for increasing the pressure, such as a gas intensifier or a pump. It is possible to produce a mixed gas around the hydrogen gas, by directly occluded in the hydrogen-absorbing alloy for a high pressure, it has become possible to store and only separated and purified hydrogen gas.

  Second, nitrogen gas is produced from compressed air by membrane separation or PSA method. First, water is injected so that the reaction tank is completely filled, and then nitrogen gas is partially discharged. It is a mixed gas with nitrogen gas by starting either after alkali metal, alkaline earth metal or magnesium is finally sent, but depending on the method, it can be reduced to as little nitrogen gas as possible. It is also possible to limit, and in a more stable form, especially with an emphasis on safety, it becomes possible to produce a mixed gas centered on high-pressure hydrogen gas. By making it occluded, only hydrogen gas can be separated, purified and stored.

  Third, when hydrogen gas is produced by reacting water of a given temperature with either alkali metal, alkaline earth metal or magnesium, the reaction is completely filled with water, sealed and completely shut off from the outside. By performing the reaction in the reaction tank, high-pressure hydrogen gas is produced by the proportion of the hydrogen gas generated by the reaction to the space resulting from the reduction of water due to the reaction in the reaction tank. Occlusion in the alloy makes it possible to produce high-pressure hydrogen gas by a simple method without having to go through a device for increasing the pressure, such as a gas intensifier or a pump with a particularly high purity. For this reason, it has become possible to store it in the hydrogen storage alloy as it is.

  Fourth, after injecting water first and then feeding either alkali metal, alkaline earth metal or magnesium, the reaction is started from a state where there is no space in the reaction tank. By effectively utilizing water, it becomes possible to produce a high-pressure hydrogen gas having a particularly high purity, and since it is high-pressure, it can be stored in a hydrogen storage alloy as it is.

  Fifth, water can be heated or cooled as necessary, so that the reaction rate during the reaction can be increased.

  Sixth, the reaction tank has a residual fluid outlet that allows the internal fluid to be discharged from the top, and a waste outlet that allows the internal waste and liquid to be discharged from the bottom. In order to make the reaction tank more completely shut off from the outside, an inert gas supply on / off valve is connected between the inert gas supply device and the solid particle storage device is opened / closed with the solid particle storage device. Between the valve and the water supply device, a water supply opening / closing valve, a high-pressure hydrogen gas opening / closing valve between the hydrogen storage container, a residual fluid discharge opening / closing valve between the residual fluid discharge port, and a waste intake outlet By disposing a waste dredge take-off on / off valve, it became possible to completely fill the inert gas containing water and nitrogen gas and water, and this reaction could be performed with a simple apparatus.

  Seventh, the hydrogen storage container can be heated and cooled from the outside, and a pressure reducing valve for depressurizing the high pressure hydrogen gas is provided between the high pressure hydrogen gas on-off valve and the hydrogen storage container. It became possible to heat and cool to the required temperature, or to reduce the pressure to the required pressure.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
Here, FIG. 1 is a diagram showing the present invention, and FIG. 2 is a diagram showing another embodiment in which an inert gas containing nitrogen gas of the present invention is not used.

  As shown in FIG. 1, reference numeral 10 denotes an inert gas supply device, which is one of nitrogen, helium, neon, argon, krypton, xenon, and radon containing an inert gas containing nitrogen gas. A high-pressure cylinder filled with the above gas or a nitrogen gas production apparatus produced from compressed air by a membrane separation method or a PSA method can be considered. However, the nitrogen gas production apparatus is not limited to the membrane separation method or the PSA method, and a cryogenic separation method in which air is cooled and separated is also conceivable.

  By the way, the PSA system is an abbreviation for Pressure Swing Adsorption, and passes compressed air through an adsorbent that is a kind of activated carbon, adsorbs a specific gas under a high pressure, and a specific gas under a low pressure. This is a method of separating nitrogen by adsorbing oxygen or the like from compressed air using the adsorbent's characteristic of exhaling. In this case, it has the same principle as a heatless dryer, and the apparatus is a two-cylinder type, which is larger than the membrane separation type, and a maintenance load such as a solenoid valve is applied. In terms of nitrogen purity, it was usually about 99 to 99.9999%.

  On the other hand, in the membrane separation method, compressed air is sent into a hollow fiber membrane, which is a hollow fiber polymer membrane, and nitrogen is removed by utilizing the difference in permeation amount of each gas component contained in the compressed air to the membrane. This is a separation method. In this case, although it is smaller than the PSA method and has a smaller maintenance load, it is about 95 to 99.9% in terms of nitrogen purity, so it is not suitable for high purity needs.

  The hollow fiber membrane is made of polyester and is made of a bundle of thousands of straw-shaped hollow fibers. By passing compressed air through the hollow fiber, each gas has its own unique hollow fiber. By utilizing the difference in the permeation speed of the membrane, the nitrogen gas most contained in the air is left.

