JP2002184436A - Hydrogen storage/feed system, device, and catalyst for hydrogen storage/feed - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve reaction efficiency of hydrogen addition reaction or dehydrogenation to be used for storage or feed of the hydrogen. SOLUTION: This hydrogen storage/feed device 70 is provided with a first liquid tank 79 having hydrogen storage body put therein or a second liquid tank 80 having hydrogen feed body put therein, a reactor 74 performing either one hydrogen reaction of the hydrogen addition reaction of the hydrogen storage body or the dehydrogenation of the hydrogen feed body and having catalyst 88 to be used for the hydrogen reaction, heaters 81 and 82 heating the hydrogen storage body or the hydrogen feed body before the hydrogen reaction, and a cooling vessel 75 cooling the hydrogen storage body or the hydrogen feed body generated in the reactor 74.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage / supply system, a hydrogen storage / supply device, and a hydrogen storage / supply catalyst for storing hydrogen and supplying hydrogen to a fuel cell for an automobile or a home.

[0002]

2. Description of the Related Art The amount of energy consumption has been increasing year by year, and in particular, power supply from power plants has been unable to keep up in urban areas. Currently, about half of Japan's electricity depends on thermal power generation, about 30 to 40% on nuclear power, and the rest on hydroelectric power and wind power.

[0003] However, petroleum, which is a fuel for thermal power generation, is a fossil fuel and its supply is limited. Furthermore, exhaust gas such as carbon dioxide and NOx generated after burning oil is a cause of global environmental deterioration such as global warming. In nuclear power, the treatment of radioactive waste or accidents at power plants has been regarded as a problem.

[0004] However, in order to seek and maintain a comfortable life, it is only in Japan that it is necessary to pay close attention to some environmental problems and risks of radiation generation and rely on thermal power generation and nuclear power generation. It is the current state of the world. In addition, hydropower has problems such as unstable power supply due to season, deforestation due to power plant construction, and low power generation efficiency.
Power supply methods are declining. In addition, wind power and geothermal power are still costly,
Staying small.

[0005] On the other hand, when looking at fuels for automobiles, hydrocarbon fuels such as gasoline, light oil and propane gas are mainly used at present. Recently, “environmentally friendly” has become a catchphrase, and a hybrid vehicle that can switch and run with both electricity and gasoline has been put to practical use in order to suppress exhaust gas as much as possible.
However, even in the case of a hybrid vehicle, a hydrocarbon fuel such as gasoline must still be used.

[0006] From the current state of power generation and vehicle development,
Recently, hydrogen fuel has been receiving attention. Hydrogen can be produced by electrolysis of water. Therefore, considering the electrolysis of seawater and river water, hydrogen fuel is inexhaustible. Hydrogen is a clean energy source that does not generate carbon dioxide after combustion. Due to these advantages, hydrogen has attracted attention as an alternative fuel to hydrocarbon fuels such as gasoline and petroleum.

However, since hydrogen is a gas at normal temperature, it is more difficult to store and transport hydrogen than liquid or solid. In addition, hydrogen is a flammable substance, and when it has a predetermined mixing ratio with air, it explodes even in the presence of a slight electric spark. For this reason, hydrogen is a fuel that requires extremely careful handling. Although it is possible to store hydrogen in a high-pressure cylinder in a gaseous state, the amount of stored hydrogen is limited and high-pressure charging is expensive.

As a technique for solving such a problem, there is known a method of reacting hydrogen with a hydrogen storage alloy and storing the same as disclosed in Japanese Patent Application Laid-Open No. 7-192746.
However, La-Ni-based, Ti-Fe-based, etc. hydrogen storage alloys are heavy and have problems as a portable hydrogen storage device. In addition, existing hydrogen storage alloys can only store about 3% by weight of hydrogen at most, and there is a demand for storing more hydrogen. Another problem is that the hydrogen storage alloy is expensive.

Accordingly, hydrocarbons such as benzene and cyclohexane have attracted attention as a hydrogen storage method excellent in safety, transportability, storage capacity, and cost reduction. Since these hydrocarbons are liquid at normal temperature, they are excellent in transportability.

[0010] Benzene and hexane are cyclic hydrocarbons having the same number of carbon atoms. Benzene is an unsaturated hydrocarbon having a double bond between carbon atoms, whereas cyclohexane is a saturated hydrocarbon having no double bond. It is a hydrocarbon. Cyclohexane is obtained by a hydrogenation reaction of benzene, and benzene is obtained by a dehydrogenation reaction of cyclohexane.
In other words, hydrogen can be stored and supplied by utilizing the hydrogen addition / dehydrogenation reaction of these hydrocarbons.

[0011]

However, in order to put hydrogen storage and supply into practical use by utilizing a hydrogen addition reaction and a dehydrogenation reaction represented by a reaction between benzene and cyclohexane, the reaction efficiency is further increased. There is a need. In particular, there is a problem with the action of the catalyst with a liquid raw material such as benzene or cyclohexane.

For practical use, it is necessary that both raw materials are not mixed and that an appropriate amount of each raw material can be used for supplying or storing hydrogen at any time.

Further, in order to obtain high-purity hydrogen, it is necessary to efficiently separate gaseous hydrogen at room temperature from raw material which is liquid at room temperature.

The present invention has been made in view of the above circumstances, and has as its object to increase the reactivity of a raw material necessary for storing or supplying hydrogen. Another object of the present invention is to prevent both raw materials from being mixed and to make it possible to use an appropriate amount of each raw material at any time for supplying or storing hydrogen. Another object of the present invention is to efficiently separate hydrogen and a liquid raw material.

[0015]

In order to achieve the above object, the present invention provides a hydrogen storage comprising an aromatic compound which reacts with hydrogen to store the hydrogen, and an aromatic compound which releases hydrogen to release the hydrogen. A hydrogen storage / supply system that stores and supplies hydrogen by utilizing a hydrogen addition reaction and a dehydrogenation reaction with a hydrogen supply that changes to a hydrogen supply, wherein the hydrogen storage or the hydrogen supply A hydrogen reactor equipped with a heater for heating before or before the dehydrogenation reaction, a hydrogen supply unit for supplying hydrogen for a hydrogen addition reaction in the hydrogen reactor, and a hydrogen reactor produced by the dehydrogenation reaction in the hydrogen reactor. A hydrogen storage / supply system including a power generation device that generates power using the generated hydrogen.

