JP2008189538A - Hydrogen generation system, operation method of hydrogen generation system and hydrogen fuel vehicle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen generation system not required of disposing of heat generated by exothermic reaction of a hydrogen generating material, and not necessitating to supply heat from outside required for other material generating hydrogen through an endothermic reaction. <P>SOLUTION: This hydrogen generation system 1 is characterized by combining a solid hydrogen-containing material A<SB>1</SB>(a first hydrogen generating material) comprising an exothermic solid hydrogen-containing material and a solid hydrogen-containing material B<SB>1</SB>(a second hydrogen generating material) comprising an endothermic solid hydrogen-containing material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrogen generation system, a method for operating the hydrogen generation system, and a hydrogen fuel vehicle.

There is a report that by reacting a mixture of a metal hydride and a metal hydroxide, hydrogen can be released by a hydrolysis reaction in a solid phase state, for example, by the reaction of the following formula (A1). (Refer nonpatent literature 1).
LiH + LiOH → Li ₂ O + H ₂ Formula (A1)
This proceeds with a smaller calorific value than the hydrolysis reaction, which is a normal solid-liquid phase reaction represented by the formula (A2).
LiH + H ₂ O → LiOH + H ₂ Formula (A2)
This technique is a technique that can cause hydrolysis in a solid state, and has a feature that it generates less heat than a hydrolysis reaction between a solid and a liquid phase that is reacted with water (H ₂ O) (non- Patent Document 2).

Further, by heating the metal hydride, a thermal decomposition reaction occurs, and as shown in the formulas (A3) and (A4), hydrogen can be released from the metal hydride.
LiH → Li + 1 / 2H ₂ −79 [kJ / mol] (formula (A3))
MgH ₂ → Mg + H ₂ −75 [kJ / mol] (formula (A4))
The reactions shown in Formula (A3) and Formula (A4) both endothermically progress and decompose into metal and hydrogen gas (see Non-Patent Document 2).
JJ Vajo, SL Skeith, F. Mertens and SW Jorgensen, “Hydrogen-generating solid-state hydride / hydroxide reactions,” J. Alloys and Compounds, 390 (2005) 55-61. Otsuka Yasuaki, “New Version of Hydrogen Storage Alloy-Its Properties and Applications-” Agne Technology Center

  However, as shown in the formula (A1), when hydrogen is released using a solid-phase hydrolysis reaction, this reaction is an exothermic reaction, so that the heat is treated as the hydrogen is released. A device is required. On the other hand, as shown in the formulas (A3) and (A4), when hydrogen is released using a thermal decomposition reaction, the reaction is an endothermic reaction, and thus the amount of heat necessary for the release of hydrogen is externally increased. It is necessary to continue to supply from.

  The present invention has been made to solve the above problems, and a hydrogen generation system according to the present invention includes a first hydrogen generating material made of an exothermic solid hydrogen-containing material and an endothermic solid-containing material. It is characterized by combining with a second hydrogen generating material made of a hydrogen material.

  The operation method of the hydrogen generation system according to the present invention is characterized in that the first hydrogen generation material is heated by supplying heat from outside the system to the hydrogen generation system according to the present invention.

  A hydrogen fuel vehicle according to the present invention uses the hydrogen generation system according to the present invention.

  According to the present invention, heat generated in the first hydrogen generating material can be absorbed by the second hydrogen generating material and hydrogen can be generated from the second hydrogen generating material. It is possible to provide a hydrogen generation system that does not process heat generated by the exothermic reaction and does not need to supply heat necessary for the reaction of the second hydrogen generating material from the outside.

  According to the present invention, since the first and second hydrogen generating materials are heated by the heat generated by the first hydrogen generating material, the hydrogen generation at a high reaction temperature can be performed without supplying energy from the outside. It becomes possible to start. In addition, according to the present invention, since the heat generated in the first hydrogen generating material is absorbed by the second hydrogen generating material, temperature changes in the system during hydrogen generation can be reduced.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to manufacture hydrogen in a vehicle with high efficiency, and it becomes possible to provide the hydrogen fuel vehicle which has a compact and long cruising distance.

Hereinafter, a hydrogen generation system, a method for operating the hydrogen generation system, and a hydrogen fuel vehicle according to the best embodiment of the present invention will be described with reference to the accompanying drawings. In the following description of the drawings, the same parts are denoted by the same or similar reference numerals. However, the drawings schematically show the hydrogen generation system, the operation method of the hydrogen generation system, and the hydrogen fuel vehicle according to the embodiment of the present invention, and the ratio of each dimension is different from the actual one. Moreover, the part from which the relationship and ratio of a mutual dimension differ also in between drawings is contained. Specific dimensions and the like should be determined in consideration of the following description. In the present embodiment, the hydrogen generator G _i is (i = 1 to N), and is generically indicated by the symbol G. Similarly, the solid hydrogen-containing material A _j (j = 1 to N) is indicated generically by the symbol A. The solid hydrogen-containing material B _k is (k = 1 to N) and is generically indicated by the symbol B.

<First Embodiment>
The hydrogen generation system according to the first embodiment of the present invention will be described with reference to FIG. FIG. 1 is a schematic diagram of a hydrogen generation system 1 according to the first embodiment of the present invention.

The hydrogen generation system 1 is mounted on a hydrogen fuel vehicle 110 shown in FIG. 14, hydrogen fuel vehicle 110 is installed mounted hydrogen generator G ₁ to the rear.

Hydrogen generation system 1 according to a first embodiment of the present invention, a hydrogen generator G _1, a pressure regulating valve 5 comprises a hydrogen fuel power plant 6, the hydrogen generator G _1, the solid hydrated material charge A _{1 (first} 1 hydrogen generating material). And the solid hydrogen-containing material B ₁ (second hydrogen generating material) inside the container 2, the heat transfer path 7 as a heat supply means for supplying heat to the solid hydrogen-containing material A ₁ , and the generated hydrogen is released. And a solenoid valve 4 as a hydrogen supply means for discharging the generated hydrogen to the hydrogen fuel power unit 6. Heating portion 7a of the heat transfer path 7 is arranged in the container 2, the heating section 7a is heated directly solid hydrous material charges A ₁ in contact with the solid hydrated material charges A _1. The heating part 7a may consist of an electric heater, or may consist of a heat medium flow path. Further, the heat transfer path 7 has a heat transfer means (not shown) for supplying heat to the heating unit 7a from the outside of the container 2, and the heat transfer means is a combustion type or heat exchange type heat source. It is connected. A predetermined amount of the solid hydrogen-containing material A ₁ and the solid hydrogen-containing material B ₁ are filled in the container 2, but there may be spaces 8 a and 8 b in the container 2.

