JP6824066B2 - Gas generator, generation system and generation method - Google Patents

Description

The present invention relates to a gas generator, a generation system and a generation method, and more particularly to a gas generator for generating hydrogen gas or oxygen gas, a gas generation system and a gas generation method.

Conventionally, a gas generator for supplying fuel gas has been used for a fuel drive device that generates electricity from fuel gas such as a gas engine and a fuel cell. In such a gas generator, as a method of taking out the fuel gas, a heating decomposition method that generates the fuel gas at a temperature of about 200 ° C. by heating, or a heating decomposition method that generates the fuel gas in the range of normal temperature to 150 ° C. by supplying water. Hydrolysis method is used. These methods have a higher gas storage density than gas cylinders and the like, and are expected methods for extending the cruising range, especially in moving objects.

In a gas generator using a thermal decomposition method, it is necessary to secure a heat source that continuously supplies heat for heating to generate fuel gas. As a heat source, exhaust heat from a fuel drive device such as a gas engine or a fuel cell, a heater, or the like is used. As one of such gas generators, there is known a device that heats a hydrogenated metal by utilizing the exhaust heat of a hydrogen engine and supplies it as a fuel gas to the hydrogen engine (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2-95760

In the above example, for example, when the exhaust heat from the fuel drive device serving as a heat source is lower than the temperature required to generate the fuel gas, it is insufficient to generate the fuel gas. In addition, a heating means for heating the low-temperature exhaust heat to the temperature at which the fuel gas is generated is required. Further, when the exhaust heat of the fuel drive device is used as a heat source, the exhaust heat is not generated when the fuel drive device is started, so that it cannot be used and it is necessary to separately provide a heating facility. ..
Furthermore, if the hydrolysis method is used to generate fuel gas, it is not necessary to install a heating facility because fuel gas is generated just by supplying water, but more water than the theoretical amount is required and gas is generated. The amount of water loaded in the device increases, and the gas storage density becomes low.

In light of the above circumstances, the present invention does not require a heating means for heating the exhaust heat or a heating facility for starting even if the exhaust heat from the fuel drive device serving as a heat source is low, and a large amount of water is used. It is an object of the present invention to provide a gas generator, a gas generation system, and a gas generation method capable of generating fuel gas in a simple and compact manner without using the above.

The present invention is a gas generator on one side. The gas generator includes a gas absorbing material that generates heat by absorbing gas, a gas releasing material that releases gas by heating, a supply port that supplies gas from outside the system, and a discharge port that discharges gas to the outside of the system. The gas absorbing material and the gas releasing material are provided with an internal closed container so as to transfer heat to each other, and the temperature reached by the gas absorbing material absorbing the gas is the gas of the gas releasing material. It is set to be higher than the thermal decomposition temperature for release, and the amount of gas released by the gas releasing material is larger than the amount of gas absorbed by the gas absorbing material.

The amount of gas released by the outgassing material can be at least twice the amount of gas absorbed by the gas absorbing material.

The gas absorbing material and the outgassing material can be a hydrogen absorbing agent and a hydrogenating agent or an oxygen absorbing agent and an oxygenating agent. The hydrogen absorber is preferably Mg ₂ Ni, Zrmn ₂ or Nb ₂ O ₅ to which Mg is added, and the hydrogenating agent is lithium aluminum hydride, sodium borohydride, active magnesium, hydrogenated. Lithium boron hydride, magnesium hydride, sodium borohydride or aluminum hydride is preferred. The oxygen absorber is preferably iron fine powder or a mixture of iron fine powder and ceramic, and the oxygen agent is preferably silver oxide.

Further, in one embodiment of the gas generator according to the present invention, the layer of the gas absorbing material and the layer of the gas releasing material are laminated, and the layer of the gas absorbing material is placed on the supply port side of the closed container. Is arranged, and the layer of the outgassing material is arranged on the discharge port side of the closed container.

Further, in the gas generator according to the present invention, in another embodiment, a plurality of layers of the gas absorbing material and the gas releasing material are laminated along the supply port to the discharge port of the closed container.

Further, in the gas generator according to the present invention, in still another embodiment, the gas absorbing material is arranged in contact with the supply port of the closed container, and the gas releasing material is placed around the gas absorbing material. It is supposed to be placed in contact.

Further, the present invention is a gas generation system in another aspect. The gas generation system is a gas generation system in which a plurality of the gas generators are arranged along the direction in which the gas is supplied, and the gas from outside the system is supplied to the plurality of gas generators independently. To a supply flow path having one end to which gas is supplied from outside the system, a plurality of other ends connected to the supply ports of the plurality of gas generators together with an on-off valve, and a discharge port of the gas generator. A cooling medium circulates inside the discharge flow path having one end to be connected and the other end to discharge the gas generated by the gas generator to the outside of the system, and heat exchanges with the plurality of gas generators. It is equipped with a temperature control flow path that contacts in sequence as possible and is equipped with a heat exchanger.

Further, the present invention is a gas generation method in another aspect. The gas generation method includes a first gas generation step of generating gas by supplying gas from outside the system to one of the plurality of gas generators and discharging the gas to the outside of the system, and the first gas generation method. When the process is completed, the cooling medium in the temperature control flow path is circulated to recover the heat stored in the one gas generator and the other of the plurality used to generate hydrogen next. The first preheating step of preheating the gas generator and the second gas generating step of generating gas by supplying gas from outside the system to the other preheated gas generator and discharging the gas to the outside of the system. I will prepare.