[0016] Therefore, in the hydrogen reactor, there is no danger that the reaction rate between the raw material and the catalyst is reduced due to a decrease in the temperature of the raw material or the catalyst, and the storage or supply efficiency of hydrogen is extremely increased. As a result, hydrogen generated when refining or reforming natural gas or petroleum can be efficiently stored.
Further, the discharged hydrogen can be used for in-house power generation for home use or hospital use, or can be used as an auxiliary in response to fluctuations in power supply from a power plant. Further, a hydrogen supplier can be produced by adding external hydrogen to the hydrogen storage. Therefore, an independent energy conversion system can be constructed at home or factory.

Another aspect of the present invention is directed to a hydrogen storage device comprising an aromatic compound which stores hydrogen by reacting with the hydrogen and a hydrogen supply device which releases the hydrogen and converts the aromatic compound into an aromatic compound. A hydrogen storage / supply system for storing and supplying hydrogen using an addition reaction and a dehydrogenation reaction, wherein a first liquid tank containing a hydrogen storage is reacted with the hydrogen storage to supply hydrogen. A hydrogen supplier manufacturing apparatus having a reactor for producing a body, and a reaction for dehydrogenating a hydrogen supplier supplied from the hydrogen supplier manufacturing apparatus using a catalyst into hydrogen and a hydrogen storage body A hydrogen production device having a furnace and a power generation device that generates power using hydrogen generated by decomposition thereof, wherein a hydrogen storage device or a hydrogen supply device is provided to at least one of the hydrogen supply device and the hydrogen production device. At least in the body The Zureka one so that the hydrogen storage and supply system with a heater for heating before reacting in the reactor.

For this reason, in the hydrogen supply device or the hydrogen production device, the temperature of the raw material or the catalyst is lowered,
There is no danger that the reaction rate between the raw material and the catalyst will decrease, and the efficiency of hydrogen storage or supply will be extremely high. And
Households and factories produce hydrogen by dehydrogenating the hydrogen supply and send the hydrogen to the fuel cell to generate electricity, while the hydrogen storage recovered from the house is distributed to regional stations located in regions. The hydrogen is returned to the hydrogen supplier in the hydrogen supplier manufacturing apparatus. As described above, by sharing the hydrogenation reaction and the dehydrogenation reaction between the regional station and the home, one fuel cycle can be formed in the entire region. Further, when the hydrogen supplier is supplied to a fuel station for an automobile, the hydrogen supplier can be supplied to an electric vehicle including a reactor, a power generator, and a hydrogen storage container. Then, the hydrogen storage body recovered from the electric vehicle is converted into a hydrogen supply body at a regional station via a fuel station.

According to another aspect of the present invention, the heater according to the above-described aspect of the invention is a hydrogen storage / supply system in which energization can be controlled according to the type of aromatic compound. For this reason, even when another raw material is used, the temperature condition can be appropriately controlled according to the boiling point of the raw material and the degree of formation of the raw material liquid film on the catalyst surface. Therefore, even if the combination of the petroleum plant as the hydrogen supply device and the power generation device changes, it is possible to cope with the change.

In another invention, the aromatic compound in the above invention is formed by converting benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene,
A hydrogen storage / supply system comprising one or a mixture of any one of biphenyl, phenathrene and their alkyl-substituted products is provided.

These raw materials store hydrogen by adding hydrogen to a double bond between carbon atoms. The hydrogen supplier after hydrogenation releases hydrogen and returns to the original hydrogen storage.
That is, the above-mentioned raw material is a raw material suitable for recycling hydrogen. On the other hand, catalysts used for the hydrogenation reaction of the above-mentioned raw materials have already been researched and developed and are well known. Therefore, when the above-mentioned raw materials are used, development costs can be suppressed in practical use.

Another aspect of the present invention relates to a hydrogen storage device comprising an aromatic compound which reacts with hydrogen to store the hydrogen and a hydrogen supply device which releases hydrogen to convert the compound into an aromatic compound. A hydrogen storage and supply device that stores or supplies hydrogen using an addition reaction or a dehydrogenation reaction,
At least one of the first liquid tank containing the hydrogen storage or the second liquid tank containing the hydrogen supply, and the hydrogen addition reaction or the hydrogen supply of the hydrogen storage sent from the liquid tank. A reaction furnace having at least one of the hydrogen reactions of the dehydrogenation reaction and a catalyst used for the hydrogen reaction, and a hydrogen storage material or a hydrogen supply material which is a raw material for the hydrogen reaction and is supplied to the reaction furnace A hydrogen storage / equipment comprising an injection mechanism having an injection nozzle for injecting mist from the plurality of injection holes toward the catalyst, and a cooling tank for cooling the hydrogen storage or hydrogen supply generated in the reaction furnace. Supply device.

For this reason, in the hydrogen reactor, the raw material covers the catalyst surface in a uniform and appropriate liquid film state, and the efficiency of hydrogen storage or supply becomes extremely high. Therefore, it can be introduced into a system including a hydrogen supply device such as a petroleum refining plant and a power generation device such as a home power generation using a fuel cell. In particular, since there are a plurality of injection holes at the tip of the injection nozzle, the supply of the raw material to the catalyst surface becomes more uniform. Therefore, the amount of generated hydrogen or the amount of stored hydrogen can be further increased.

According to another aspect of the present invention, the injection mechanism in the above-described invention is provided with a common injection path for injecting the hydrogen storage body and the hydrogen supply body into the reaction furnace. Is stopped, the pressure in the injection nozzle is released to prevent the hydrogen storage or the hydrogen supply from dripping into the reaction furnace.

For this reason, it is not necessary to supply an extra raw material remaining in the supply pipe after supplying the raw material into the reaction furnace.
In particular, when switching between the hydrogen storage unit and the hydrogen supply unit, the possibility that the previous raw material is mixed is reduced. Therefore, the amount of generated hydrogen or the amount of stored hydrogen can be increased.

In another aspect of the present invention, the control unit for controlling the injection condition of the hydrogen storage or the hydrogen supply in the above-described invention is a hydrogen storage / supply device further provided. For this reason, even when another raw material is used, the injection conditions can be appropriately controlled in accordance with how the raw material forms a liquid film on the catalyst surface. Therefore, highly efficient hydrogen storage or hydrogen supply corresponding to any raw material can be performed.