  And as the speed which the gas which comprises compressed air permeate | transmits the membrane of a hollow fiber, there exist gas which discharge | releases quickly and gas which is hard to discharge | release, and the remaining gas will be nitrogen gas. In particular, when the hollow fiber membrane is made of polyester, water vapor is most permeable, followed by hydrogen and helium, followed by carbon dioxide and carbon monoxide, and finally oxygen, argon and nitrogen are most permeable. The nitrogen gas is the gas that is most difficult to permeate.

  Here, when the temperature does not change, the purity of the generated nitrogen gas depends on the pressure and time of the compressed air, that is, the flow rate. In addition to polyester, resins such as polyolefin and polypropylene are also conceivable as the hollow fiber membrane.

  On the other hand, any one of the inert gases including the nitrogen gas from the inert gas supply device 10 includes an inert gas supply pipe 101, an inert gas supply opening / closing valve 201 that manually opens and closes, and an inert gas. Via the gas supply pipe 102, it is sent to the reaction tank 30A for performing a reaction for producing hydrogen gas. The inert gas supply device 10 is connected with a nitrogen gas concentration meter 202 that can measure the internal concentration in order to confirm whether or not the supply of the nitrogen gas is ensured when the nitrogen gas is supplied. Yes.

  In this case, the reaction tank 30A can be fed from the solid particle storage device 20 with a small amount or powder of any required amount of alkali metal, alkaline earth metal, or magnesium. Yes. More specifically, a small piece or powder of alkali metal, alkaline earth metal, or magnesium is manually opened and closed from the solid particle inlet 301 and the solid particle storage pipe 111. A solid particle storage on / off valve 205, a solid particle storage pipe 112, a solid particle storage device 20, a solid particle input pipe 113, a solid particle input on / off valve 204 that manually opens and closes, and a solid particle input pipe 114. It is sent to the reaction tank 30A via

  That is, the solid particle storage device 20 is charged with a necessary fixed amount of alkali metal, alkaline earth metal, or magnesium in small pieces or powder, and the like. Is stored. Then, after storage, by opening the solid particle input opening / closing valve 204, it is possible to input small pieces or powders of alkali metal, alkaline earth metal, or magnesium stored in the reaction tank 30A. By closing the solid particle storage on-off valve 205, the gas in the reaction tank 30A is prevented from leaking outside through the solid particle storage device 20 when the solid particle charging on-off valve 204 is opened. It is.

  Furthermore, water at a temperature required by the water supply device 40A can be fed into the reaction tank 30A by the pressure of any of the inert gases including nitrogen gas from the inert gas supply device 10. Yes. That is, any one of the inert gases including nitrogen gas from the inert gas supply device 10 is added to the pressurizing inert gas pipe 131 which is the water supply means 131 and the water supply means 209 which is manually opened and closed. Pressurize the water stored in the water supply device 40A from above by sending it into the water supply device 40A via the pressure inert gas on-off valve 209 and the pressurizing inert gas pipe 132 which is the water supply means 132. The water is fed into the reaction tank 30 </ b> A via a water supply pipe 133, a water supply opening / closing valve 210 that is manually opened and closed, and a water supply pipe 134.

  When the pressure of any one of the inert gases including the nitrogen gas from the inert gas supply device 10 is to be increased, the gas is placed in any of the pressurizing inert gas pipes 131 and 132. It is also conceivable to provide a pressure increasing valve that can increase the pressure of the pressure.

  In this case, water supply means 131, 132, and 209 are connected in such a way that water can be supplied at a predetermined pressure by any one of inert gases including nitrogen gas from the inert gas supply device 10. The reason for this is that by using the pressure of air, it is considered that the adverse effect of oxygen gas contained in the air is prevented by flowing into the reaction tank 30A. The water supply means 131, 132, and 209 need not be limited to this, and the water supply device 40A may be positioned higher than the residual fluid discharge port 303 to supply water by dropping naturally. Conceivable.

  Here, in the water supply apparatus 40A, the heating / cooling means 50 can heat or cool the water to a required temperature. Although the heating / cooling means 50 is located in the water supply device 40A in FIG. 1, the heating / cooling means 50 is not limited to this location, and is located in the water supply pipes 133, 134 and the reaction tank 30A. It doesn't matter. In particular, when it is positioned in the reaction tank 30A, it can be said that it is very effective for cooling the heat generated when the reaction is performed.

  The heating / cooling means 50 is not shown in detail, but as an example, a heating means comprising a nichrome wire and a cooling means using various refrigerants such as freon gas are mixed. Such a device, or a device in which piping that allows both hot water and cold water to be located outside is conceivable. It is also effective to add fins to the heating / cooling means 50 itself and to the periphery where the heating / cooling means 50 is located so that the cooling can be performed smoothly, that is, the heat radiation is performed smoothly. Means.

  Accordingly, in the reaction tank 30A, water is reacted with either alkali metal, alkaline earth metal or magnesium to produce hydrogen gas. For this purpose, the reaction tank 30A includes the solid particle storage device 20 and the water supply device 40A. Both are connected so that the substances required for the reaction can be supplied. Moreover, the heating / cooling means 50 is installed so that the water of the required temperature can be supplied from the necessity of using hot water, normal temperature water, or cold water as needed during the reaction. By the way, the heating / cooling means 50 may be used for the purpose of heating the generated heat when heat is generated during the reaction in the reaction tank 30A by utilizing the cooling function.