Further, the gas generation system according to the present invention is, in one embodiment, a gas generation system in which a plurality of the gas generators are arranged along a direction in which the gas is supplied, and the plurality of gases from outside the system are provided. A supply having one end to which gas is supplied from outside the system and a plurality of other ends connected to the supply ports of the plurality of gas generators together with an on-off valve so as to independently supply the gas generators of the above. A flow path, one end connected to the discharge port of the gas generator, the other end of discharging the gas generated by the gas generator to the outside of the system, a thermometer, and a first discharge flow path having an on-off valve. One end connected to the first discharge flow path of one of the plurality of gas generators so as to supply the gas generated by the one gas generator to the other gas generator, and the other. The other end connected to the discharge port of the gas generator of the above via a supply flow path to the other gas generator, a temperature control flow path having an on-off valve, and the one gas generator side to the supply flow path. One end connected between the on-off valve and the on-off valve on the other gas generator side, the other end for discharging a part of the gas generated by the one gas generator to the outside of the system, and the on-off valve. It is provided with a second discharge flow path having the same.

Further, the gas generation method according to the present invention is a gas generation method using the gas generation system according to the embodiment, and supplies gas from outside the system to one of the plurality of gas generation devices. By doing so, when the temperature of the first gas generation step of generating gas and discharging it to the outside of the system and the temperature of the gas generated in the first gas generation step become equal to or higher than a predetermined temperature, the first supply flow A second preheating step of preheating the other gas generator by supplying the generated gas to the other gas generator among the plurality of gas while discharging the gas from the path to the outside of the system, and the preheated other It is provided with a second gas generation step of generating gas and discharging it to the outside of the system by supplying gas from outside the system to the gas generator of the above.

According to the present invention, even if the exhaust heat from the fuel drive device as a heat source is low, a large amount of water is used without the need for a heating means for heating the exhaust heat or a heating facility for starting. A gas generator, a gas generation system, and a gas generation method capable of generating fuel gas in a simple and compact manner are provided.

FIG. 1 is a conceptual diagram conceptually showing the configuration of the gas generator according to the present invention. FIG. 2A is a schematic view showing the configuration of the first embodiment of the gas generator according to the present invention, and FIG. 2B is a second view of the gas generator according to the present invention. FIG. 2C is a schematic view showing the configuration of the device for the embodiment, and FIG. 2C is a schematic view showing the configuration of the device for the third embodiment of the gas generator according to the present invention. FIG. 3 is a schematic view showing the configuration of the gas generation system and the first embodiment of the gas generation method according to the present invention. 4 (A) and 4 (B) are schematic views showing the configuration of the gas generation system and the second embodiment of the gas generation method according to the present invention.

Hereinafter, embodiments of a gas generator, a gas generation system, and a gas generation method according to the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the embodiments described below. In addition, the attached drawings are diagrams for explaining the outline of the present embodiment, and some of the attached devices are omitted.

[1. Gas generator]
First, the concept of the gas generator according to the present invention will be described with reference to FIG. The gas generator 10 according to the present invention includes a gas generator 3 and a closed container 5.
The gas generator 3 is composed of a gas absorbing material that generates heat by absorbing gas supplied from the outside of the gas generating device 10 and a gas releasing material that releases gas by heating. The gas absorbent is a material whose temperature reached by absorbing the gas is higher than the thermal decomposition temperature for the outgassing material to release the gas. Further, the outgassing material is a material in which the amount of released gas is larger than the amount of gas absorbed by the gas absorbing material.
Further, the closed container 5 is an airtight container, and the gas absorbing material and the gas releasing material of the gas generator 3 are contained therein so as to transfer heat to each other. Further, the closed container 5 supplies gas (hereinafter, also referred to as supply gas) from the outside (outside the system) of the closed container 5 from one end thereof, and the other end communicates with the supply port of the closed container 5. It is provided with 5a and a discharge flow path 5b in which gas generated in the closed container 5 (hereinafter, also referred to as generated gas) is discharged from one end thereof and the other end communicates with the discharge port of the closed container 5.
That is, the gas generator 10 is configured to generate a gas generated in an amount equal to or larger than the amount of the gas supplied from the outside of the closed container 5, preferably twice or more as much as the gas supplied from the outside of the closed container 5. It is configured to generate gas.

With the above configuration, when the supply gas is supplied into the closed container 5, the gas absorbent absorbs the supply gas and generates heat. As a result, both the gas absorbing material and the gas releasing material of the gas generator 3 are heated. The outgassing material releases gas when heated, and starts outgassing (pyrolysis) at a predetermined temperature, for example, about 150 ° C. In this case, an endothermic reaction occurs and the gas absorber is cooled.
As a result, the gas generator 10 can generate more gas than the amount of gas supplied from outside the system. For example, when the supply gas is hydrogen gas, the calorific value when Mg ₂ Ni used as the gas absorbing material occludes the hydrogen gas is 74 kJ / mol, and the aluminum hydride used as the gas releasing material releases the hydrogen gas. The amount of heat absorbed at this time is 5.1 kJ / mol. Therefore, considering the balance of the amount of heat, 14.5 mol of hydrogen gas can be generated by occluding 1 mL of hydrogen gas in the gas absorber.
Therefore, gas can be generated even when the supply gas is at a low temperature, and gas can be generated without using an electric or mechanical heating means such as a heater or a burner. Further, even if the heat source is exhaust heat of a fuel drive device such as a hydrogen engine or a fuel cell, gas can be generated without the need for heating equipment required for starting the fuel drive device. Therefore, efficient gas generation can be realized.