In the hydrogen generation system 1 according to the first embodiment of the present invention, the material that generates hydrogen is composed of a solid hydrogen-containing material A ₁ made of an exothermic solid hydrogen-containing material and an endothermic solid hydrogen-containing material. since a combination of solid hydrated material fee B _1, the heat generated in the solid hydrated material charges a ₁ is absorbed by the solid hydrated material fee B _1, not only from a solid hydrated material charges a _1, solid hydrous material fees it can be generated even hydrogen from B _1. Thus, solid hydrous material fee A it is not necessary to handle the heat generated by _one of the exothermic reaction and heat is not necessary to externally supplied required for the reaction of the solid hydrated material charge B _1.

In general, an exothermic reaction is a reaction toward a more stable state, and therefore the reaction proceeds spontaneously only by giving a heat amount necessary to exceed the activation energy of the reaction. For this reason, the exothermic reaction starts at a lower temperature than the endothermic reaction. Then, once the exothermic reaction is started using the slight amount of heat, the material itself is heated by the reaction heat. When the solid hydrogen-containing material B ₁ is heated using the heat, the temperature reaches a temperature at which hydrogen release by the endothermic reaction of the solid hydrogen-containing material B ₁ starts without adding a large amount of heat to the hydrogen generation system. Further, the solid hydrogen-containing material B ₁ absorbs the reaction heat of the solid hydrogen-containing material A ₁ , thereby suppressing the excessive temperature rise of the whole material.

In addition, the heat exchange between the solid hydrogen-containing material A ₁ and the solid hydrogen-containing material B ₁ may be via gas or may use heat conduction of the material itself, and a solid or liquid heat medium is always used. There is no need to do. The supply of heat from the outside does not necessarily supply the heat itself. For example, a form of supplying energy called “electric power” from outside the system and operating a heating element inside the system may be used. . Further, the solid hydrogen-containing material A ₁ needs to supply heat from the outside to the whole or part of the solid hydrogen-containing material A ₁ as a trigger for the reaction to generate hydrogen. ₁ may be supplied with heat from the outside, or may not be supplied.

Material generating hydrogen contained in the container 2, the solid hydrated material charge A ₁ is a mixture of a metal hydride with a metal hydroxide, solid hydrous material charge B ₁ represents made of metal hydroxides. When a metal hydride and a metal hydroxide are reacted, a solid phase hydrolysis reaction occurs, and hydrogen is released by an exothermic reaction. On the other hand, when a metal hydride is heated to a high temperature, a thermal decomposition reaction occurs, and hydrogen is released by an endothermic reaction.

Solid hydrous material charge A ₁ includes a first, a second and a Group 13 metal hydrides, metal hydride selected from the group of the first and second metals boron hydride and aluminum hydride And a mixture of metal hydroxides selected from Group 1, Group 2 and Group 13 metal hydroxides or hydroxide hydrates thereof. As metal _{hydride, LiH, MgH 2, CaH 2} , AlH 3, LiAlH 4, NaAlH 4, KAlH 4, LiBH 4, NaBH 4 and KBH ₄ can be used, metal hydroxides, LiOH, Mg (OH) ₂ , Ca (OH) ₂ , Al (OH) ₃ , NaOH, KOH and LiOH.H ₂ O can be used.

The solid hydrogen-containing material B ₁ is a metal hydride selected from Group 1, 2 and 13 metal hydrides, Group 1 and Group 2 borohydrides, or Aluminum hydrides. As metal _{hydride, LiH, MgH 2, CaH 2} , AlH 3, LiAlH 4, NaAlH 4, KAlH 4, LiBH 4, NaBH 4 and KBH ₄ can be used.

A metal hydride alone releases hydrogen by a thermal decomposition reaction, and reacts with a metal hydroxide to release hydrogen by a solid phase hydrolysis reaction. By proceeding these two reactions simultaneously, the amount of hydrogen released per unit weight is increased compared to the case of solid phase hydrolysis alone. Further, compared to the case of only the thermal decomposition reaction, hydrogen can be released at a low heating temperature, that is, at a low energy supply. The metal hydride in the solid hydrogen-containing material A1 and the metal hydride of the solid hydrogen-containing material B1 may be the same or different. When compared with the same metal species, since towards the metal hydride has a higher hydrogen content than metal hydroxides (e.g., LiH 12.7wt%, LiOH 4wt% ), solid hydrous material charge _{A 1} total When the content of the metal hydride in the material increases, the hydrogen content as a whole material is improved.

Here, an example in which the solid hydrogen-containing material A ₁ is LiH + LiOH and the solid hydrogen-containing material B ₁ is LiH is shown. The solid hydrogen-containing material A ₁ and the solid hydrogen-containing material B ₁ are prepared as powders, mixed together, and then filled in a container 2 equipped with an external heat supply mechanism is used as a hydrogen generator G ₁ . . In this case, the heat transfer path capable of heat exchange between the solid hydrogen-containing material A ₁ and the solid hydrogen-containing material B ₁ is the gas existing in the container 2 and the solid hydrogen-containing material A ₁ and the solid hydrogen-containing material B _1. Be yourself. In this case, the mixture of the solid hydrogen-containing material A ₁ and the solid hydrogen-containing material B _{1 is} the same as the mixture of LiH and LiOH because the hydride contained in both is common.
When LiH + LiOH generates hydrogen by solid phase hydrolysis, a reaction like (Formula B1) proceeds.
LiH + LiOH → Li ₂ O + H ₂ (exothermic reaction) (Formula B1)
On the other hand, when LiH generates hydrogen by a thermal decomposition reaction, a reaction like (Formula B2) proceeds.
LiH → Li + 1 / 2H ₂ (endothermic reaction) (Formula B2)
(Formula B1), that is, when hydrogen is generated only by solid-phase hydrolysis, the hydrogen release amount per unit mass is 6.3 [% by mass]. On the other hand, when hydrogen is generated only by (formula B2), that is, the thermal decomposition reaction, the hydrogen release amount per unit mass is 12.7 [% by mass]. However, when hydrogen is released by the thermal decomposition reaction, it is necessary to supply a heat quantity of about 157 [kJ / mol H ₂ ]. Thus, the amount of heat generated in (Formula B1) is supplied to (Formula B2) to promote the reaction of (Formula B2).

  When the ratio of (Formula B1) and (Formula B2) is 1: 0.4, the hydrogen generation amount at this time is about 6.9 [% by mass]. At this time, the calorific value from (Formula B1) and the endothermic amount from (Formula B2) are balanced, and the hydrogen releasing reaction proceeds without heat supply from the outside.