Further, another invention is directed to a hydrogen storage device comprising an aromatic compound which reacts with hydrogen to store the hydrogen and a hydrogen supply device which releases hydrogen to convert the compound into an aromatic compound. A hydrogen storage and supply device that stores or supplies hydrogen using an addition reaction or a dehydrogenation reaction,
At least one of the first liquid tank containing the hydrogen storage or the second liquid tank containing the hydrogen supply, and the hydrogen addition reaction or the hydrogen supply of the hydrogen storage sent from the liquid tank. A reactor for performing at least one of the dehydrogenation reactions and a catalyst used for the hydrogen reaction, a heater for heating the hydrogen storage or the hydrogen supply before the hydrogen reaction, and a reaction furnace. And a cooling tank for cooling the hydrogen storage unit or the hydrogen supply unit generated in step (1).

For this reason, the reaction efficiency between the injected raw material and the catalyst increases. In particular, by providing a mechanism for heating the raw material, a decrease in temperature immediately after the raw material comes into contact with the catalyst can be reduced. Therefore, the amount of stored hydrogen or the amount of supplied hydrogen can be increased.

In another aspect of the present invention, the heater in the above-described invention is a hydrogen storage / supply device in which the heater is capable of heating up to the boiling point of the hydrogen storage or the hydrogen supply. For this reason, the reaction between the raw material and the catalyst can be further enhanced by raising the raw material temperature to slightly lower than the boiling point of the raw material. Specifically, the boiling point is 1 to 5 ° C.
Heating to a lower temperature is preferred.

Another aspect of the present invention is directed to a hydrogen storage device comprising an aromatic compound which reacts with hydrogen to store the hydrogen and a hydrogen supply device which releases hydrogen to convert the compound into an aromatic compound. A hydrogen storage and supply device that stores or supplies hydrogen using an addition reaction or a dehydrogenation reaction,
At least one of the first liquid tank containing the hydrogen storage or the second liquid tank containing the hydrogen supply, and the hydrogen addition reaction or the hydrogen supply of the hydrogen storage sent from the liquid tank. A reaction furnace equipped with a catalyst used for the hydrogen reaction while performing at least one of the hydrogen reactions in the dehydrogenation reaction, and a heater for heating the catalyst, wherein the catalyst was attached to the surface of the heater. The hydrogen storage / supply device includes a catalyst-integrated heater and a cooling tank that cools a hydrogen storage body or a hydrogen supply body generated in the reaction furnace.

Therefore, it is possible to efficiently prevent the temperature of the catalyst from decreasing. That is, since the heater is in direct contact with the catalyst and heat transfer to the catalyst is fast, the temperature of the catalyst does not easily decrease. Therefore, the amount of stored hydrogen or the amount of supplied hydrogen can be increased.

Further, another invention relates to a catalyst-integrated heater according to the above-described invention, wherein the catalyst is attached to a lattice-shaped heater surface, and a spiral catalyst in which a catalyst is attached to a spiral heater surface. The hydrogen storage / supply device is a heater, an embedded catalyst heater in which a heater is embedded in a catalyst, or an enclosed catalyst heater in which the catalyst is surrounded by a cylindrical heater. Therefore, the contact area between the catalyst and the heater can be increased. In addition, the inside of a reaction furnace that causes a hydrogen reaction together with the catalyst can be heated. Therefore, the amount of stored hydrogen or the amount of supplied hydrogen can be increased.

Another aspect of the present invention is a hydrogen storage / supply device further including a control unit for controlling the heater according to the above-described aspect. For this reason, even when another raw material is used, the temperature condition can be appropriately controlled according to the boiling point of the raw material and the degree of formation of the raw material liquid film on the catalyst surface.

Another aspect of the present invention is a path for discharging hydrogen from the reaction furnace according to the above-described invention, wherein a filter is provided outside the cooling tank, and a hydrogen storage material or hydrogen attached to the filter is provided on the filter. The hydrogen storage / supply device is provided with a filter heater for heating and volatilizing the supply body. For this reason, it is possible to prevent a filter such as an activated carbon filter from deteriorating in function due to adhesion of a liquid raw material. Therefore, there is no need to hinder the discharge of hydrogen.

Another aspect of the present invention is that the first liquid tank and the second liquid tank in the above-described invention are disposed adjacent to each other in one container, and the valve of the container is switched so that the hydrogen storage unit or the hydrogen storage unit is connected to the reaction furnace. A hydrogen storage / supply device configured to supply a hydrogen supply body is provided. For this reason, the device can be made more compact. Therefore, it is advantageous when it is installed at home or mounted on a car.

Another aspect of the present invention is a hydrogen storage / supply device having one common pump for supplying hydrogen flowing into the reaction furnace and discharging hydrogen from the reaction furnace in the above invention. . For this reason, the apparatus can be made more compact and the cost can be reduced.

Further, another invention is a hydrogen storage / supply device in which the catalyst in the above invention is a honeycomb-shaped catalyst or a catalyst supported on felt.
For this reason, since the contact area of the raw material with the catalyst can be increased, the amount of stored hydrogen or the amount of generated hydrogen can be increased. In addition, the catalyst can be formed into an arbitrary shape by being supported on the felt. Therefore, the size of the apparatus can be reduced because the space for the catalyst is not taken up.

In another aspect, the aromatic compound according to the above-mentioned invention is obtained by converting benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene,
A hydrogen storage / supply device is prepared by mixing any one or a plurality of any of biphenyl, phenathrene and their alkyl-substituted products.

These raw materials store hydrogen by adding hydrogen to a double bond between carbon atoms. The hydrogen supplier after hydrogenation releases hydrogen and returns to the original hydrogen storage.
That is, the above-mentioned raw material is a raw material suitable for recycling hydrogen. On the other hand, catalysts used for the hydrogenation reaction of the above-mentioned raw materials have already been researched and developed and are well known. Therefore, when the above-mentioned raw materials are used, development costs can be suppressed in practical use.