The gas absorbing material constituting the gas generator 3 is a hydrogen absorbing agent or an oxygen absorbing agent, and the gas releasing material is a hydrogenating agent or an oxygening agent.
Here, the temperature reached by the gas absorbing material by absorbing the gas is set higher than the thermal decomposition temperature for releasing the gas of the gas releasing material. The temperature to be reached can be appropriately set by selecting the gas absorber and the gas release material so that the amount of gas released by the gas release material is larger than the amount of gas absorbed by the gas absorber.
The hydrogen absorber is preferably a hydrogen storage alloy, for example, Mg ₂ Ni, Zrmn ₂ , Niobium oxide (Nb ₂ O ₅ ) to which Mg is added, or the like. Examples of the hydrogenating agent include lithium aluminum hydride (LiAlH ₄ ), sodium aluminum hydride (NaAlH ₄ ) to which a titanium catalyst is added, active magnesium, lithium borohydride (LiBH ₄ ), and sodium borohydride (NaBH ₄ ). , Magnesium borohydride (MgH ₂ ), Aluminum hydride (AlH ₃ ), etc. As the combination of the hydrogen absorber and the hydrogenating agent, it is preferable to select a combination in which the amount of hydrogen gas released by the hydrogenating agent is at least twice the amount of hydrogen gas absorbed by the hydrogen absorbing agent. .. The oxygen absorber is iron fine powder, iron fine powder mixed with ceramic, and the like, and the oxygen agent is silver oxide and the like. It is preferable to select a combination of the oxygen absorber and the oxygen agent so that the amount of oxygen gas released by the oxygen agent is at least twice the amount of oxygen gas absorbed by the oxygen storage material.
By the above combination, gas such as hydrogen gas and oxygen gas can be efficiently generated, so that the power generation efficiency of the fuel drive device such as a fuel cell can be improved.

When the supply gas is hydrogen gas, the supply gas supplied into the closed container 5 includes hydrogen gas in a hydrogen gas cylinder, a small amount of hydrogen gas generated by hydrolysis, a small amount of hydrogen gas obtained by vaporizing liquid hydrogen, and the like. Hydrogen gas can be used. The purity of the supplied hydrogen gas is preferably 99.9999% or more from the viewpoint of the generation efficiency of the generated gas (hydrogen gas). When the supply gas is oxygen gas, oxygen gas such as oxygen gas in the oxygen gas cylinder, a small amount of oxygen gas generated by hydrolysis, and a small amount of oxygen gas vaporized from liquid oxygen can be used. The purity of the supplied oxygen gas is preferably 99.99999% or more from the viewpoint of the generation efficiency of the generated gas (oxygen gas).
As a result, gases such as hydrogen gas and oxygen gas can be efficiently generated without using a large amount of water.

1.1. First Embodiment Next, the gas generator according to the first embodiment will be described with reference to FIG. 2 (A). In addition, about FIG. 1, the same structure as the above-mentioned structure is given the same number, and the description is omitted. Further, in the embodiment described below, a case where the target gas is hydrogen gas (H ₂ ) will be described as an example.

As shown in FIG. 2A, in the gas generator 10A according to the first embodiment, the layer of the hydrogen absorbing agent 3a and the layer of the hydrogenating agent 3b are laminated so as to be able to transfer heat to each other, and a closed container. A layer of the hydrogen absorber 3a is arranged on the supply port side of No. 5, and a layer of the hydrogenating agent 3b is arranged on the discharge port side of the closed container 5. That is, the layer of the hydrogen absorber 3a and hydrogen so that the hydrogen gas supplied from outside the system first contacts the hydrogen absorber 3a along the direction from the supply port of the closed container 5 to the discharge port of the closed container 5. The layers of the agent 3b are arranged in order. In the present specification, words such as "upper", "lower", "upstream", and "downstream" are used along the direction in which hydrogen gas flows.

With the above configuration, when hydrogen gas is supplied from outside the system into the closed container 5 via the supply flow path 5a, the hydrogen gas first comes into contact with the hydrogen absorber 3a, and the hydrogen absorber 3a occludes the hydrogen gas. The temperature rises. When the hydrogen storage capacity of the hydrogen absorber 3a decreases and its temperature rises, the supplied hydrogen gas is heated in the upper layer of the hydrogen absorber 3a and flows to the lower layer of the hydrogen absorber 3b. As a result, the layer of the hydrogenating agent 3b is gradually heated, and the generation of hydrogen gas is started by the thermal decomposition of the hydrogenating agent 3b in the lower stage. When the supply of hydrogen gas from outside the system is stopped, heat is less likely to be transferred to the hydrogenating agent 3b, and the generation of hydrogen gas is stopped by self-cooling by thermal decomposition of the hydrogenating agent 3b.