  Furthermore, in the reaction, the reaction was made in an atmosphere of any one of inert gases including nitrogen gas when the reaction was reacted with water. The gas is a mixed gas of hydrogen gas and any one of inert gases including nitrogen gas, but it is easy to store only hydrogen gas in the hydrogen storage alloy because of high pressure. Has been developed as a high-pressure gas mixture that may be used without any problems.

  In addition, in order to perform such a reaction smoothly in the reaction tank 30A, water is overflowed when the air in the reaction tank 30A is discharged in advance or water is injected before the reaction. A conduit leading to the residual fluid discharge port 303 is formed in the upper part so that it can be confirmed that it is completely filled. In addition, a pressure gauge 203 is connected so that the internal pressure can be measured in order to confirm whether the reaction is ensured. Further, a pipe line leading to the unnecessary soot removal outlet 302 is formed at the bottom of the reaction tank 30A for taking out the unnecessary soot that has settled at the bottom.

  As described so far, the mixed gas containing any one of the hydrogen gas and the inert gas including nitrogen gas produced in the reaction tank 30A is used to supply only hydrogen gas to the hydrogen storage container 70 containing the hydrogen storage alloy. It can be stored. More specifically, from the reaction tank 30A, the high-pressure hydrogen gas pipe 103, the high-pressure hydrogen gas on-off valve 208 that manually opens and closes, the high-pressure hydrogen gas pipe 104, and the pressure that requires high-pressure hydrogen gas. A gas mixture having a constant pressure of depressurized hydrogen gas and inert gas including nitrogen gas is fed into the hydrogen storage container 70 via the pressure reducing valve 211 that can be depressurized and the hydrogen gas pipe 105. It is possible to separate and purify the hydrogen gas by storing only the hydrogen gas in the hydrogen storage alloy.

  In this case, from the hydrogen storage container 70, the hydrogen gas release pipe 141, the hydrogen gas release opening / closing valve 212 that is manually opened / closed, and the hydrogen gas release pipe 142 are passed through the hydrogen storage pipe 70, so that the hydrogen that could not be occluded at some time. It is possible to discharge a mixed gas containing any of an inert gas including a gas and a nitrogen gas, and it is possible to use the stored hydrogen gas at another time.

  The hydrogen storage container 70 generates heat when it is occluded and needs to be heated when the occluded hydrogen gas is used. Therefore, in order to easily serve both the purpose of cooling and heating, As one example, while using a long tube-type container containing a hydrogen storage alloy, it is conceivable to facilitate heat transfer by forming fins. Therefore, it is also conceivable that warm or cold air is sent to the hydrogen storage container 70 as necessary, or hot water or cold water is sent around the hydrogen storage container 70 by placing a serpentine tube on the outer periphery.

  Moreover, the hydrogen storage container 70 of the device of the present invention mainly describes storing hydrogen, including FIG. However, as a matter of course, it is necessary to use the hydrogen gas stored after separating the hydrogen storage container 70 from the hydrogen gas pipe 105 after storing the hydrogen. It may be considered that contrivances such as providing a joint and an on-off valve are taken into consideration so as not to discharge more hydrogen gas.

  By the way, in the description so far, it has been described that all of the various on-off valves 201, 204, 205, 206, 207, 208, 209, 210, 212 are manually opened / closed. It is also possible to open and close by full-automatic or semi-automatic.

  It should be noted that the solid particle input pipe 114 connected to the solid particle input on / off valve 204, the high pressure hydrogen gas pipe 103 connected to the high pressure hydrogen gas on / off valve 208, and the pressure gauge 203 are, in particular, the pressure gauge 203 as much as possible. It is desirable that the length of the pipe is short, and in some cases, it is desirable to directly connect the solid particle charging on / off valve 204, the high-pressure hydrogen gas on / off valve 208, and the pressure gauge 203 directly to the reaction tank 30A. If the reason is described, immediately before the reaction, the solid particle injection pipe 114, the high-pressure hydrogen gas pipe 103, etc. are in a state where no air remains, and any of the inert gases including water and nitrogen gas is used. This is to ensure a fully satisfied state.

  Here, in the present invention, when hydrogen gas is produced by reacting water at a predetermined temperature with either alkali metal, alkaline earth metal, or magnesium, the reaction is performed with any one of inert gases including water and nitrogen gas. It is carried out in a reaction tank 30A that is completely filled with gas, sealed and completely shut off from the outside. The reason why the reaction is performed in an atmosphere of any one of inert gases including nitrogen gas together with water is that the reaction tank 30A completely filled with water, sealed, and completely shut off from the outside is filled with alkali metal. Alternatively, when either alkaline earth metal or magnesium is to be introduced, by providing a space of any atmosphere of inert gas including nitrogen gas, water enters the solid particle storage device 20 side. This is one of the main reasons for preventing this. Therefore, the reaction tank 30A and its periphery can be configured in a simple form.