Another aspect of the present invention is directed to a hydrogen storage device comprising an aromatic compound which reacts with hydrogen to store the hydrogen and a hydrogen supply device which releases hydrogen to convert the compound into an aromatic compound. A hydrogen storage / supply catalyst used for an addition reaction or a dehydrogenation reaction, wherein the catalyst is attached to the surface of a heater for heating the catalyst so that the catalyst and the heater are integrated into a hydrogen storage / supply catalyst. I have to.

Thus, the catalyst has a low temperature drop.
That is, since the heater is in direct contact with the catalyst and heat transfer to the catalyst is fast, the temperature of the catalyst does not easily decrease. Therefore, by using this catalyst, the amount of stored hydrogen or the amount of supplied hydrogen can be increased.

Another aspect of the present invention is a heater according to the above-described invention, which comprises a grid-shaped catalyst heater having a catalyst attached to a grid-shaped heater surface, a spiral catalyst heater having a catalyst attached to a spiral heater surface, and a catalyst. The catalyst for hydrogen storage / supply is an embedded catalyst heater in which a heater is embedded therein, or an enclosed catalyst heater in which the catalyst is surrounded by a cylindrical heater.

Therefore, the contact area between the catalyst and the heater can be increased. In addition, the inside of a reaction furnace that causes a hydrogen reaction together with the catalyst can be heated. Therefore, the amount of stored hydrogen or the amount of supplied hydrogen can be increased.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of a hydrogen storage / supply system, a hydrogen storage / supply device, and a catalyst for hydrogen addition reaction / dehydrogenation reaction according to the present invention will be described with reference to the drawings.

FIG. 1 shows the storage or supply of hydrogen utilizing a hydrogenation reaction of an aromatic compound and a dehydrogenation reaction of a compound (hereinafter referred to as a chemical hydride) produced by the hydrogenation reaction of the aromatic compound. It is a figure showing a principle.

An aromatic compound 1 such as benzene undergoes a hydrogenation reaction with hydrogen 2 generated by electrolysis of water or the like to form a chemical hydride 3 such as cyclohexane. Specifically, hydrogen 2 is added to a double bond between carbons of the aromatic compound 1. That is, hydrogen 2 is converted to chemical hydride 3
Will be stored in the form of

The chemical hydride 3 is converted into an aromatic compound 1 and hydrogen 2 by a dehydrogenation reaction. On the other hand, hydrogen 2 is supplied into fuel cell 5 together with oxygen 4. The fuel cell 5 generates electricity according to the reverse principle of electrolysis of water.

As described above, the aromatic compound 1 functions as a hydrogen storage for storing hydrogen, and the chemical hydride 3 functions as a hydrogen supplier for supplying hydrogen to the outside. Therefore, a hydrogen storage / supply system using a cycle of the aromatic compound 1 and the chemical hydride 3 can be formed.

Next, an example of a hydrogen storage / supply system utilizing the principle shown in FIG. 1 will be described. In the following, raw materials such as chemical hydride will not be numbered.

FIG. 2 is a diagram schematically showing a hydrogen storage / supply system using an energy self-contained home power generation as an example.

The hydrogen storage / supply system provided in the house 10 mainly includes a solar cell 11, a wind generator 12, an electrolysis device 13, a hydrogen reaction device 14, and a fuel cell 15 installed on a roof or the like. Have.

The hydrogen reactor 14 includes a hydrogen storage container 16 serving as a first liquid tank containing a hydrogen storage made of an aromatic compound represented by benzene, and a hydrogen storage made of a chemical hydride represented by cyclohexane. A hydrogen supply container 17 as a second liquid tank containing a supply, and a reaction furnace 18
And a cooler 19.

The hydrogen storage container 16 and the hydrogen supply container 17 are provided with a heater 20 for heating the hydrogen storage and the hydrogen supply inside the containers 16 and 17. Further, the reaction furnace 18 is provided with a catalyst 21 required for the hydrogen addition reaction and the dehydrogenation reaction. The catalyst 21 is provided with a heater 22 for heating the catalyst. Further, the reaction furnace 18 is provided with an injection nozzle 23 for injecting a liquid material called a hydrogen storage or hydrogen supply.

The electricity generated by the solar cell 11 or the wind power generator 12 is converted into an alternating current via an inverter 24. The converted electricity is used for household electrical equipment 25 or when not using electrical equipment 25, the converted electricity is supplied to electrolysis device 13. In the electrolysis device 13, hydrogen (H2) and oxygen (O2) are generated by electrolysis of water. The generated hydrogen is supplied to the reaction furnace 18 of the hydrogen reactor 14.

When the electricity generated by the solar cell 11 or the wind power generator 12 is excessive, that is, when the electricity is generated more than the electricity used by the household electric appliance 25, the extra electricity is It is sent to the electrolysis device 13. The hydrogen generated in the electrolysis device 13 is supplied to the reaction furnace 1
8 On the other hand, a hydrogen storage material represented by benzene in the hydrogen storage container 16 is injected by the injection nozzle 23 to the catalyst 21 in the reaction furnace 18.

Then, hydrogen is added to the hydrogen storage material, and the hydrogen storage material is changed to a hydrogen supply material represented by cyclohexane. Here, the hydrogen storage body is heated by the heater 20 to near the boiling point of 80 ° C. For this reason, the ratio of the hydrogen storage involved in the hydrogenation reaction increases. The catalyst 21
Are heated to 60 to 120 ° C. by the heater 22. As a result, the rate of generation of the hydrogen supplier by the hydrogenation reaction becomes very high.

The hydrogen supply generated in the reactor 18 is:
It is liquefied by the cooler 19 and sent to the hydrogen supply container 17. On the other hand, excess hydrogen is sent to the fuel cell 15 during the hydrogen addition reaction.

The solar cell 11 or the wind power generator 12
In the case where the electricity generated by the electric power cannot supply the electric power of the electric device 25, the hydrogen supply body in the hydrogen supply container 17 is injected to the catalyst 21 in the reaction furnace 18 by the injection nozzle 23 constituting the injection mechanism. Is done.

Then, a dehydrogenation reaction of the hydrogen supplier occurs, and hydrogen is generated with a hydrogen storage material such as benzene. Here, the hydrogen supplier in the hydrogen supplier container 17 is the heater 2
It is heated to near the boiling point of 80 ° C. by 0. For this reason, the ratio of the hydrogen supplier involved in the dehydrogenation reaction increases. In addition, the catalyst 21 is heated 220 to 220 by the heater 22.
Heated to 400 ° C. For this reason, the generation rate of the hydrogen storage material by such a dehydrogenation reaction becomes very high. In addition,
Considering the efficiency of the dehydrogenation reaction, the catalyst 21 is 240 to 2
It is more preferable that the temperature is adjusted to 60 ° C. by the heater 22.