According to the present embodiment, the heat generated by the gas absorber can be efficiently used for generating gas. Therefore, the amount of the gas absorbing material loaded can be reduced. Further, by controlling the amount of gas supplied from outside the system, it is possible to control the amount of gas generated in the closed container and control the amount of gas generated outside the system.

1.2. Second Embodiment Next, the gas generator according to the second embodiment will be described with reference to FIG. 2 (B). In addition, about FIG. 1, the same structure as the above-mentioned structure is given the same number, and the description is omitted.

As shown in FIG. 2B, in the gas generator 10B according to the second embodiment, the hydrogen absorber 3a and hydrogenation are carried out along the direction from the supply port of the closed container 5 to the discharge port of the closed container 5. A plurality of layers of the agent 3b are laminated. That is, the layers of the hydrogen absorber 3a and the layers of the hydrogenating agent 3b are alternately arranged in order from the supply port side of the closed container 5. By laminating a plurality of layers of the hydrogen absorber 3a and the hydrogenating agent 3b in this way, the upstream side in the closed container 5 can be used as the preheating zone, and the downstream side thereof can be used as the hydrogen gas generation zone. Therefore, the amount of hydrogen gas generated from the hydrogenating agent 3b can be increased by reacting the hydrogen gas supplied from outside the system with the hydrogen absorbing agent 3a without waste. That is, by setting the upstream side in the closed container 5 as the preheating zone and the downstream side as the gas generation zone, the gas supplied from outside the system is reacted with the gas absorbing material without waste, and the gas from the outgassing material is discharged. The amount generated can be increased.

1.3. Third Embodiment Next, the gas generator according to the third embodiment will be described with reference to FIG. 2C. In addition, about FIG. 1, the same structure as the above-mentioned structure is given the same number, and the description is omitted.

As shown in FIG. 2C, in the gas generator 10C according to the third embodiment, the hydrogen absorber 3a is placed in contact with the supply port of the closed container 5, and the hydrogenating agent 3b is placed in contact with the hydrogen absorbing agent 3a. It is placed in contact with the surroundings of. According to the present embodiment, all of the hydrogen gas supplied into the closed container 5 is absorbed by the hydrogen absorber 3a, and the heat is transferred by the hydrogen absorber 3a and the hydrogenating agent 3b is thermally decomposed. Hydrogen gas is generated. According to the present embodiment, there is a particular advantage when the supply gas is oxygen gas and the outgassing material is an oxygenating agent.

[2. Gas generation system and gas generation method]
2.1. First Embodiment

Next, the first embodiment of the gas generation system according to the present invention will be described with reference to FIG. As shown in FIG. 3, the gas generation system according to the present embodiment includes, for example, any of the gas generators according to the first to third embodiments described above, the supply flow path 20, the discharge flow path 30, and the discharge flow path 30. It is provided with at least a temperature control flow path 40. In the present embodiment, a case where the target gas is hydrogen gas will be described as an example. Further, in the following embodiments, "outside the system" refers to the outside of the system.

The gas generators 11 to 13 are arranged in order along the direction in which hydrogen gas is supplied. That is, the plurality of gas generators 11 to 13 are sequentially generated from one end side of the discharge path 20 so that hydrogen can be generated in the order of the gas generator 11, the gas generator 12, and the gas generator 13. They are arranged in parallel.

The supply flow path 20 opens and closes at one end to which hydrogen gas is supplied and at the supply ports of the plurality of gas generators 11 to 13 so as to independently supply hydrogen gas to the plurality of gas generators 11 to 13. It has a plurality of other ends connected together with valves 24 to 26. Specifically, the supply flow path 20 supplies hydrogen gas to one end to which hydrogen gas is supplied, a supply flow path 21 branched so as to supply hydrogen gas to the gas generator 11, and the gas generator 12. The supply flow path 22 branched at a position beyond the branch point with the supply flow path 21 and the supply flow path 22 branched at a position beyond the branch point with the supply flow path 22 so as to supply hydrogen gas to the gas generator 13. It is provided with a supply flow path 23. That is, the other ends of the supply channels 21 to 23 communicating with the supply ports of the gas generators 11 to 13 correspond to the plurality of other ends of the supply channels 20. Further, on the other end side of the supply flow paths 21 to 23, on-off valves 24 to 26 for supplying hydrogen gas from outside the system to the gas generators 11 to 13 are provided, respectively.

The discharge flow path 30 has a discharge flow path having one end connected to each discharge port of the gas generators 11 to 13 and the other end of discharging the gas generated by each of the gas generators 11 to 13 to the outside of the system. It is equipped with 31 to 33. Specifically, the discharge flow path 30 includes a discharge flow path 31 having one end for discharging the hydrogen gas discharged by the gas generator 11 to the outside of the system and the other end communicating with the discharge port of the gas generator 11, and gas generation. A discharge flow path 32 having one end for discharging the hydrogen gas discharged by the device 12 and the other end communicating with the discharge port of the gas generator 12 and the hydrogen gas discharged by the gas generator 13 are discharged to the outside of the system. It is provided with a discharge flow path 33 having one end and the other end communicating with the discharge port of the gas generator 13. The discharge flow path 31 is provided with a thermometer 31a for measuring the temperature of the hydrogen gas generated by the gas generator 11. Although omitted in the drawing, thermometers having the same configuration are also provided in the discharge channels 32 and 33.