  The method and apparatus for producing hydrogen gas according to the present invention is configured as described above, and its operation will be described below.

  Before that, a reaction formula for producing hydrogen gas by reacting water with any one of an alkali metal, an alkaline earth metal, or magnesium, and the contents generally mentioned in the reaction will be shown.

  In this case, as the alkali metal, all of Li, Na, K, Rb, and Cs react with water at room temperature to generate hydrogen and become hydroxide. In particular, Na, K, Rb, and Cs react violently. Therefore, considerable heat is generated during the reaction. As an example, when Na and water react, hydrogen gas is generated in the form as shown in [Equation 1].

  As alkaline earth metals, all of Ca, Sr, Ba, and Ra react with cold water to generate hydrogen and become hydroxide. As an example, when Ca and water react with each other, hydrogen gas is generated in the form shown in [Equation 2].

  Further, Mg reacts with hot water to generate hydrogen and become a hydroxide. In addition, when Mg and water react, hydrogen gas is generated in the form as seen in [Equation 3].

  In particular, the point to be described in the present invention is that, for example, specifically with respect to the reaction formula [Equation 1], 36 g of water is reduced by the reaction, that is, 36 cc of water is reduced, and a space is generated. In other words, it was noted that when 22400 cc of hydrogen gas is generated in the space, it becomes high-pressure hydrogen gas. The same can be said for [Equation 2] and [Equation 3], and the reaction formulas are not specifically described for other substances, but similar I can say.

  However, in the present invention, since any one of the inert gases containing nitrogen gas is fed prior to the reaction, the space of any one of the inert gases containing nitrogen gas is also taken into consideration. There must be. That is, it is generated by reacting to the sum of the space occupied by any of the inert gases including the initial nitrogen gas in the reaction tank 30A and the space due to the reduction of water due to the reaction in the reaction tank 30A. Depending on the proportion of the hydrogen gas, a large amount of gas is generated in a small volume, so that it is a mixed gas with any one of inert gases including nitrogen gas, but becomes high-pressure hydrogen gas.

  Therefore, the solid particle storage device 20 is prepared with a predetermined amount of any substance of alkali metal, alkaline earth metal, or magnesium, and supplied with water having a temperature suitable for reacting with the substance. Prepare the device 40A. As a matter of course, the prepared water is controlled at a temperature suitable for reaction by the heating / cooling means 50, and as shown below, the inert gas supply device 10 contains nitrogen gas. It may be considered that any of the inert gases can be sent.

  In this case, regarding the water supply device 40A, the portion for supplying water from the outside is omitted in FIG. 1, but it naturally exists. The water supply portion can be used to discharge the internal gas when the internal gas is replaced with water or any inert gas including nitrogen gas as necessary. It is like that. For example, it is conceivable that a double pipe structure is used, and the air inside is discharged from between the outer and inner pipes while water flows through the inner pipe. Further, it is conceivable to discharge the internal air from between the outer and inner pipes while the inner pipe is closed while supplying any one of the inert gases including nitrogen gas. Therefore, it may be considered that at the time immediately before water supply is performed, the lower part of the water supply device 40A is filled with water and the upper part is filled with any of inert gas gases including nitrogen gas.

  First, the inert gas supply on / off valve 201, the solid particle input on / off valve 204, the high-pressure hydrogen gas on / off valve 208, the feed water on / off valve 210, the unnecessary dredging take-off on / off valve 207, and the pressurizing inert gas on / off valve 209 that is the water supply means 209. In the closed state and with the residual fluid discharge opening / closing valve 206 opened, the inert gas opening / closing valve 209 for pressurization related to the water supply device 40A and the water supply opening / closing valve 210 are opened to react water. Feed into tank 30A. Therefore, since the residual fluid discharge opening / closing valve 206 is opened, the gas in the reaction tank 30A is discharged, and the water overflows, and the reaction tank 30A is completely filled with water. Therefore, the water supply opening / closing valve 210 and then the pressurizing inert gas opening / closing valve 209 are closed. In FIG. 1, although the size of the reaction tank 30A appears to be smaller than that of the water supply device 40A, it may be considered that sufficient water can be supplied.

  Subsequently, by opening the inert gas supply opening / closing valve 201, any one of inert gases including nitrogen gas is fed into the reaction tank 30A. By the way, as for the amount of any one of the inert gases including nitrogen gas fed in, naturally, if it is small, hydrogen gas with high purity can be obtained, and if it is large, the certainty of the reaction is ensured. .