The hydrogen storage generated in the reaction furnace 18 is liquefied by the cooler 19 and sent to the hydrogen storage container 16. On the other hand, hydrogen generated by the dehydrogenation reaction is sent to the fuel cell 15.

In the fuel cell 15, electricity is generated by a reaction between hydrogen sent from the hydrogen reactor 14 and oxygen supplied from the air. The electricity thus produced is used for the home electric appliance 25 and is also supplied to the power of the electric vehicle 26. As described above, the hydrogen reactor 14 stores energy in the form of a hydrogen supplier such as cyclohexane, or generates energy from the hydrogen supplier by a dehydrogenation reaction, depending on the demand of household electric power.

FIG. 3 shows a dedicated regional station for converting a hydrogen storage material composed of an aromatic compound represented by benzene into a hydrogen supply material composed of a chemical hydride represented by cyclohexane, and a hydrogen supply material from the regional station. 1 is a diagram showing a hydrogen storage / supply system including a home, a factory (hereinafter, referred to as a home, etc.) and a fuel station for an automobile, which receive supply of hydrogen.

This hydrogen storage / supply system differs from the hydrogen storage / supply system of FIG. 2 in that it is not a system for establishing energy independence in a home or the like, but for establishing energy independence in the entire region. It is. Therefore, households and the like that generate energy by generating hydrogen 31
And a local station 3 that collects a hydrogen storage from the home 31 and adds hydrogen to the hydrogen storage to produce a hydrogen supply.
2 is responsible for the conversion of raw materials.

The regional station 32 includes a hydrogen storage container 33 as a first liquid tank containing a hydrogen storage, and a reaction furnace 34 for producing a hydrogen supply by a hydrogen addition reaction between the hydrogen storage and hydrogen. It is a hydrogen supplier manufacturing apparatus. Hydrogen supplied to the regional station 32 includes a wind generator 3
Hydrogen produced in the electrolyzer 36 using electricity from 5,
Hydrogen produced in the electrolyzer 38 using electricity from the solar cell 37, hydrogen produced in the process of producing organic matter using the zeolite catalyst 40 in the naphtha decomposition plant, biological waste disposal plant 39, etc., is included. .

The hydrogen storage materials such as benzene are produced in the process of producing organic substances using the zeolite catalyst 40. The hydrogen storage in the hydrogen storage container 33 is injected by an injection nozzle 41 into a reaction furnace 34 under a hydrogen atmosphere. The injected hydrogen storage is
A uniform and appropriate liquid film is formed on the surface of the catalyst 42. As a result, a hydrogen addition reaction with hydrogen on the surface of the catalyst 42 is promoted, and a hydrogen supplier is generated with high efficiency. Catalyst 42
Are heated to 60 to 120 ° C. by the heater 43.
Therefore, the hydrogen supply is produced with higher conversion efficiency. In addition, considering the conversion efficiency, the catalyst 42 is 95 to
It is more preferable to heat the heater 43 so as to reach 105 ° C.

The hydrogen supply generated in the reactor 34 is
It is sent to the home 31 or the like. The home or the like 31 is provided with a hydrogen production device 44. The hydrogen production apparatus 44 includes the reactor 4
5, a hydrogen storage container 46, and a fuel cell 47 as a power generation device. The hydrogen supply sent from the regional station 32 is injected from an injection nozzle 48 as an injection mechanism in the reaction furnace 45 to form a uniform and appropriate liquid film on the surface of the catalyst 49.

As a result, a hydrogen storage body and hydrogen are generated by the dehydrogenation reaction on the surface of the catalyst 49. The catalyst 49 is
The heater 50 is heated to 220 to 400 ° C. Therefore, hydrogen storage is produced with high conversion efficiency.
In consideration of the conversion efficiency, the catalyst 42 is 240 to 26
It is more preferable that the temperature be adjusted to 0 ° C. by the heater 50.

The mixture of the hydrogen storage and the hydrogen is cooled in the hydrogen storage container 46 and separated into the hydrogen storage and the hydrogen. Hydrogen, which is a gas at normal temperature, is sent to the fuel cell 47. In the fuel cell 47, electricity is generated by a reaction between hydrogen and oxygen. This electricity is used for various electric appliances such as the home 31. On the other hand, the hydrogen storage medium that is liquid at room temperature is sent to the hydrogen storage container 33 of the regional station 32.

In addition to the home 31 and the like, a hydrogen production apparatus 51 can be provided. The configuration of the hydrogen production device 51 is the same as the configuration of the hydrogen production device 44. The electricity produced by the hydrogen production device 51 is used for regulating electricity supplied from the power plant 52. That is, when the local power demand is not enough, the power supply from the hydrogen production device 51 is increased, and when the local power demand is sufficient, the power supply from the hydrogen production device 51 is reduced. Hydrogen production equipment 5
The hydrogen storage from 1 is sent to the regional station 32 to a hydrogen storage container 33 and then converted to a hydrogen supply.

Further, the hydrogen supply from the regional station 32 can be used as fuel for automobiles. The hydrogen supply body sent from the regional station 32 to the fuel supply station 53 can be supplied to the hydrogen production device 55 of the automobile 54. The hydrogen production device 55 includes a reaction furnace 56, a hydrogen storage container 57, and a fuel cell 58 as a power generation device. The hydrogen supply body supplied from the fuel supply stand 53 is injected from an injection nozzle 59 as an injection mechanism in the reaction furnace 56 to form a liquid film on the surface of the catalyst 60.

As a result, a hydrogen storage medium and hydrogen are generated by the dehydrogenation reaction on the surface of the catalyst 60. The catalyst 60 is heated to 220 to 400 ° C. by the heater 61. Therefore, the hydrogen storage is generated with high conversion efficiency. In consideration of the conversion efficiency, the catalyst 60 is 240 to 260
It is more preferable that the heating is performed by the heater 61 so that the temperature becomes ° C.