A cooling medium circulates inside the temperature control flow path 40, and the temperature control flow path 40 is in contact with the gas generators 11 to 13 in order so as to be heat exchangeable, and includes a heat exchanger 41. Specifically, in the temperature control flow path 40, the temperature circulation flow path 40 is in contact with the gas generators 11 to 13 in the order in which hydrogen gas is supplied, and the heat exchanger 41 and the cooling medium to the heat exchanger 41 are contacted. The on-off valves 42 and 43 for supplying and stopping the cooling medium and the circulation pump P ₄₀ for circulating the cooling medium are provided. The circulation pump P ₄₀ is electrically connected to the thermometer 31a of the discharge flow path 31, and is connected to the thermometer 31a by a control signal from a control device (not shown) or by inputting a start or stop command to the control device. It is configured to be able to drive and stop based on the temperature measured in. Further, the on-off valves 42 and 43 are electrically connected to the thermometer 31a, and are independently connected to each other by a control signal from a control device (not shown) or by inputting a start or stop command to the control device. It is configured to be openable and closable. The on-off valves 42 and 43 are also electrically connected to the thermometers (not shown) of the discharge flow paths 32 and 33 described above, respectively, and are started or stopped by a control signal from a control device (not shown) or to the control device. It is configured to be independently openable and closable by inputting a command.

Next, the first embodiment of the gas generation method will be described below by explaining the operation mode of the gas generation system having the above configuration. The gas generation method according to the present embodiment includes at least a first gas generation step, a first preheating step, and a second gas generation step.

First, in the first gas generation step, with the on-off valve 24 opened and the on-off valves 25 and 26 closed, hydrogen gas outside the system is supplied to the first gas generator 11 via the supply channels 20 and 21. By supplying the gas, the gas generator 11 generates hydrogen gas.

In the first preheating step, when or after the generation of hydrogen gas in the gas generator 11 is almost completed, the circulation pump P ₄₀ is driven with the on-off valve 24 open, and the cooling medium is moved to the temperature control flow path 40. The heat stored in the gas generator 11 is recovered by circulating the heat. The cooling medium that has recovered the heat preheats the inside of the gas generator 12 used for generating hydrogen gas next through the temperature control flow path 40.

In the second gas generation step, the on-off valve 24 is closed, the on-off valve 25 is closed, and hydrogen gas is supplied to the second gas generator 12 via the supply channels 20 and 22 during preheating or after the preheating is completed. As a result, hydrogen gas is generated in the preheated gas generator 12. After that, the gas generator 13 is similarly preheated and hydrogen is generated.

Further, the gas generation method according to the present embodiment can optionally further include a first temperature control step and a cooling step.
In the first temperature control step, the temperature of the hydrogen gas supplied to the user is measured by the thermometer 31a of the discharge flow path 31 while the hydrogen gas is generated by the gas generator 11. When the hydrogen gas temperature measured by the thermometer 31a is high (for example, 80 ° C.), the user requests the hydrogen gas temperature by circulating the cooling medium in the temperature control flow path 40 by the circulation pump P _40. Control to reduce to a degree. When the user is a fuel cell, the temperature of the cooling medium to be controlled is preferably a temperature lower than the temperature for generating electricity of the fuel cell. The temperature for generating electricity in the fuel cell is, for example, in the range of 40 ° C. to 80 ° C.

Further, the cooling step is applied when the gas generation system is stopped for a long time. In this step, the on-off valves 24 to 26 are closed in order to stop the gas generation system for a long time. The cooling medium is circulated in the temperature control flow path ₄₀ by the circulation pump P ₄₀ , and the cooling medium flows into the heat exchanger 41 by closing the on-off valve 42 and opening the on-off valve 43. In the heat exchanger 41, the temperature of the cooling medium is lowered by exchanging heat between the cooling medium and a medium (air, seawater, etc.) outside the system. The inside of the gas generators 11 to 13 is deheated by circulating the cooling medium in the temperature control flow path 40 while cooling it in the heat exchanger 41.

According to the gas generation system and the gas generation method of the present embodiment, the gas is supplied next to the gas generator 11 that generated the gas, similarly to the gas generator according to the first to third embodiments described above. Since the inside of the gas generating measure 12 can be preheated, the amount of the gas absorbing material for heating the gas discharging material in the gas discharging body 3 can be reduced in the gas generating devices 11 to 13. Therefore, the amount of the gas generator 3 mounted in the gas generators 11 to 13 and the gas generation system including them is reduced, and the amount of gas supplied to the gas generators 11 to 13 and the gas generators 11 to 13 are provided. The amount of gas used in the gas generation system can be reduced.

2.2. Second Embodiment Next, the second embodiment of the gas generation system according to the present invention will be described with reference to FIG. 4 (A). As shown in FIG. 4A, the gas generation system according to the present embodiment is, for example, along the direction in which hydrogen gas is supplied to any of the gas generators according to the first to third embodiments described above. It is provided with at least a supply flow path 20, a first discharge flow path 30, a temperature control flow path 140, and a second discharge flow path 50. The description of the same configuration as that of the first embodiment of the gas generation system described above will be omitted. Further, also in the present embodiment, the case where the gas is hydrogen gas will be described as an example.