  However, what can be said at a minimum is that the solid particle storage opening / closing valve 204 on the solid particle storage device 20 side reacts even after any of alkali metal, alkaline earth metal, or magnesium is charged into the reaction tank 30A. Based on the premise that water should not enter from the tank 30A and that no air remains in the portion in contact with the inside of the reaction tank 30A or as little as possible, the solid particle input pipe 114 and the high-pressure hydrogen gas That is, it is desirable that a space by any of inert gas containing nitrogen gas can be secured at a slight height above the piping 103, the piping leading to the pressure gauge 203, and the upper portion of the reaction tank 30A. Therefore, it is desirable that each of the above-mentioned pipes and related pipes be as short as possible. If all shapes of the upper part of the reaction tank 30A are taken into consideration, the connection positions of the solid particle input pipe 114 and the fluid discharge pipe 121 with respect to the reaction tank 30A. As for the connection position of the fluid discharge piping 121 to the reaction tank 30A, it is best to connect the fluid discharge piping 121 to the connection portion of the solid particle charging opening / closing valve 204 and the solid particle charging piping 114.

  When any of the inert gas containing nitrogen gas is nitrogen gas, by measuring the nitrogen gas concentration with the nitrogen gas concentration meter 202 connected to the inert gas supply device 10, It can be judged whether the purity of the nitrogen gas is perfect. Even when the gas is an inert gas, it is possible to determine whether or not the purity of the inert gas is complete by measuring the concentration of the oxygen gas.

  In this way, by supplying any inert gas including nitrogen gas from the state where water is completely supplied, and measuring the amount of water overflowing from the residual fluid outlet 303, the reaction It can be confirmed that any desired amount of inert gas containing nitrogen gas is reliably supplied to the tank 30A. Therefore, the inert gas supply opening / closing valve 201 is closed, and the residual fluid discharge opening / closing valve 206 is closed. The solid particle storage on / off valve 204 is opened while the solid particle storage on / off valve 205 is closed, so that the total amount of any one of alkali metal, alkaline earth metal, or magnesium is solidified from the solid particle storage device 20. The particles are charged into the reaction tank 30A, and then the solid particle charging on / off valve 204 is closed when the charging is completed. It is important to prepare either the alkali metal, alkaline earth metal or magnesium in the solid particle storage device 20 for the next supply while the solid particle input opening / closing valve 204 is closed. It is.

  In such a situation, the reaction formulas for all solid particles are not described, but the reaction including nitrogen gas is caused by reactions such as those shown in [Equation 1], [Equation 2], and [Equation 3]. Hydrogen gas is generated in the atmosphere of any one of the active gases, and a high-pressure mixed gas containing any of the inert gas including hydrogen gas and nitrogen gas is created. In this case, the timing of supplying any one of the inert gases including nitrogen gas to the reaction tank 30A may be supplied in accordance with the supply of water. Therefore, while one time of water supply and one of inert gas containing nitrogen gas are supplied, the introduction of solid particles is repeated a plurality of times. The purity of the gas will increase. Moreover, when supplying any gas of the inert gas containing nitrogen gas to the upper part of the reaction tank 30A, it is also one idea to supply it to the solid particle storage device 20 as well. In that case, if the solid particle storage on-off valve 205 is opened momentarily, it is possible to discharge air to the inside.

  On the other hand, by measuring the pressure inside the reaction tank 30 </ b> A with the pressure gauge 203, it is possible to confirm whether the correct reaction has been performed by grasping the increase in pressure.

  When the pressure inside the reaction tank 30A rises to a predetermined pressure due to the reaction, the hydrogen gas discharge on / off valve 212 is opened and the high-pressure hydrogen gas on / off valve 208 is opened, so that the inert gas containing hydrogen gas and nitrogen gas A high-pressure mixed gas of any one of the gases is reduced to a pressure required by the pressure reducing valve 211 so that hydrogen gas can be stored in the hydrogen storage alloy in the hydrogen storage device 70 and stored. In addition, when storing and storing hydrogen gas in the hydrogen storage device 70, it is one of the important ideas to cope with cooling because it generates heat.

  In this case, the high-pressure hydrogen gas on-off valve 208 is opened because it has risen to a predetermined pressure, and a high-pressure mixed gas of any of inert gases including hydrogen gas and nitrogen gas is supplied via the pressure-reducing valve 211. In the process of storing and storing in the hydrogen storage container 70, the hydrogen gas can be supplied and stored until the pressure indicated by the pressure gauge 203 drops to a certain value. Measure the total weight of the hydrogen storage container 70 not specifically shown, in which the hydrogen gas generated by the reaction caused by introducing the solid particles a plurality of times is stored in one hydrogen storage container 70. This means that the storage can not be stored any more if it shows the required weight. In other cases, the hydrogen gas generated by the reaction caused by a single injection of solid particles. Duplicate It is one that stored in the hydrogen storage container 70, with each other to correspond to thereby absorb hydrogen gas in the hydrogen storage container 70 by opening and closing appropriate high-pressure hydrogen gas on-off valve 208 Both.

  As a matter of course, when measuring the total weight of the hydrogen storage container 70, it is necessary to measure the hydrogen gas pipe 105 and the hydrogen storage container 70 separately. Therefore, it is a very effective method to connect with a one-touch type joint that can prevent easy separation and gas leakage.