  When the ratio of (Formula B1) and (Formula B2) is 1: 0.8, the hydrogen generation amount at this time is about 7.3 [mass%]. At this time, the heat balance between (Formula B1) and (Formula B2) is an endothermic reaction of about 20 [kJ / mol], and by supplying a heat amount of 20 [kJ / mol] from the outside, a hydrogen releasing reaction Progresses.

Next, an example in which the solid hydrogen-containing material A ₁ is LiH + LiOH and the solid hydrogen-containing material B ₁ is MgH ₂ is shown. The apparatus at this time is the same as described above, and is equivalent to a mixture of LiH, LiOH and MgH ₂ . When LiH + LiOH generates hydrogen by solid phase hydrolysis, the reaction of (Formula B1) proceeds. On the other hand, when MgH ₂ generates hydrogen by a thermal decomposition reaction, a reaction like (Formula B3) proceeds.
MgH ₂ → Mg + H ₂ (endothermic reaction) (Formula B3)
When hydrogen is generated only by (Formula B1), that is, LiH + LiOH solid-phase hydrolysis, the hydrogen release amount per unit mass is 6.3 [% by mass]. On the other hand, in the case where hydrogen is generated only by (formula B3), that is, the thermal decomposition reaction of MgH ₂ , the hydrogen release amount per unit mass is 7.6 [% by mass]. However, when hydrogen is released by the pyrolysis reaction, it is necessary to supply a calorie of about 75 [kJ / molH ₂ ]. Therefore, by supplying the amount of heat generated in (Formula B1) to (Formula B3), the reaction of (Formula B3) is promoted.

  When the ratio of (Formula B1) to (Formula B3) is 1: 0.4, the hydrogen generation amount at this time is about 6.7 [% by mass]. At this time, the calorific value from (Formula B1) and the endothermic amount from (Formula B2) are balanced, and the hydrogen releasing reaction proceeds without heat supply from the outside.

  When the ratio of (Formula B1) and (Formula B3) is 1: 1, the hydrogen generation amount at this time is about 6.9 [% by mass]. At this time, the heat balance between (Equation B1) and (Equation B2) is an endothermic reaction of about 20 [kJ / mol], and by supplying a heat quantity of 20 [kJ / mol] from the outside, hydrogen release The reaction proceeds.

As described above, the hydrogen generation system 1 according to the first embodiment of the present invention includes a solid hydrogen-containing material A ₁ made of an exothermic solid hydrogen-containing material and a solid hydrogen-containing material made of an endothermic solid hydrogen-containing material. By combining the material B ₁ , there is no need to separately process heat generated by the exothermic reaction of the solid hydrogen-containing material A ₁ , and heat necessary for the reaction of the solid hydrogen-containing material B ₁ is supplied from the outside. There is no need.

Second Embodiment
Next, a hydrogen generation system 11 according to a second embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 2 is a schematic diagram of the hydrogen generation system 11 according to the second embodiment of the present invention.

Hydrogen generation system 11 according to a second embodiment of the present invention, a hydrogen generator G _2, a pressure regulating valve 5 comprises a hydrogen fuel power plant 6, the hydrogen generator G ₂ is, solid hydrous material fee A ₂ and solid A container 2 provided with a hydrogen-containing material B ₂ therein, a heat transfer path 7 as a heat donating means for supplying heat to the solid hydrogen-containing material A ₂ , a hydrogen discharge port 3 for releasing generated hydrogen, and generated hydrogen And a solenoid valve 4 serving as a hydrogen supply means for discharging the fuel to the hydrogen fuel power unit 6. Heating portion 7a of the heat transfer path 7 is arranged in the container 2, the heating unit 7a is directly heat the solid hydrated material fee A ₂ in contact with the solid hydrated material fee A _2. A predetermined amount of the solid hydrogen-containing material A ₂ and the solid hydrogen-containing material B ₂ are filled in the container 2, but there may be spaces 18 a and 18 b in the container 2. The container 2, the first chamber containing the solid hydrated material fee A ₂ (not shown), a second chamber containing a solid water material fee B ₂ (not shown), the first chamber (not shown ) And a second chamber (not shown) and a thermally conductive partition 12 is provided. With such a configuration, without direct contact with the solid hydrated material fee A ₂ and the solid hydrated material fee B ₂ in the container 2, and a solid water-containing material fee A ₂ and the solid hydrated material fee B ₂ There is no mixing. The partition 12 is capable of heat transfer.

Thus, in the hydrogen generation system 11 according to the second embodiment of the present invention, the partition 12 separates the solid hydrogen-containing material A ₂ and the solid hydrogen-containing material B ₂ , and the heat is passed through the partition 12. Since the movement is possible, the mixing of the two materials is suppressed, and the separation of the materials during the recovery of the waste material after releasing the hydrogen is facilitated. The partition 12 does not necessarily need to be a dense solid, and may be a material that transmits gas, liquid, or the like. Moreover, the partition 12 may be fixed with respect to the container 2, and does not need to be fixed. For example, the case where each material or only one material is filled in a plastic bag and disposed in the container 2 is also included.

<Third Embodiment>
Next, a hydrogen generation system 21 according to a third embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 3 is a schematic view of a hydrogen generation system 21 according to the third embodiment of the present invention.

A hydrogen generation system 21 according to the third embodiment of the present invention includes a hydrogen generation device G ₃ , a pressure regulating valve 5, and a hydrogen fuel power device 6. Hydrogen generator G ₃ are a container 2 comprising a solid water material fee A ₃ and solid hydrated material fee B ₃ therein, a heat transfer path 7 as a heat donor means that donates heat to the solid hydrated material fee A _3, A hydrogen discharge port 3 for discharging the generated hydrogen and an electromagnetic valve 4 as hydrogen supply means for discharging the generated hydrogen to the hydrogen fuel power unit 6 are provided. Heating portion 27a of the heat transfer path 27 is disposed in the container 2, the heating section 27a is directly heated solid hydrated material fee A ₃ in contact with the solid hydrated material fee A _3. A predetermined amount of the solid hydrogen-containing material A ₃ and the solid hydrogen-containing material B ₃ are filled in the container 2, but there may be spaces 28 a and 28 b in the container 2.