The mixture of the hydrogen storage and the hydrogen is cooled in the hydrogen storage container 57 and separated into the hydrogen storage and the hydrogen. Hydrogen that is a gas at normal temperature is sent to the fuel cell 58. In the fuel cell 58, electricity is generated by a reaction between hydrogen and oxygen, and is used for powering an automobile. On the other hand, the hydrogen storage material that is liquid at normal temperature is collected by the fuel supply stand 53. Thereafter, the hydrogen storage is sent to the regional station 32 and then converted to a hydrogen supplier by reaction with hydrogen.

As described above, the conversion from the hydrogen storage material to the hydrogen storage material is performed in the regional station 32, and the conversion from the hydrogen storage material to the hydrogen storage material is performed in the home 31, etc., the power generator 51 or the automobile 54. By returning the hydrogen storage to the regional station 32, a supply and recovery cycle of the raw material is formed throughout the region. Since only water is generated by the reaction between hydrogen and oxygen, it is possible to prevent global warming caused by carbon dioxide and pollution caused by generation of harmful substances such as NOX.

In the hydrogen storage / supply system shown in FIGS. 2 and 3, instead of benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenathrene, and their alkyl-substituted products are used instead of benzene. Any one of them or a mixture of any one of them may be used.

Next, the structure of a hydrogen storage / supply device corresponding to the hydrogen reactor 14 will be described with reference to FIGS.

FIG. 4 is a diagram schematically showing a configuration of a hydrogen storage / supply device capable of performing both storage and supply of hydrogen. FIG. 5 is a schematic diagram of the hydrogen storage and storage shown in FIG.
It is an external view of a supply apparatus. This hydrogen storage and supply device 70
Are mainly composed of a raw material supply tank 71, a pressurized tank 72, a pump 73, a reaction furnace 74, a cooling tank 75, and a filter 76.
And a pump 77.

The raw material supply tank 71 is provided with a benzene tank 79 as a first liquid tank and a cyclohexane as a second liquid tank separated by a partition 78 with benzene as a hydrogen storage material and cyclohexane as a hydrogen supply material. These are containers placed in hexane tanks 80, respectively. The raw material supply tank 71 is provided with a heater 81 and a heater 82 for heating the respective raw materials. The reason why the heaters 81 and 82 are provided is to reduce the influence of the temperature drop of the raw material during the injection onto the catalyst surface by supplying the raw material after heating it to near its boiling point.

The boiling points of benzene and cyclohexane are 80.1 ° C. and 80.9 ° C., respectively. Therefore, the heaters 81 and 82 control each raw material to a temperature of about 80 ° C. below the boiling point and close to the boiling point regardless of whether benzene is supplied or cyclohexane is supplied.
Each raw material can be supplied in a liquid state.

The pressurized tank 72 is configured to apply a pressure for injecting a raw material into the reaction furnace 74 to benzene or cyclohexane introduced into the pressurized tank 72 through a three-way valve 83 serving as a three-way valve. Department. This pressurization is performed by a pump 73 arranged between the pressurized tank 72 and the raw material supply tank 71. The pressurized tank 72 is provided with a valve 84 for discharging the raw material to the outside.

In order to adjust the pressure in the pressurized tank 72, when the value of the pressure gauge 85 exceeds a predetermined pressure value, the valve 86 and the three-way valve 87 serving as a three-way valve are opened to open the pressurized tank 72. The raw material is returned to the benzene tank 79 or the cyclohexane tank 80 in which the raw material has been stored. Conversely, when the value of the pressure gauge 85 becomes lower than the predetermined pressure value, the three-way valve 83 is opened and the benzene tank 79 is opened.
Alternatively, the same raw material as the raw material in the pressurized tank 72 is supplied from the cyclohexane tank 80 to the pressurized tank 72.

The reaction furnace 74 is a component for injecting benzene or cyclohexane into the catalyst 88 to cause a hydrogen addition reaction or a dehydrogenation reaction. In order to detect the pressure in the reaction furnace 74, the reaction furnace 74 is provided with a pressure gauge 74a. The injection of benzene or cyclohexane is performed from the injection nozzle 91 by opening the valve 89 and the valve 90. By injecting the raw material from the injection nozzle 91, a liquid film of the raw material is easily formed on the surface of the catalyst 88 in the container 93. The injection nozzle 91
The pressure tank 72 and the pump 73 are main components of the injection mechanism.

The valve 89 is a valve that enables instantaneous injection of the raw material, that is, pulse injection, by controlling the opening and closing time. The time of injection can be varied in the range of 0.5 to 30 seconds. Further, the time during which the injection is stopped can be varied in the range of 0.0 to 30 seconds. However, during normal operation, the injection time is set so that the upper limit is 5.0 seconds.

The valve 90 is a valve that closes when the supply of the raw material is stopped and opens when the supply of the raw material is stopped. The valve 90a is a valve that opens when the supply of the raw material is stopped to prevent dripping of the raw material. Valve 90a
The opening / closing timing of will be described later.

The injection nozzle 91 has an injection range angle X for the raw material.
Is designed to be 50 degrees at a pressure of 0.3 MPa. The injection amount of the raw material is 5.0 to 4 in one second of continuous injection.
It can be adjusted in the range of 0.0 ml.

The catalyst 88 has a diameter of 13
A structure in which a platinum catalyst is supported on a honeycomb cylindrical activated carbon material having a height of 0 mm and a height of 100 mm is used. The weight of the catalyst 88 is 100 g. The activated carbon ground may be a simple cylindrical shape having a diameter of 130 mm and a height of 100 mm.

Further, the reaction furnace 74 is provided with a heater 92 for heating the catalyst 88. The heater 92 is connected to the catalyst 8
8 is housed in the outer peripheral wall of the container 93. Also,
The heater 92 can heat up to 600 ° C.
Control is possible in the range of 0 to 600 ° C. When generating cyclohexane by the hydrogenation reaction of benzene, it is heated to about 60 to 120 ° C. Considering the conversion efficiency, it is preferable to heat to 95 to 105 ° C.

Further, when benzene is produced by the dehydrogenation of cyclohexane, it is heated to about 220 to 400 ° C. Similarly, considering the conversion efficiency, preferably, 2
It is good to heat to 50-300 ° C. This is because the hydrogenation reaction is an exothermic reaction and the dehydrogenation reaction is an endothermic reaction, and the latter reaction requires thermal energy.