  Then, while the reaction for producing hydrogen gas inside the reaction tank 30A is continued, the pressure displayed by the pressure gauge 203 increases again. In this way, when the pressure displayed on the pressure gauge 203 rises to a certain value, the high-pressure hydrogen gas on-off valve 208 is opened again, and any high-pressure mixed gas of inert gas including hydrogen gas and nitrogen gas is added. The hydrogen storage container 70 is occluded and stored via the pressure reducing valve 211. If the pressure displayed on the pressure gauge 203 drops to a certain value, the mixed gas of hydrogen gas and inert gas including nitrogen gas produced in the reaction tank 30A is as hydrogen as possible. Since it is considered that the fuel has been sent to the storage container 70, the high-pressure hydrogen gas on-off valve 208 is closed, and the reaction in the reaction tank 30A is started again.

  Here, as a pre-stage for storing and storing the hydrogen gas in the hydrogen storage container 70, when the hydrogen gas is produced by reacting either alkali metal, alkaline earth metal or magnesium with water at a predetermined temperature, the reaction is performed. By performing the reaction in the reaction tank 30A that is completely filled and sealed with water or an inert gas containing nitrogen gas and is completely shut off from the outside, the inert gas containing the initial nitrogen gas in the reaction tank 30A is obtained. Compared to the sum of the space occupied by any of the gases and the space where water is reduced due to the reaction in the reaction tank 30A, the proportion of the hydrogen gas generated by the reaction causes the inert gas containing nitrogen gas Although it becomes a mixed gas with high-pressure hydrogen gas containing any gas, as described above, it is generated in a plurality of hydrogen storage containers 70 in one reaction. It may be a case for storing the hydrogen gas, it is conceivable to store a plurality of reaction with hydrogen gas generated to a single hydrogen cylinder 70.

  Note that the hydrogen storage container 70 that has been filled is removed from the high-pressure hydrogen gas pipe 105. However, although not specifically described in FIG. 1, it may be considered that consideration is given so as not to leak from the connected portion. And the hydrogen storage container 70 is newly connected and filling is repeated. If the reaction of generating hydrogen gas by introducing any one of alkali metal, alkaline earth metal, or magnesium becomes worse, fill the water again with the residual fluid discharge on-off valve 206 opened. Then, the inert gas supply opening / closing valve 201 is opened to supply any one of the inert gases containing nitrogen gas to the reaction tank 30A, and then the inert gas supply opening / closing valve 201 is closed to leave the residual fluid discharge opening / closing valve. 206 is closed, and any one of the substances of alkali metal, alkaline earth metal or magnesium is dropped into the reaction tank 30A, and the reaction for generating hydrogen gas is performed again.

  If the degree of reaction that generates hydrogen gas further deteriorates while continuing the above reaction, this time, the waste take-off opening / closing valve 207 is opened, and the inside of the reaction tank 30A is completely emptied. After that, the waste trap opening / closing valve 207 is closed, the remaining fluid discharge opening / closing valve 206 is opened, and water is filled again. The inert gas supply opening / closing valve 201 is opened, and any inert gas containing nitrogen gas is opened. The gas is supplied to the reaction tank 30A, the inert gas supply on / off valve 201 is closed, the residual fluid discharge on / off valve 206 is closed, and any one of alkali metal, alkaline earth metal, or magnesium is closed. These substances are dropped into the reaction tank 30A, and a reaction for generating hydrogen gas is performed again.

  However, regarding the supply of substances required for the reaction, first, water, then any inert gas including nitrogen gas, and finally any one of alkali metal, alkaline earth metal, or magnesium. So far, it describes a kind of substance. However, it is not necessary to limit in this order. First, any one of alkali metal, alkaline earth metal, or magnesium, then any one of inert gases including nitrogen gas, and finally a small amount of gas. It is also possible to supply water. Furthermore, it is also conceivable to first supply any one of inert gases including nitrogen gas, then any one of alkali metal, alkaline earth metal, or magnesium, and finally a small amount of water. . In this case, it is conceivable to supply any gas of inert gas including nitrogen gas to the solid particle storage device 20 in all cases.

  In addition, when the high-pressure mixed gas of any of the inert gas containing hydrogen gas and nitrogen gas is occluded and stored in the hydrogen storage container 70, any of the inert gas containing nitrogen gas is stored. In order to reduce the amount of hydrogen and increase the purity of the hydrogen gas, one method is to throw away the high-pressure mixed gas of any of the inert gas including hydrogen gas and nitrogen gas generated at the beginning of the reaction. This corresponds to any combination of the above-described order of supplying any one of the inert gas including water and nitrogen gas and any one of alkali metal, alkaline earth metal, and magnesium. Further, before supplying any of an inert gas containing water and nitrogen gas and any of alkali metal, alkaline earth metal or magnesium to start the reaction, the inert gas containing nitrogen gas is used. It is also conceivable to discharge any of these gases. In this case, the residual fluid on-off valve 206 may be used for discharging.