The supply flow path 20 has substantially the same configuration as that of the first embodiment and the supply flow path 20. That is, the supply flow path 20 is provided to one end to which hydrogen gas is supplied and to the supply ports of the plurality of gas generators 11 to 13 so that hydrogen gas is independently supplied to the plurality of gas generators 11 to 13. Each has a plurality of other ends connected together with the on-off valves 24 to 26. Further, the on-off valves 24 to 26 are electrically connected to the thermometer 31a, respectively, and are independently connected to each other by a control signal from a control device (not shown) or by inputting a start or stop command to the control device. It is configured to be openable and closable.

The first discharge flow path 30 has substantially the same configuration as that of the first embodiment and the discharge flow path 30. That is, the first discharge flow path 30 has a discharge flow having one end connected to the discharge port of the gas generators 11 to 13 and the other end for discharging the hydrogen gas generated by the gas generators 11 to 13 to the outside of the system. Roads 31 to 33 are provided independently of each other. The discharge flow path 31 is provided with an on-off valve 31b that controls the opening and closing of the hydrogen gas generated by the gas generator 11 to the outside of the system. The on-off valve 31b is electrically connected to the thermometer 31a and is configured to be openable and closable by a control signal from a control device (not shown) or by inputting a start or stop command to the control device. ing. Although omitted in the drawing, the discharge flow paths 32 and 33 are also provided with on-off valves having the same configuration.

The temperature control flow path 140 opens and closes the discharge flow path 31 of the gas generator 11 with a thermometer 31a so as to supply the hydrogen gas generated by the gas generator 11 to the gas generator 12 that supplies the hydrogen gas next. It has one end connected to the valve 31b, the other end connected to the supply port of the gas generator 12 via the supply flow path 22 of the gas generator 12, and an on-off valve 142. The other end of the temperature control flow path 140 is connected to the supply flow path 22 between the on-off valve 24 and the supply port of the gas generator 12. Further, the on-off valve 142 is electrically connected to the thermometer 31a, and is configured to be openable and closable by a control signal of a control device (not shown) or by inputting a start or stop command to the control device. Has been done. Although omitted in the drawing, the discharge flow path 31 and the gas of the gas generator 12 are supplied so that the hydrogen gas generated by the gas generator 12 is supplied to another gas generator 13 that supplies hydrogen gas next. A configuration similar to that of the temperature control flow path 140 is provided between the supply flow path 22 of the generator 13.

The second discharge flow path 50 has one end connected between the on-off valve 24 on the gas generator 11 side and the on-off valve 25 on the gas generator 12 side in the supply flow path 20, and hydrogen generated by the gas generator 11. It has an other end that discharges a part of gas to the outside of the system, and an on-off valve 51 that controls opening and closing of discharge of hydrogen gas to the outside of the system. Further, the on-off valve 51 is electrically connected to the thermometer 31a of the discharge flow path 31, and can be opened and closed by inputting a control signal from a control device (not shown) or a start or stop command to the control device. It is configured to be controlled.

Next, the second embodiment of the gas generation method will be described below by explaining the operation mode of the gas generation system having the above configuration with reference to FIGS. 4 (A) and 4 (B). The gas generation method according to the present embodiment includes at least a first gas generation step, a second preheating step, and a second gas generation step.

In the first gas generation step, with the on-off valve 24 opened and the on-off valves 25 and 26 closed, hydrogen gas outside the gas generation system system is supplied to the supply flow path 20 via the supply flow paths 20 and 21. Hydrogen gas is generated in the gas generator 11 by supplying the gas to the gas generator 11.

In the second preheating step, the temperature of the hydrogen gas generated from the gas generator 11 is measured by the temperature system 31a of the discharge flow path 31 while the hydrogen gas is being generated by the gas generator 11, and the temperature of the hydrogen gas is predetermined. (For example, 50 ° C. to 200 ° C.) or higher, the on-off valve 31b is closed and the on-off valve 142 is opened. By supplying the hydrogen gas generated by the gas generator 11 to the gas generator 12 via the temperature control flow path 140, the inside of the gas generator 12 used for generating hydrogen gas next is preheated. Further, the hydrogen gas from the supply flow path 20 is supplied to the user side by opening the on-off valve 51 of the second discharge flow path 50 [FIG. 4 (B)] together with the preheating of the gas generator 12.

In the second gas generation step, the on-off valve 24 is closed, the on-off valve 25 is opened, and hydrogen gas outside the gas generation system system is supplied to the supply flow path 20 via the supply flow paths 20 and 22 during preheating or after the preheating is completed. By supplying to the second gas generator 12, hydrogen gas is generated in the preheated gas generator 12. After that, the gas generator 13 is similarly preheated and hydrogen is generated.

Further, the gas generation method according to the present embodiment can optionally further include a second temperature control step.
In the second temperature control step, a part of the hydrogen gas generated by the gas generator 11 in the preheating step is supplied to the user side, and the on-off valve 25 is opened to open the supply flow path 22. , The rest of the hydrogen gas generated by the gas generator 11 can be merged with the hydrogen gas from the cylinder or the like. For example, when the temperature of the hydrogen gas from the cylinder or the like is 30 ° C. and the temperature of the hydrogen gas generated from the gas generator 11 is 150 ° C., the hydrogen gas that supplies the rest of the hydrogen gas generated by the gas generator 11 By merging with a ratio of 2: 1 to hydrogen gas at about 70 ° C. Regarding the temperature control, it is preferable to set the temperature to be substantially equal to or lower than the user's operating temperature such as the power generation temperature of the fuel cell.