In the hydrogen generation system 21 according to the third embodiment of the present invention, as shown in FIG. 3, a hydrogen discharge port 3 is provided in the container 2, and the solid hydrogen-containing material B ₃ is hydrogenated from the solid hydrogen-containing material A _3. It is arranged at a position close to the discharge port 3. By arranging in this way, a heat source can be placed on the upstream side of the hydrogen flow, and heat transfer between the solid hydrogen-containing material A ₃ and the solid hydrogen-containing material B ₃ can be efficiently performed via the hydrogen flow. . That is, hydrogen is released by the exothermic reaction of the solid hydrogen-containing material A ₃ heated by the heat from the outside, and this hydrogen passes through the solid hydrogen-containing material B ₃ and is released from the hydrogen discharge port 3 to the outside of the container. The For this reason, hydrogen flows in the container 2. Since hydrogen generated by the solid hydrogen-containing material A _{3 is} due to an exothermic reaction, the hydrogen gas passing through the solid hydrogen-containing material B ₃ has a relatively high temperature. For this reason, when the heated hydrogen gas is considered as a heat-conducting medium that gives the solid hydrogen-containing material B ₃ , when the solid hydrogen-containing material B ₃ is disposed near the hydrogen discharge port 3, the efficiency is increased. It is possible to generate hydrogen well.

Thus, in the hydrogen generation system 21 according to the third embodiment of the present invention, the hydrogen discharge port 3 is provided in the container 2, and the solid hydrogen-containing material B ₃ is closer to the hydrogen discharge port 3 than the solid hydrogen-containing material A _3. It becomes possible to generate hydrogen efficiently by arrange | positioning to. In the present embodiment, there may be a partition capable of gas flow between the solid hydrogen-containing material A ₃ and the solid hydrogen-containing material B ₃ .

<Fourth embodiment>
Next, a hydrogen generation system 31 according to a fourth embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 4 is a schematic view of a hydrogen generation system 31 according to the fourth embodiment of the present invention.

A hydrogen generation system 31 according to the fourth embodiment of the present invention includes a hydrogen generation device G ₄ , a pressure regulating valve 5, and a hydrogen fuel power device 6. The hydrogen generator G ₄ are a container 2 comprising a solid water material fee A ₄ and solid hydrated material fee B ₄ therein, a heat transfer path 7 as a heat donor means that donates heat to the solid hydrated material fee A _4, A hydrogen discharge port 3 for discharging the generated hydrogen and an electromagnetic valve 4 as hydrogen supply means for discharging the generated hydrogen to the hydrogen fuel power unit 6 are provided. Heating portion 7a of the heat transfer path 7 is arranged in the container 2, the heating unit 7a is directly heat the solid hydrated material fee A ₄ in contact with the solid hydrated material fee A _4. A predetermined amount of the solid hydrogen-containing material A ₄ and the solid hydrogen-containing material B ₄ are filled in the container 2, but there may be spaces 38 a and 38 b in the container 2.

In the hydrogen generation system 31 according to the fourth embodiment of the present invention, as shown in FIG. 4, the solid hydrogen-containing material A ₄ and the solid hydrogen-containing material B ₄ are alternately laminated, and the lamination is performed in the radial direction of the container 2. Is going to. That is, the solid hydrogen-containing material A ₄ and the solid hydrogen-containing material B ₄ are arranged so as to be concentric. The container 2 holding such a material has a very large heat capacity. Therefore, when the solid hydrated material fee A ₄ emits hydrogen by exothermic reaction, the container 2 and the solid hydrated material fee A ₄ are in contact, the heat generation from a solid hydrated material fee A ₄ via the container 2 , It will be diffused out of the container 2. In this case, energy loss occurs. Therefore, so as to surround the solid hydrated material fee A ₄ in solid hydrous material fee B ₄ by (e.g., concentrically) arranged, so that significantly reduce the contact between the solid water-containing material fee A ₄ and the container 2 . Then, the heat generated from the solid hydrogen-containing material A _{4 is} prevented from being transmitted to the outside through the container 2, and almost all the heat can be supplied to the solid hydrogen-containing material B ₄ .

Thus, in the hydrogen generation system 31 according to the fourth embodiment of the present invention, the solid hydrogen-containing material A ₄ and the solid hydrogen-containing material B ₄ are alternately laminated, and this lamination is performed in the radial direction of the container 2. As a result, almost all of the heat generated from the solid hydrogen-containing material A ₄ can be supplied to the solid hydrogen-containing material B ₄ . In the present embodiment, there may be a partition capable of gas flow between the solid hydrogen-containing material A ₄ and the solid hydrogen-containing material B ₄ .

<Fifth Embodiment>
Next, a hydrogen generation system 41 according to a fifth embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 5 is a schematic diagram of a hydrogen generation system 41 according to the fifth embodiment of the present invention.

Hydrogen generation system 41 according to a fifth embodiment of the present invention includes a hydrogen generator G _5, the pressure regulating valve 5, and a hydrogen fuel power plant 6. The hydrogen generator G ₅ includes a container 2 comprising a solid water material fee A ₅ and solid hydrated material fee B ₅ therein, a heat transfer path 7 as a heat donor means that donates heat to the solid hydrated material fee A _5, A hydrogen discharge port 3 for discharging the generated hydrogen and an electromagnetic valve 4 as hydrogen supply means for discharging the generated hydrogen to the hydrogen fuel power unit 6 are provided. Heating portion 7a of the heat transfer path 7 is arranged in the container 2, the heating unit 7a for heating the solid hydrated material fee A ₅ directly contacts the solid hydrated material fee A ₄ and solid hydrated material fee B _5. A predetermined amount of the solid hydrogen-containing material A ₅ and the solid hydrogen-containing material B ₅ are filled in the container 2, but there may be spaces 48 a and 48 b in the container 2. In the hydrogen generation system 41 according to the fifth embodiment of the present invention, as shown in FIG. 5, the solid hydrogen-containing material A ₅ and the solid hydrogen-containing material B ₅ are alternately laminated, and the lamination is performed in the axial direction of the container 2. Is going to. With such a configuration, the contact area between the solid water-containing material fee A ₅ and solid hydrated material fee B ₅ is increased. In addition, the lamination direction may be any direction in the container 2 and may be a plurality of laminated structures. The laminated structure may be a flat laminated structure, for example, a curved laminated structure such as an onion. Further, the laminated structure may be interlocked with the shape of a device that supplies heat from the outside. For example, when using a heat exchange device having a heat dissipating fins are stacked, it may be in accordance with the pitch of the heat radiating fins arranged and solid hydrated material fee A ₅ and solid hydrated material fee B _5, solid hydrous material fee A ₅ and nipping the solid hydrated material fee B ₅ from both sides, it may have a structure sandwiched by further radiating fins it.