In the reaction furnace 74, a valve 94 for supplying hydrogen into the furnace, a valve 95 for extracting raw material in the furnace, and a valve 96 for collecting hydrogen gas generated from the furnace are provided. Are provided. The valve 94 is opened before injecting benzene from the injection nozzle 91. This is because supplying benzene after setting the reaction furnace 74 in a hydrogen atmosphere is more suitable for increasing the efficiency of cyclohexane generation. The valve 96 is opened when analyzing the hydrogen gas by gas chromatography. Also,
The reaction furnace 74 is provided with two viewing windows 97 for observing the inside of the furnace.

The cooling tank 75 is a water-cooled circulation type cooling device. The cooling tank 75 is provided to completely liquefy benzene or cyclohexane sent from the reaction furnace 74 and separate it from hydrogen. Cooling is performed at 10 to 20 ° C., and can be changed in 1 ° C. units using a water temperature controller 98. As the refrigerant, a mixed solution of 30% by weight of ethylene glycol and 70% by weight of water is used.

When the valve 99 is opened after the hydrogenation reaction between benzene and hydrogen in the reaction furnace 74, the gas of cyclohexane mainly flows through the pipe 100 and is sent to the cooling tank 75. Here, the cyclohexane is cooled and liquefied. The liquefied cyclohexane is supplied to a cyclohexane tank 80
Valve which becomes a three-way valve so that only the side is open
After opening 1, it is sent to the cyclohexane tank 80.

On the other hand, when the valve 99 is opened after the dehydrogenation reaction of cyclohexane in the reaction furnace 74, a mixed gas of benzene and hydrogen mainly flows through the pipe 100 and the cooling tank 75
Will be sent to Here, the benzene is cooled and liquefied. The liquefied benzene is sent to the benzene tank 79 after opening the three-way valve 101 so that only the benzene tank 79 side is opened.

The filter 76 has a structure packed with activated carbon, and is provided for trapping benzene or cyclohexane mixed with hydrogen and discharging only hydrogen to the outside. Although not shown, the filter 76 can be heated by a heater. By periodically heating the filter to forcibly volatilize the trapped benzene and cyclohexane,
In order to extend the life of the device. Further, a gas vent valve 102 and a valve 103 that is opened for gas analysis are provided outside the filter 76.

The hydrogen that has passed through the filter 76 flows through the pipe 104 shown in FIG. 4 through the valve 105, the valve 107, the pump 77, the valve 109,
Then, it is discharged outside. At this time, the valve 10
6. The valve 108 is closed and the pump 77
It rotates in the direction of exhausting from the valve 108 to the valve 106.

On the other hand, when hydrogen is sent into the reaction furnace 74 from the outside, the valves 110, 108, 10
6. Open the valve 111 and switch the pump 77 to the valve 108.
To the direction in which hydrogen is introduced in the direction of the valve 106. At this time, the valve 109, the valve 107, and the valve 112 are in a closed state. In this way, the hydrogen is
Through the reactor 74. The piping 113
Is also used when the reaction furnace 74 is placed in a nitrogen atmosphere. When introducing nitrogen into the reaction furnace 74, the valve 112 and the valve 111 are opened to flow nitrogen.

Here, a procedure for storing hydrogen by a hydrogenation reaction of benzene using the hydrogen storage / supply device 70,
An example of a procedure for supplying hydrogen to the outside by a dehydrogenation reaction of cyclohexane will be briefly described with reference to FIG.

In the case of storing hydrogen from the outside, first, the inside of the reaction furnace 74 is filled with hydrogen while operating the pump 77 to adjust the initial pressure in the reaction furnace 74. Next, the temperature of the benzene tank 79 is adjusted to bring the benzene to 80 ° C. Next, the heater 92 of the reaction furnace 74 is turned on to adjust the temperature of the catalyst 88 to 100 ° C. Next, the three-way valve 8
3 and the pump 73 is operated to guide benzene in the benzene tank 79 to the pressurized tank 72 and
Adjust the initial pressure inside. Next, the temperature of the cooling water in the cooling tank 75 is adjusted to 10 ° C. Then, after opening the valve 90,
While the valve 89 is pulse-controlled, benzene is supplied to the reactor 7.
The pulse is injected toward the fourth catalyst 88. As a condition of the pulse injection, a method of repeating injection for 1.0 second and stopping for 1.0 second is optimal.

On the other hand, when supplying hydrogen to the outside, the valve 112 is opened and the reaction furnace 74 is filled with nitrogen. This is for performing gas analysis in advance. Next, the temperature of the cyclohexane tank 80 was adjusted, and cyclohexane was heated to 80 ° C.
To Next, the heater 92 of the reaction furnace 74 is turned on,
The temperature of the catalyst 88 is adjusted to 250 ° C. Next, the three-way valve 83 and the pump 73 are operated, and the cyclohexane tank 80 is operated.
While introducing the cyclohexane therein into the pressurized tank 72,
The initial pressure in the pressurized tank 72 is adjusted. Next, the cooling tank 75
Adjust the temperature of the cooling water to 10 ° C. And valve 9
After opening 0, cyclohexane is pulse-injected toward the catalyst 88 of the reaction furnace 74 while the valve 89 is pulse-controlled. As a condition of the pulse injection, a method of repeating injection for 1.0 second and stopping for 1.0 second is optimal.

A hydrogen tank 1 having a role as a hydrogen buffer as shown in FIG.
20 may be attached. This hydrogen tank 120
Is joined to the right end S of the hydrogen storage / supply device 70 shown in FIG. In the hydrogen tank 120, a pipe 121 jointed with the right end S of the hydrogen storage / supply device 70, a pipe 122 for pressure adjustment, and hydrogen flowing into the hydrogen tank 120,
Or a pipe 12 for discharging hydrogen from the hydrogen tank 120
3 are provided.

The pipe 122 has a valve 12 for pressure adjustment.
4 are provided. In addition, the pipe 123 includes the pipe 12
Temperature control device 125 for controlling the temperature of the third and valve 126
Are provided. The temperature control device 125 is provided in order to raise the temperature of hydrogen in advance in order to increase the power generation efficiency in the fuel cell when sending the hydrogen discharged from the hydrogen storage / supply device 70 side to the fuel cell. It is. Also,
When a liquid raw material such as benzene or cyclohexane is mixed in from the hydrogen storage / supply device 70 side, it can be volatilized and discharged to the outside.