  As seen in FIG. 2, the second embodiment is different from the first embodiment in that the inert gas supply device 10 provided in the first embodiment and the inert gas supply pipe 101 connected thereto are not connected. Active gas supply on / off valve 201, inert gas supply pipe 102, pressurizing inert gas pipe 131 serving as water supply means 131, pressurizing inert gas on / off valve 209 serving as water supply means 209, and pressurizing non-use serving as water supply means 132 The active gas pipe 132 is not configured.

  Therefore, in the second embodiment, the reaction tank 30B is not connected to the piping from the inert gas supply device 10, and the water supply device 40B is provided with the water supply means 132 from the inert gas supply device 10. A certain pressurizing inert gas pipe 132 is not connected. That is, the difference from the first embodiment is that any one of inert gases including nitrogen gas is not supplied.

  The method and apparatus for producing hydrogen gas according to the present invention is configured as described above, and its operation will be described below.

  In this case, the point in which Example 2 differs from Example 1 is that any gas of the inert gas containing nitrogen gas is not used. Therefore, the major difference from Example 1 is that when hydrogen gas is produced by reacting either alkali metal, alkaline earth metal or magnesium with water at a predetermined temperature, the reaction is completely filled with water alone and sealed. It is performed in the reaction tank 30B that is completely cut off from the outside.

  By not using any of the inert gas containing nitrogen gas, there will be no buffer part of any of the inert gas containing nitrogen gas between the solid particles and water. When any one of metal, alkaline earth metal, or magnesium is charged into the reaction tank 30B, the water in the reaction tank 30B easily enters the solid particle storage device 20, and the intruded water and the alkali metal or alkaline earth metal Or it may cause the problem that the magnesium reacts, so it is necessary to pay considerable attention to these operations.

  Therefore, it is conceivable that the amount of water when the reaction tank 30B is completely filled with water is confirmed in advance, and the amount of water is reduced and supplied in consideration of the volume of solid particles. In addition, it is one method to discard the gas that was initially generated in consideration of air mixing. Therefore, a method of filling the reaction tank 30B with water, a method of storing and storing high-pressure hydrogen gas in the hydrogen storage container 70, and a method of charging one of alkali metal, alkaline earth metal, or magnesium into the reaction tank 30B In addition, the heating / cooling means 50 is omitted because it has the same contents except that any of inert gases including nitrogen gas is not supplied to the reaction tank 30B.

  Among them, when producing hydrogen gas by reacting either alkali metal or alkaline earth metal or magnesium with water at a predetermined temperature, the reaction was completely filled with water and sealed and completely shut off from the outside. By performing the reaction in the reaction tank 30B, the high-pressure hydrogen gas is produced according to the proportion of the hydrogen gas generated by the reaction in the space due to the reduction of water due to the reaction in the reaction tank 30B.

  In that case, water is first injected and then either alkali metal, alkaline earth metal or magnesium is fed, and then the reaction is started from a state where there is no space in the reaction tank 30B. However, one method is to first send in either alkali metal, alkaline earth metal or magnesium, then inject water into a small amount, throw away the initially generated gas, and use the generated gas later. It is. In this case, the air is driven out by water to start the reaction.

  The present invention relates to a method and apparatus for producing high-pressure hydrogen gas, and more specifically, from a state where the gas is completely filled with any one of water and an inert gas including nitrogen gas. Chemical reaction between water and any of alkali metals, alkaline earth metals, or magnesium, considering the space occupied by any of the inert gases including nitrogen gas as necessary from the state completely filled with water Depending on the proportion of the hydrogen gas generated by the reaction in the space generated by reducing the amount of water due to water, sometimes it is a mixed gas, but high pressure hydrogen gas is produced, and the generated high pressure hydrogen gas is converted into a hydrogen storage alloy Describes technology for providing hydrogen production equipment, hydrogen storage containers, hydrogen refining equipment, and hydrogen transport equipment by storing in a hydrogen storage container with built-in hydrogen Those were.

  Diagram showing the present invention   The figure which showed another Example which does not use the inert gas containing nitrogen gas of this invention

Explanation of symbols

10. Inert gas supply device 20 Solid particle storage device 30A Reaction tank 30B Reaction tank 40A Water supply device 40B ... Water supply device 50 ... Heating / cooling means 70 ... Hydrogen storage container 101 ... Inert gas supply pipe 102 ... Inert gas supply pipe 103 ... ... High-pressure hydrogen gas pipe 104 ... High-pressure hydrogen gas pipe 105 ... Hydrogen gas pipe 111 ... Solid particle storage pipe 112 ... Solid particle storage pipe 113 ... ····························································································································································・ Fluid discharge pipe 131 ... Inert gas pipe for pressurization (supply Means)
132 .. Inert gas piping for pressurization (water supply means)
133... Water supply pipe 134... Water supply pipe 141... Hydrogen gas discharge pipe 142... Hydrogen gas discharge pipe 201. ············································································································································································ Open valve 207 ... Unnecessary dredging take-off valve 208 ... High-pressure hydrogen gas on-off valve 209 ... Pressurizing inert gas on-off valve (water supply means)
210 ...... Water supply opening / closing valve 211 ...... Pressure reducing valve 212 ...... Hydrogen gas discharge opening / closing valve 301 ...... Solid particle inlet 302 ... Unnecessary intake outlet 303 .... Residual fluid outlet