As described above, in the hydrogen generation system 41 according to the fifth embodiment of the present invention, the solid hydrogen-containing material A ₅ and the solid hydrogen-containing material B ₅ are alternately laminated, and this lamination is performed in the axial direction of the container 2. As a result, the contact area between the solid hydrogen-containing material A ₅ and the solid hydrogen-containing material B ₅ is increased, and heat exchange between the solid hydrogen-containing material A ₅ and the solid hydrogen-containing material B ₅ is efficiently performed. Done. In the present embodiment, between the solid water-containing material fee A ₅ and solid hydrated material fee B _5, there may be capable of gas flow divider.

<Sixth Embodiment>
Next, a hydrogen generation system 51 according to a sixth embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 6 is a schematic diagram of a hydrogen generation system 51 according to the sixth embodiment of the present invention.

A hydrogen generation system 51 according to the sixth embodiment of the present invention includes a hydrogen generation device G ₆ , a pressure regulating valve 5, and a hydrogen fuel power device 6. The hydrogen generator G ₆ includes a container 2 comprising a solid water material fee A ₆ and solid hydrated material fee B ₆ therein, a heat transfer path 7 as a heat donor means that donates heat to the solid hydrated material fee A _6, A hydrogen discharge port 3 for discharging the generated hydrogen and an electromagnetic valve 4 as hydrogen supply means for discharging the generated hydrogen to the hydrogen fuel power unit 6 are provided. Heating portion 7a of the heat transfer path 7 is arranged in the container 2, the heating portion 7a directly solid hydrous material fee A ₆ and solid hydrogen-containing contact with the solid hydrated material fee A ₆ and solid hydrated material fee B ₆ heating the material _{B 6.} A predetermined amount of the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ are filled in the container 2, but there may be spaces 58 a and 58 b in the container 2.

In the hydrogen generation system 51 according to the sixth embodiment of the present invention, as shown in FIG. 6, the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ are mixed. For example, if the solid hydrated material fee A ₆ is one type of metal hydride and one of the metal hydroxide, solid hydrous material fee B ₆ is made of the same metal hydrides one solid hydrated material fee A _6, By simply mixing the metal hydride and the metal hydroxide at a predetermined ratio, a mixture AB of the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ is formed. Further, even when the metal hydride of the solid hydrogen-containing material A _{6 and} the metal hydride of the solid hydrogen-containing material B ₆ are different, in the process for producing the solid hydrogen-containing material A ₆ in which the metal hydride and the metal hydroxide are mixed, solid hydrous material fee B ₆ also be mixed simultaneously, it is possible to easily create a mixture AB with a solid water-containing material fee a ₆ and solid hydrated material fee B _6. Further, the mixing of the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ does not need to be uniform, and the region where the solid hydrogen-containing material A ₆ is high and the content of the solid hydrogen-containing material B ₆ are high. It may be divided into areas. Further, the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ may be formed into a powder and mixed, and each of the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ has a lump. Also good. With this configuration, the contact area between the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ is increased, and the heat between the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ is increased. Exchange can be performed efficiently. In addition, since it can be handled as one kind of powder, that is, a mixture of the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ , the material can be easily filled in the container.

Thus, in the hydrogen generation system 51 according to the sixth embodiment of the present invention, since the solid hydrogen-containing material A ₆ and the solid hydrogen-containing material B ₆ are mixed, efficient heat exchange is possible, Material handling becomes easy.

<Seventh embodiment>
Next, a hydrogen generation system 61 according to a seventh embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 7 is a schematic diagram of a hydrogen generation system 61 according to the seventh embodiment of the present invention.

A hydrogen generation system 61 according to a seventh embodiment of the present invention includes a hydrogen generation device G ₇ , a pressure regulating valve 5, and a hydrogen fuel power device 6. The hydrogen generator G ₇ is a container 2 comprising a solid water material charges A ₇ and solid hydrated material fee B ₇ therein, the heat transfer path 67 as a heat donor means that donates heat to the solid hydrated material fee A _7, A hydrogen discharge port 3 for discharging the generated hydrogen and an electromagnetic valve 4 as hydrogen supply means for discharging the generated hydrogen to the hydrogen fuel power unit 6 are provided. Heating portion 67a of the heat transfer path 67 is disposed in the container 2, the heating section 67a is in contact with a portion of the solid water-containing material charges A ₇ for heating the solid hydrated material charges A _7. A predetermined amount of the solid hydrogen-containing material A ₇ and the solid hydrogen-containing material B ₇ are filled in the container 2, but there may be spaces 68 a and 68 b in the container 2.

In the hydrogen generation system 61 according to the seventh embodiment of the present invention, as shown in FIG. 7, the supply of heat from the material outside, it is preferred that for heating the solid hydrated material charges A _7. The heating of the solid hydrogen-containing material A ₇ may be entire, or only a small part of the solid hydrogen-containing material A ₇ may be heated as shown in FIG. For heating of only a small portion of the solid water-containing material fee A _7, than to heat the entire solid hydrous material fee A _7, heating can be easily performed, it is possible to facilitate the start of hydrogen generation.

Thus, in the hydrogen generation system 61 according to the seventh embodiment of the present invention, by heating part 67a is in contact with a portion of the solid water-containing material charges A ₇ for heating the solid hydrated material fee A _7, the heating It can be done easily.

<Eighth Embodiment>
Next, a hydrogen generation system 71 according to an eighth embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 8 is a schematic diagram of a hydrogen generation system 71 according to the eighth embodiment of the present invention.

Hydrogen generation system 71 according to the eighth embodiment of the present invention includes a hydrogen generator G _8, the pressure regulating valve 5, and a hydrogen fuel power plant 6. In the hydrogen generating apparatus G _8, the container 72 comprises a solid water material charges A ₇ and solid hydrated material fee B ₇ therein consists of pressure-resistant container. In this case, the generated hydrogen can be held in the container 72. Further, by holding hydrogen in the container 72, rapid hydrogen release is possible. Furthermore, the hydrogen pressure can be improved in the container 72, and the hydrogen discharge pressure to the outside of the container 72 can be increased. The container 72 is filled with a predetermined amount of the solid hydrogen-containing material A ₈ and the solid hydrogen-containing material B ₈ , but there may be spaces 78 a and 78 b in the container 72.

  Thus, in the hydrogen generation system 71 according to the eighth embodiment of the present invention, since the container 72 is a pressure vessel, the generated hydrogen can be easily managed.

<Ninth Embodiment>
Next, a hydrogen generation system 81 according to a ninth embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 9 is a schematic diagram of a hydrogen generation system 81 according to the ninth embodiment of the present invention.