According to the gas generation system and the gas generation method of the present embodiment, similarly to the first embodiment described with reference to FIG. 3, the gas generation measure 12 for supplying gas next to the gas generation device 11 for generating gas. Since the inside can be preheated, it is possible to reduce the amount of the gas absorbent material for heating the gas discharge material in the gas discharger 3 in the gas generators 11 to 13. Therefore, the amount of the gas generator 3 mounted in the gas generators 11 to 13 and the gas generation system including them is reduced, and the amount of gas supplied to the gas generators 11 to 13 and the gas generators 11 to 13 are provided. The amount of gas used in the gas generation system can be reduced.

In the gas generation system and the gas generation method according to the first and second embodiments, a configuration including three gas generators 11 to 13 is illustrated. The present invention is not limited to this. Any gas generation system and gas generation method having two or more gas generators may be used, and a gas generation system and gas having two or more gas generators according to the amount of gas or power generation requested by the user. It can be a generation method.

Further, in the gas generation system and the gas generation method according to the first and second embodiments, the gas generator 12 adjacent to the gas generator 11 is preheated and gas is generated during or after the gas is generated by the gas generator 11. The configuration and method used to generate the gas are illustrated. The present invention is not limited to this. The gas generator preheated during or after the gas generation of the first gas generator may be the target to be used for the next generation of hydrogen. For example, in the first embodiment, the temperature control flow path 40 may be configured to include a flow path passing through only the gas generator 11 and the gas generator 13, and in the second embodiment, the temperature control flow path 140 may be provided. May be configured to communicate the discharge flow path 31 of the gas generator 11 and the supply port of the gas generator 13.

Further, in the gas generator according to the first to third embodiments and the gas generation system and the gas generation method according to the first and second embodiments, the supplied gas is supplied to the gas generator from outside the system to supply the gas. It is illustrated that the generated gas is discharged to the outside of the system and used. The present invention is not limited to this. According to the present invention, since the amount of generated gas can be increased more than the amount of supplied gas, the flow path for circulating the generated gas is outside the system of the gas generator, inside or outside the gas generation system. The amount of generated gas finally obtained can be increased by providing a step of circulating the gas generated by the provided configuration or the gas generation method and reusing it as a supply gas.

According to the gas generator, the generation system, and the generation method according to the present invention, even if the exhaust heat from the heat source is low, a large amount of the exhaust heat does not need a heating means for heating the exhaust heat or a heating facility for starting. Fuel gas can be generated simply and compactly without using water.

3 Gas generator 3a Hydrogen absorber 3b Hydrogenating agent 5 Closed container 5a, 20, 21, 22, 23 Supply flow path 5b, 30, 31, 32, 33, 50 Discharge flow path (first discharge flow path)
10, 10A, 10B, 10C, 11, 12, 13 Gas generator 24, 25, 26, 31b, 42, 51, 142 On-off valve 31a Thermometer 40, 140 Temperature control flow path 50 Second discharge flow path P ₄₀ Circulation pump

Claims (13)