Claims (10)

  When hydrogen gas is produced by reacting either alkali metal or alkaline earth metal or magnesium with water at a predetermined temperature, the reaction is completely filled and sealed with either an inert gas containing water and nitrogen gas. By performing the reaction in the reaction tank (30A) that is completely disconnected from the outside, the space occupied by any of the inert gases including the initial nitrogen gas in the reaction tank (30A) and the reaction tank (30A) Hydrogen, characterized in that high-pressure hydrogen gas is produced by the proportion of hydrogen gas generated by reaction against the sum of space due to water loss due to reaction, and the high-pressure hydrogen gas is occluded in a hydrogen-absorbing alloy Gas storage method.   Nitrogen gas is produced from compressed air by a membrane separation method or a PSA method. First, water is injected so that the reaction tank (30A) is completely filled, and then nitrogen gas is partially discharged. 2. The method for storing hydrogen gas according to claim 1, wherein the reaction is started after the alkali metal, the alkaline earth metal, or magnesium is finally fed.   When hydrogen gas is produced by reacting either alkali metal or alkaline earth metal or magnesium with water at a predetermined temperature, the reaction is completely filled with water, sealed, and completely shut off from the outside (30B ) In the reaction tank (30B), the high-pressure hydrogen gas is produced by the proportion of the hydrogen gas generated by the reaction to the space resulting from the reduction of water by the reaction in the reaction tank (30B). A method for storing hydrogen gas, comprising storing a hydrogen in a hydrogen storage alloy.   The reaction is started from a state where there is no space in the reaction tank (30B) after first injecting water and then injecting either alkali metal, alkaline earth metal or magnesium. 4. The method for storing hydrogen gas according to 3.   The method for storing hydrogen gas according to any one of claims 1 to 4, wherein the water can be heated or cooled as necessary.   Any of inert gas containing nitrogen gas is sealed in a sealed reaction tank (30A) that generates hydrogen gas by reacting either alkali metal, alkaline earth metal or magnesium with water at a predetermined temperature, and completely shut off from the outside. Connect an inert gas supply device (10) that can supply water, connect a water supply device (40A) that can feed water, and drop either alkali metal or alkaline earth metal or magnesium The reaction tank (30A) is connected to a solid particle storage device (20) that can be stored, and the reaction tank (30A) is completely filled with water or an inert gas containing nitrogen gas. By reducing the amount of water due to the reaction in the reaction tank (30A) and the space occupied by any of the inert gases including the initial nitrogen gas A hydrogen storage container (70) containing high-pressure hydrogen gas from the upper part of the reaction tank (30A) and containing a hydrogen-occlusion alloy in accordance with the proportion of hydrogen gas generated by the reaction with respect to the sum of the spaces. The hydrogen gas storage device is characterized in that it is occluded.   A water supply device that can feed water into a sealed reaction tank (30B) that generates hydrogen gas by reacting either alkali metal, alkaline earth metal, or magnesium with water at a predetermined temperature, and is completely shut off from the outside. 40B) and a solid particle storage device (20) storing either alkali metal, alkaline earth metal or magnesium in a dropable manner, and the reaction tank (30B) is completely filled with water. From the state, the high-pressure hydrogen gas is formed by the proportion of the hydrogen gas generated by the reaction to the space due to the reduction of water by the reaction in the reaction tank (30B), and the high-pressure hydrogen gas is converted into the reaction tank. (30B) is stored in a hydrogen storage container (70) containing a hydrogen storage alloy from above. Storage devices of the hydrogen gas.   The heating / cooling means (50) for heating or cooling water to a necessary temperature is disposed in or around the water supply device (40A, 40B) or the reaction tank (30A, 30B). Alternatively, the hydrogen gas storage device according to claim 7.   The reaction tank (30A, 30B) has a residual fluid discharge port (303) that can discharge the internal fluid from the upper part, and an internal waste and liquid from the lower part. In order to form the unused waste outlet (302) and to make the reaction tank (30A, 30B) more completely shut off from the outside, the inert gas supply device (10) is inert. Between the gas supply opening / closing valve (201) and the solid particle storage device (20), the solid particle charging opening / closing valve (204) and between the water supply device (40A, 40B), the water supply opening / closing valve (210). The high-pressure hydrogen gas on-off valve (208) is connected to the hydrogen storage container (70), the residual fluid discharge on-off valve (206) is connected to the residual fluid discharge port (303), and the unnecessary intake port ( 302) and a waste take-off opening / closing valve Storage device of hydrogen gas of any one of claims 5 to 8, characterized in that the 207) is disposed.   The hydrogen storage container (70) can be heated and cooled from the outside, and the high-pressure hydrogen gas is decompressed between the high-pressure hydrogen gas on-off valve (208) and the hydrogen storage container (70). 10. The hydrogen gas storage device according to claim 9, further comprising a pressure reducing valve (211).

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