Hydrogen generation system 81 according to a ninth embodiment of the present invention includes a hydrogen generator G _9, the pressure regulating valve 5, and a hydrogen fuel power plant 6. The hydrogen generator G ₉ includes a container 82 comprising a solid water material fee A ₉ and solid hydrated material fee B ₉ therein, the heat transfer path 7 as a heat donor means that donates heat to the solid hydrated material fee A _9, A hydrogen discharge port 3 for discharging the generated hydrogen and an electromagnetic valve 4 as hydrogen supply means for discharging the generated hydrogen to the hydrogen fuel power unit 6 are provided. Heating portion 7a of the heat transfer path 7 is arranged in the container 82, the heating portion 7a is in contact with a portion of the solid water-containing material fee A ₉ for heating the solid hydrated material fee A _9. A predetermined amount of the solid hydrogen-containing material A ₉ and the solid hydrogen-containing material B ₉ are filled in the container 82, but there may be spaces 88 a and 88 b in the container 82. The container 82 has an inlet 83 for charging the solid hydrogen-containing material A ₉ and the solid hydrogen-containing material B ₉ from the outside. The charging port 83 may function as an outlet for taking out the solid hydrogen-containing material A ₉ and the solid hydrogen-containing material B ₉ from the outside.

  With such a configuration, after releasing hydrogen, the material in the container 82 can be taken out and filled with new material, and the operation as a hydrogen generation system can be performed again. The charging port 83 may be on the bottom surface of the container 82 or on the side surface of the container 82. Further, with such a configuration, the material can be replaced without removing the container 82.

  Thus, in the hydrogen generation system 81 according to the ninth embodiment of the present invention, since the container 82 has the inlet 83, the hydrogen generation system can be reused.

<Tenth Embodiment>
Next, a hydrogen generation system 91 according to a tenth embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 10 is a schematic diagram of a hydrogen generation system 91 according to the tenth embodiment of the present invention.

A hydrogen generation system 91 according to a tenth embodiment of the present invention includes a hydrogen generator G _10a to a hydrogen generator G _10d , a pressure regulating valve 5, and a hydrogen fuel power unit 6. Each of the hydrogen generators G _10a to G _10d includes a solid hydrogen-containing material A _10a to a solid hydrogen-containing material A _10d , and a container 2 having a solid hydrogen-containing material B _10a to a solid hydrogen-containing material B _10d therein. Solid hydrogen-containing material A _10a to solid hydrogen-containing material A _10d heat transfer path 7 as a heat donating means for donating heat, hydrogen discharge port 3 for releasing generated hydrogen, and hydrogen generated by hydrogen fuel power unit 6 And a solenoid valve 4 serving as a hydrogen supply means for releasing the gas. Heating portion 7a of the heat transfer path 7 is arranged in the container 2, the heating section 7a is in contact with a portion of the solid water-containing material fee A _{10a ~} solid hydrous material fee A _10d solid hydrous material fee A _{10a ~} solid hydrogenous Heat material A _10d . Each of the hydrogen generators G _10a to G _10d is connected to the hydrogen supply line 100 by a detachable connecting portion 99 (so-called coupling portion). Hydrogen generated in each of the hydrogen generators G _10a to G _10d is sent to the hydrogen fuel power unit 6 through the hydrogen supply line 100.

As described above, the hydrogen generation system 91 according to the tenth embodiment of the present invention has a plurality of containers 2 for holding materials, and the plurality of containers 2 are used as a common pipe as shown in FIG. Hydrogen may be supplied to the hydrogen fuel power unit 6 through the hydrogen supply line 100 or may be supplied through individual piping. Moreover, the filling form of the material in all the containers 2 does not need to be the same, and the filling ratio of the material does not need to be the same. Thus, by dividing the container 2 into a plurality of parts, it becomes easy to estimate the amount of residual hydrogen that can be released by the system. Moreover, it becomes easy to control the hydrogen flow rate and the hydrogen pressure supplied by the system by changing the number of containers 2 to be operated. In addition, it is desirable that the container 2 has a structure that can be detached from the system. For example, a structure in which the solid hydrogen-containing material is exchanged for each container 2 by fastening with a pipe to the system by quick coupling is preferable. By adopting such a configuration, it is easy to exchange the solid hydrogen-containing material for each container 2. Further, even if the hydrogen content in the system does not become zero, it is possible to separately replace the hydrogen generators G _10a to G _10d .

<Eleventh embodiment>
Next, a hydrogen generation system 101 according to an eleventh embodiment of the present invention will be described with reference to FIG. Since it has the structure substantially the same as 1st Embodiment and 10th Embodiment, the same code | symbol is attached | subjected to the same structure location and the description is abbreviate | omitted. FIG. 11 is a schematic diagram of the hydrogen generation system 101 according to the first embodiment of the present invention.

A hydrogen generation system 101 according to an eleventh embodiment of the present invention includes a hydrogen generator G _11a to a hydrogen generator G _11d , a pressure regulating valve 5, and a hydrogen fuel power unit 6. Each of the hydrogen generators G _11a to G _11d includes a solid hydrogen-containing material A _11a to a solid hydrogen-containing material A _11d , and a container 2 having a solid hydrogen-containing material B _11a to a solid hydrogen-containing material B _11d therein. Solid hydrogen-containing material A _11a to solid hydrogen-containing material A _11d heat transfer path 7 as a heat donating means for donating heat, hydrogen discharge port 3 for releasing generated hydrogen, and hydrogen generated by hydrogen fuel power unit 6 And a solenoid valve 4 serving as a hydrogen supply means for releasing the gas. Heating portion 7a of the heat transfer path 7 is arranged in the container 2, the heating section 7a is in contact with a portion of the solid water-containing material fee A _{11a ~} solid hydrous material fee A _11d solid hydrous material fee A _{10a ~} solid hydrogenous Heat material A _10d . Each of the hydrogen generators G _11a to G _11d is connected to the hydrogen supply line 100 by a detachable connecting portion 99 (so-called coupling portion). Hydrogen generated in each of the hydrogen generators G _11a to G _11d is sent to the hydrogen fuel power unit 6 through the hydrogen supply line 100. The hydrogen generators G _11a to G _11d are connected to the hydrogen supply line 100 through the connecting portion 99, and the heat transfer sections 102a to 102c are connected between the hydrogen generators G _11a to G _11d. , And heat is transferred between the devices. For example, heat generated by the hydrogen generator G _11a is transferred to another hydrogen generator G _11b by the heat transfer section 102a. Thus, by supplying heat from outside the system of the hydrogen generator _{G 11a} ~ hydrogen generator _{G 11d,} solid hydrous material itself and other hydrogen generator _{G 11a} ~ hydrogen generator _{G 11d} fee _{A 11a} ~ solid The hydrogen-containing material A _11d can be heated.