A gas absorbent that generates heat by absorbing gas,
Outgassing materials that release gas by heating and
It is provided with a supply port for supplying gas from outside the system and a discharge port for discharging gas to the outside of the system, and is provided with an internal closed container so as to transfer heat between the gas absorbing material and the gas releasing material.
The temperature reached by the gas absorbing material by absorbing the gas is higher than the thermal decomposition temperature for releasing the gas of the gas releasing material, and the amount of gas released by the gas releasing material is the gas absorption. More than the amount of gas absorbed by the material,
The gas absorber and the gas release material are a hydrogen absorber and a hydrogenating agent, the hydrogen absorbing agent is Mg ₂ Ni, Zrmn ₂ or Nb ₂ O ₅ to which Mg is added, and the hydrogenating agent is , Lithium aluminum hydride, sodium aluminum hydride, active magnesium, lithium boron hydride, magnesium hydride, sodium borohydride or aluminum hydride,
The hydrogen absorbing agent layer and the hydrogenating agent layer are alternately laminated and arranged in order from the supply port side of the closed container, and the hydrogen absorbing agent layer is arranged on the supply port side of the closed container. A gas generator in which a layer of hydrogenating agent is arranged on the discharge port side of a closed container. The gas generator according to claim 1, wherein the amount of gas released by the hydrogenating agent is at least twice the amount of gas absorbed by the hydrogen absorbing agent. A gas absorbent that generates heat by absorbing gas,
Outgassing materials that release gas by heating and
It is provided with a supply port for supplying gas from outside the system and a discharge port for discharging gas to the outside of the system, and is provided with an internal closed container so as to transfer heat between the gas absorbing material and the gas releasing material.
The temperature reached by the gas absorbing material by absorbing the gas is higher than the thermal decomposition temperature for releasing the gas of the gas releasing material, and the amount of gas released by the gas releasing material is the gas absorption. More than the amount of gas absorbed by the material,
The gas absorber and the outgassing material are an oxygen absorber and an oxygenating agent, the oxygen absorbing agent is iron fine powder or a mixture of iron fine powder and ceramic, and the oxygenating agent is silver oxide. ,
The oxygen absorber layer and the oxygen scavenger layer are alternately laminated and arranged in order from the supply port side of the closed container, and the oxygen absorber layer is arranged on the supply port side of the closed container. A gas generator in which a layer of oxygen scavenger is arranged on the discharge port side of a closed container. The gas generator according to claim 3 , wherein the amount of gas released by the oxygen scavenger is at least twice the amount of gas absorbed by the oxygen absorber. A gas generation system in which a plurality of gas generators according to any one of claims 1 to 4 are arranged along a direction in which gas is supplied.
One end of the gas supply from the outside of the system and the supply ports of the plurality of gas generators are connected together with an on-off valve so that the gas from the outside of the system is independently supplied to the plurality of gas generators. A supply channel having a plurality of other ends and
A discharge flow path having one end connected to the discharge port of the gas generator and the other end for discharging the gas generated by the gas generator to the outside of the system.
A gas generation system in which a cooling medium circulates in contact with the plurality of gas generators in order, and a temperature control flow path provided with a heat exchanger is provided. A gas generation method using the gas generation system according to claim 5 .
A first gas generation step of generating gas by supplying gas from outside the system to one of the plurality of gas generators and discharging the gas to the outside of the system.
When the first gas generation step is completed, the cooling medium in the temperature control flow path is circulated to recover the heat stored in the one gas generator and to be used for hydrogen generation next. The first preheating step, which preheats other gas generators among several, and
A gas generation method including at least a second gas generation step of generating gas by supplying gas from outside the system to the other preheated gas generator and discharging the gas to the outside of the system. A gas generation system in which multiple gas generators are arranged along the direction in which gas is supplied.
One end of the gas supply from the outside of the system and the supply ports of the plurality of gas generators are connected together with an on-off valve so that the gas from the outside of the system is independently supplied to the plurality of gas generators. A supply channel having a plurality of other ends and
One end connected to the discharge port of the gas generator, the other end of discharging the gas generated by the gas generator to the outside of the system, a thermometer, and a first discharge flow path having an on-off valve.
One end connected to the first discharge flow path of one of the plurality of gas generators and the other so as to supply the gas generated by the one gas generator to the other gas generator. The other end connected to the discharge port of the gas generator via the supply flow path to the other gas generator, the temperature control flow path having the on-off valve, and the temperature control flow path.
One end connected between the on-off valve on the one gas generator side and the on-off valve on the other gas generator side and a part of the gas generated by the one gas generator are connected to the supply flow path. A second discharge flow path having an on-off valve and an other end for discharging to the outside is provided.
The gas generator has a gas absorbing material that generates heat when it absorbs gas, a gas releasing material that releases gas by heating, a supply port that supplies gas from outside the system, and a discharge port that discharges gas to the outside of the system. It is provided with an internal closed container so as to transfer heat between the gas absorbing material and the gas releasing material.
The temperature reached by the gas absorbing material by absorbing the gas is higher than the thermal decomposition temperature for releasing the gas of the gas releasing material, and the amount of gas released by the gas releasing material is the gas absorption. A gas generation system that exceeds the amount of gas absorbed by the material. The gas generation system according to claim 7 , wherein the amount of gas released by the outgassing material is at least twice the amount of gas absorbed by the gas absorbing material. The gas absorbing material and the outgassing material are a hydrogen absorbing agent and a hydrogenating agent, or an oxygen absorbing agent and an oxygenating agent.
The hydrogen absorber is Mg ₂ Ni, Zrmn ₂ or Nb ₂ O ₅ to which Mg is added, and the hydrogenating agent is lithium aluminum hydride, sodium borohydride, active magnesium, lithium boron hydride, hydrogenation. Magnesium, sodium borohydride or aluminum hydride,
The gas generation system according to claim 7 or 8 , wherein the oxygen absorber is iron fine powder or a mixture of iron fine powder and ceramic, and the oxygen agent is silver oxide. The layer of the gas absorbing material and the layer of the gas releasing material are laminated, the layer of the gas absorbing material is arranged on the supply port side of the closed container, and the layer of the gas releasing material is arranged on the discharging port side of the closed container. The gas generation system according to any one of claims 7 to 9 , wherein the gas generation system is arranged. The gas generation system according to claim 10 , wherein a plurality of layers of the gas absorbing material and the gas releasing material are laminated along the discharge port from the supply port of the closed container. The gas generation according to any one of claims 7 to 9 , wherein the gas absorbing material is arranged in contact with the supply port of the closed container, and the gas releasing material is arranged in contact with the periphery of the gas absorbing material. system. A gas generation method using the gas generation system according to any one of claims 7 to 12 .
A first gas generation step of generating gas by supplying gas from outside the system to one of the plurality of gas generators and discharging the gas to the outside of the system.
When the temperature of the gas generated in the first gas generation step becomes equal to or higher than a predetermined temperature, the generated gas is discharged from the first supply flow path to the outside of the system, and the generated gas is discharged from the plurality. A second preheating step of preheating the other gas generator by supplying it to another gas generator, and
A gas generation method including a second gas generation step of generating gas by supplying gas from outside the system to the other preheated gas generator and discharging the gas to the outside of the system.

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