As described above, since the heat can be transferred between the plurality of divided containers, the material filled in one container 2 may be the solid hydrogen-containing material A alone or the solid hydrogen-containing material. The material B alone may be used. Further, by adopting such a configuration, hydrogen can be released by the heat balance between the hydrogen generators G _11a to G _11d , and finer control of hydrogen release becomes possible.

<Twelfth embodiment>
Next, a method for operating the hydrogen generation system according to the twelfth embodiment of the present invention will be described with reference to FIG. In the present embodiment, an example in which the hydrogen generation system 1 of the first embodiment is operated will be described. FIG. 12 shows a control flow P1 of the operation method of the hydrogen generation system according to the twelfth embodiment. The control flow P1 proceeds to step S1 when the operation starts.

  In step S1, a heating command from the electric heater is issued to the heat transfer means. When the predetermined time has passed, the process proceeds to the next step S2.

  In step S2, hydrogen is supplied to the hydrogen fuel power unit 6, and the process proceeds to the next step S3.

  In step S3, it is determined whether or not the temperature T of the solid hydrogen-containing material B is a specified value. If T> specified value (YES), the process proceeds to step S4. If T ≦ the specified value (NO), the process proceeds to step S1.

  In step S4, the electric heater is turned off, and the process returns to step S2.

  That is, in the operating method of the hydrogen generation system according to the twelfth embodiment of the present invention, the solid hydrogen-containing material A is heated in whole or in part to start the hydrogen releasing reaction. Due to the exothermic reaction of the solid hydrogen-containing material A, the temperature of the solid hydrogen-containing material A itself is raised, and the endothermic reaction of the solid hydrogen-containing material B is started. After the temperature of the solid hydrogen-containing material A itself is increased by the exothermic reaction of the solid hydrogen-containing material A, the endothermic reaction of the solid hydrogen-containing material B starts, but the amount of heat generated by the exothermic reaction and the amount of heat absorbed by the endothermic reaction are balanced. Together, the hydrogen release proceeds while the temperature of the solid hydrogen-containing material A is kept constant. For this reason, in the operation method of the hydrogen generation system according to the twelfth embodiment of the present invention, it is only necessary to advance hydrogen generation of an exothermic reaction that operates at a relatively low temperature, so that the apparatus can be easily started. Moreover, since it is self-heating due to heat generation from the material, it becomes possible to start generation of hydrogen at a high reaction temperature without supplying energy from the outside. Furthermore, since the temperature can be kept constant by maintaining the heat balance in the material, stable hydrogen release can be realized. Thus, the solid hydrogen-containing material A and the solid hydrogen-containing material B are heated by the reaction heat accompanying the hydrogen release of the solid hydrogen-containing material A. When the solid hydrogen-containing material B exceeds a predetermined temperature, the supply of heat from outside the system is shut off.

<13th Embodiment>
Next, an operation method of the hydrogen generation system according to the thirteenth embodiment of the present invention will be described with reference to FIG. In the present embodiment, an example in which the hydrogen generation system 101 of the eleventh embodiment is operated will be described. FIG. 13 shows a control flow P2 of the operation method of the hydrogen generation system according to the thirteenth embodiment. The control flow P2 proceeds to step S11 when the operation starts.

  In step S11, the system temperature and the internal pressure of the container are measured, and the process proceeds to the next step S12.

  In step S12, the number of heating containers is determined based on the measurement result, and the process proceeds to the next step S13.

  In step S13, the material hydride and hydride mixture are heated with an electric heater, and the process proceeds to step S14.

  In step S14, hydrogen is supplied to the hydrogen power source, and the process proceeds to step S15.

  In step S15, it is determined whether or not the temperature T of the solid hydrogen-containing material A is a specified value. If T> specified value (YES), the process proceeds to step S16. If T ≦ the specified value (NO), the process proceeds to step S17.

  In step S16, the electric heater is turned off and the process proceeds to step S17.

  In step S17, it is determined whether pressure P> specified value or (please replenish) ρ> specified value. If P> specified value and ρ> specified value (YES), the process returns to step S14. If P ≦ the specified value and ρ ≦ the specified value (NO), the process returns to step S12.

  That is, in the operation method of the hydrogen generation system according to the thirteenth embodiment of the present invention, in the case of a system consisting of a plurality of containers, hydrogen is released from one container, and the hydrogen release pressure or hydrogen discharge flow rate from that container. It is preferable to start the generation of hydrogen from the next container in accordance with the change of. In this way, not only hydrogen is generated in order from each container, but, for example, hydrogen may be released from two containers first, and then hydrogen release may be started from another container. It is also possible to measure the pressure or temperature in each container and determine the number and type of hydrogen containers to be activated accordingly. For example, when the temperature in the container rises above a reference value, the temperature of the entire system can be controlled by transferring heat to the container containing a large amount of the endothermic material. Thus, by changing the number of containers for generating hydrogen, the generated hydrogen flow rate and the generated hydrogen pressure can be controlled. Further, the flow rate of hydrogen discharged from the system and the hydrogen pressure can be kept constant. Thus, hydrogen generation in another container containing the solid hydrogen-containing material A and the solid hydrogen-containing material B is started in accordance with the hydrogen generation amount in the container or the hydrogen flow rate in the hydrogen donating means, Delivered to hydrogen donating means.

<Fourteenth embodiment>
Next, a hydrogen fuel vehicle 110 according to a fourteenth embodiment of the present invention will be described with reference to FIG. In the present embodiment, the hydrogen generation system according to the first to eleventh embodiments is used. FIG. 14 shows a hydrogen fuel vehicle 101 according to the fourteenth embodiment. In FIG. 14, a hydrogen fuel vehicle 110 has a hydrogen generator G installed and mounted at the rear.

  The hydrogen fuel vehicle 110 according to the fourteenth embodiment of the present invention is installed in a vehicle using hydrogen as a fuel to supply hydrogen to the power source. The power source may be anything as long as it operates using hydrogen as a fuel. For example, it may be a direct hydrogen fuel cell or an internal combustion engine using hydrogen combustion. Moreover, when arrange | positioning a hydrogen generation system in a vehicle, there is no restriction | limiting in particular in a position. For example, it may be the lower part of the rear seat or a trunk room. In the hydrogen fuel vehicle 110 according to the fourteenth embodiment of the present invention, since the hydrogen generation system according to the present invention is used, hydrogen can be produced in the vehicle with high efficiency, and the vehicle has a compact and long cruising distance. Can be provided.

  Although the embodiment of the present invention has been described above, it should not be understood that the description and drawings that constitute part of the disclosure of the embodiment limit the present invention. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

1 is a schematic diagram of a hydrogen generation system according to a first embodiment of the present invention. It is a schematic diagram of the hydrogen generation system which concerns on 2nd Embodiment of this invention. It is a schematic diagram of the hydrogen generation system which concerns on 3rd Embodiment of this invention. It is a schematic diagram of the hydrogen generation system which concerns on 4th Embodiment of this invention. It is a schematic diagram of the hydrogen generation system which concerns on 5th Embodiment of this invention. It is a schematic diagram of the hydrogen generation system which concerns on 6th Embodiment of this invention. It is a schematic diagram of the hydrogen generation system which concerns on 7th Embodiment of this invention. It is a schematic diagram of the hydrogen generation system which concerns on 8th Embodiment of this invention. It is a schematic diagram of the hydrogen generation system which concerns on 9th Embodiment of this invention. It is a schematic diagram of the hydrogen generation system which concerns on 10th Embodiment of this invention. It is a schematic diagram of the hydrogen generation system which concerns on 11th Embodiment of this invention. It is a control flow of the operating method of the hydrogen generation system concerning a 12th embodiment of the present invention. It is a control flow of the operating method of the hydrogen generation system concerning a 13th embodiment of the present invention. It is a side view which shows the hydrogen fuel vehicle which concerns on 14th Embodiment of this invention.

Explanation of symbols

G Hydrogen generator A, B Solid hydrogen-containing material 1 Hydrogen generation system 2 Container 3 Hydrogen discharge port 4 Solenoid valve 5 Pressure regulating valve 6 Hydrogen fuel power unit 7 Heat transfer path 7a Heating part 8a, 8b Space

Claims (32)

  A hydrogen generation system comprising a combination of a first hydrogen generating material made of an exothermic solid hydrogen-containing material and a second hydrogen generating material made of an endothermic solid hydrogen-containing material.   The hydrogen generation system according to claim 1, further comprising a heat supply unit that supplies heat to the first hydrogen generation material. The first hydrogen generating material is a mixture of a metal hydride and a metal hydroxide,
The hydrogen generation system according to claim 1 or 2, wherein the second hydrogen generation material is made of a metal hydroxide.   The first hydrogen generating material is a metal hydride selected from the group consisting of metal hydrides of Group 1, 2 and 13 and boron hydrides and aluminum hydrides of metals of Groups 1 and 2. And a mixture of metal hydroxides selected from Group 1, Group 2 and Group 13 metal hydroxides or hydroxide hydrates thereof.   The second hydrogen generating material is a metal hydride selected from Group 1, 2 and 13 metal hydrides, Group 1 and Group 2 borohydrides, or Aluminum hydrides. The hydrogen generation system according to claim 3 or 4.   6. The apparatus according to claim 1, further comprising: a container that accommodates the first hydrogen generating material and the second hydrogen generating material; and a hydrogen supply unit that supplies hydrogen from the container to the outside. The hydrogen generation system according to any one of the above.   The container defines a first chamber containing the first hydrogen generating material, a second chamber containing the second hydrogen generating material, the first chamber, and the second chamber. The hydrogen generation system according to claim 6, further comprising a thermally conductive partition.   The container is provided with a hydrogen discharge port for discharging hydrogen to the hydrogen supply means, and the second hydrogen generating material is disposed closer to the hydrogen discharge port than the first hydrogen generating material. The hydrogen generation system according to claim 6 or 7.   The hydrogen generation system according to claim 6 or 7, wherein the second hydrogen generation material is arranged around the first hydrogen generation material.   The hydrogen generation system according to claim 6 or 7, wherein the first hydrogen generation material and the second hydrogen generation material are alternately stacked.   The hydrogen generation system according to claim 10, wherein the stacking is performed in an axial direction of the container.   The hydrogen generation system according to claim 10, wherein the stacking is performed in a radial direction of the container.   The hydrogen generation system according to claim 6, wherein the first hydrogen generation material and the second hydrogen generation material are mixed.   14. The hydrogen generation system according to claim 13, wherein the first hydrogen generation material and the second hydrogen generation material are formed in a powder form and mixed.   The hydrogen generation system according to claim 6, wherein the heat donating unit heats at least a part of the first hydrogen generation material.   The hydrogen generation system according to claim 6, wherein the heat donating unit includes a heating unit that directly heats the first hydrogen generation material in the container.   The hydrogen generation system according to claim 16, wherein the heating unit includes an electric heater.   The hydrogen generation system according to claim 16, wherein the heating unit includes a flow path of a heat medium.   The hydrogen generation system according to claim 16, wherein the heat supply unit includes a heat transfer unit that supplies heat to the heating unit from the outside of the container.   The hydrogen generation system according to claim 19, wherein the heat transfer means is connected to a combustion type or heat exchange type heat source.   The hydrogen generation system according to any one of claims 6 to 20, wherein the container is a pressure-resistant container.   The hydrogen according to any one of claims 6 to 21, wherein the container has an inlet for charging the first hydrogen generating material and the second hydrogen generating material from the outside. Generating system.   The hydrogen generation system according to claim 22, wherein the container has an outlet for taking out the first hydrogen generation material or the second hydrogen generation material from the outside.   The hydrogen generation system according to claim 6, wherein the hydrogen supply unit includes a hydrogen supply line having a connection portion.   25. The container according to any one of claims 6 to 24, wherein the container includes a first container and a second container for storing the first hydrogen generating material and the second hydrogen generating material, respectively. The hydrogen generation system described.   26. The hydrogen generation system according to claim 25, wherein the heat supply means includes heat transfer means for transferring heat from the first container to the second container.   27. A method for operating a hydrogen generation system, wherein the first hydrogen generation material is heated by supplying heat from outside the system to the hydrogen generation system according to any one of claims 6 to 26.   28. The hydrogen generation system according to claim 27, wherein the first hydrogen generation material and the second hydrogen generation material are heated by the reaction heat accompanying the hydrogen release of the first hydrogen generation material before. how to drive.   The operation method of the hydrogen generation system according to claim 27 or 28, wherein when the second hydrogen generating material exceeds a predetermined temperature, supply of heat from the outside of the system is cut off.   According to the hydrogen generation amount in the container or the hydrogen flow rate in the hydrogen donating means, hydrogen generation in another container containing the first hydrogen generating material and the second hydrogen generating material is started, and the hydrogen 30. The method of operating a hydrogen generation system according to any one of claims 27 to 29, wherein the hydrogen is supplied to the hydrogen donating means.   A hydrogen fuel vehicle using the hydrogen generation system according to any one of claims 6 to 30.   32. The hydrogen fuel vehicle according to claim 31, wherein the hydrogen fuel vehicle is a fuel cell vehicle.

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