When supplying hydrogen to the hydrogen tank 120 from the outside, the valve 126 is opened to supply hydrogen to the hydrogen tank 120. The hydrogen in the hydrogen tank 120 is used for storing hydrogen.
By operating the pump 77 in the supply device 70,
It flows from the pipe 121 to the hydrogen storage / supply device 70.

On the other hand, when discharging hydrogen to the outside, the hydrogen from the hydrogen storage / supply device 70 is stored until the hydrogen tank 120 is pressurized to some extent, and then the valve 126 is discharged.
Open. The pressure in the hydrogen tank 120 can be adjusted by a valve 124.

Next, the appearance and internal structure of the raw material supply tank 71 of the hydrogen storage / supply device 70 will be described. FIG.
As shown in the figure, a discharge port 130 and a discharge port 13 for discharging each raw material to the pressurized tank 72 are provided below the benzene tank 79 and the cyclohexane tank 80 of the raw material supply tank 71.
1 are provided. In addition, an inlet 132 and an inlet 133 are provided above the benzene tank 79 and the cyclohexane tank 80, respectively, for each raw material to be recovered from the cooling tank 75.

The benzene tank 79 and the cyclohexane tank 80 are each provided with a throw-in type heater 8.
1, 82 are arranged. Note that a heater other than the throw-in heater may be used. As described above, the heater 8
1, 82 are heated to make each raw material 80 ° C., and then sent to the reaction furnace 74. When heating is performed to exceed the boiling point of each raw material, the feeding of each raw material tends to be hindered. On the other hand, as the temperature becomes lower than the boiling point, the reaction efficiency of the hydrogen addition reaction and the dehydrogenation reaction at the time of injection to the catalyst 88 decreases. . Therefore, a temperature in the range of 75 ° C. to 80 ° C. is preferable, and an ideal temperature range is 78 to 80 ° C.

Next, an opening and closing mechanism of a valve connected to the pressurized tank 72 of the hydrogen storage / supply device 70 will be described with reference to FIG. When the valve 89 is closed after injecting the raw material from the injection nozzle 91, the pulse injection of the raw material is stopped. By opening the valve 90a almost at the same time as closing the valve 89, the surplus raw material in the pipe 140 is sucked into the lower-pressure pipe 141 without dripping the raw material from the injection nozzle 91. Valve 86 shown
And between the three-way valve 87. Thereafter, a three-way valve 87 is used to open a benzene tank 79 or a cyclohexane tank 8.
Returned to 0.

The reason for this is that, if the dripping of the raw material is left, a predetermined amount or more of benzene or cyclohexane will be applied to the catalyst 88, and an appropriate liquid film cannot be formed on the surface of the catalyst 88. This is because there is a risk that the rate will decrease. In addition, the accuracy of switching between the hydrogen addition reaction and the dehydrogenation reaction is lacking, and the mixing of the previous raw material may cause a reduction in the reaction rate of a newly performed hydrogen reaction using another raw material. Specifically, when the valve 90a is opened 200 msec after the valve 89 is closed,
The smoothest stop of raw material supply with the least dripping can be achieved. However, by controlling the opening and closing of the valve 89, 200
The time loss of msec can vary. Therefore,
It is preferable to determine the timing of closing the valve 89 and the timing of opening the valve 90a according to the device.

Next, the appearance and the internal structure of the reaction furnace 74 of the hydrogen storage / supply device 70 will be described with reference to FIG. As shown in FIG. 9A, the upper part of the reactor 74 is
An outlet 150 for sending the reaction product to the cooling tank 75;
Attachment port 151 to which injection nozzle 91 is attached, inflow port 152 for introducing hydrogen or nitrogen into reaction furnace 74, and outflow port 1 to which valve 95 for extracting raw material in the furnace are connected.
53 are provided.

As shown in FIG. 9B, a plurality of small holes 91b are provided at the nozzle tip 91a of the injection nozzle 91 attached to the attachment port 151. Each raw material is injected toward the catalyst 88 from the fine holes 91b. Therefore, it is easy to form a liquid film having a uniform thickness on the surface of the catalyst 88.

Although a method of supplying the raw material in the form of droplets is conceivable, the supply tends to be biased to a part of the catalyst 88, and the excess raw material flows from the catalyst 88 and does not contribute to the reaction.
In addition, the material that has flowed down is wasted. Therefore, the supply of the raw material by the injection method using the injection nozzle 91 is preferable to the supply by the droplet. The nozzle tip 9
A single hole may be provided in 1a to inject the raw material.

Next, the form of the catalyst 88 used in the hydrogen storage / supply device 70 will be described with reference to FIG.
FIG. 10A is a diagram showing a cross section inside the reaction furnace 74 in FIG. As shown in FIG. 10A, the catalyst 88 is placed in a cylindrical container 93 having a bottom and an open top. FIG. 10B is a diagram illustrating an upper surface and a side surface of the catalyst 88.
Thus, the catalyst 88 has a honeycomb-like honeycomb shape. With such a honeycomb shape, the surface area contributing to the reaction per volume of the catalyst 88 can be increased. Therefore, the reaction rates of both the hydrogenation and dehydrogenation reactions via the catalyst 88 are improved.

Further, the catalysts 88 of various shapes shown in FIG. 11 can be employed. FIG. 11A is a diagram illustrating a catalyst-integrated heater 155 in which a catalyst 88 is attached to the surface of a mesh-shaped heater 92. FIG. 11B is a diagram showing a catalyst-integrated heater 156 in which a catalyst 88 is attached to the surface of a spiral heater 92.

The heaters 155, 156 with catalyst integrated type
By attaching the catalyst 88 to the surface of the heater 92 as described above, even if the temperature of the catalyst 88 temporarily drops during the injection of the raw material, the catalyst 88 immediately recovers to the initial temperature. For this reason,
The risk that the reaction rates of the hydrogenation reaction and the dehydrogenation reaction decrease can be reduced. In particular, since the dehydrogenation reaction is an endothermic reaction, the reaction rate is sensitive to the temperature drop of the catalyst 88. Therefore, in the case of a dehydrogenation reaction, the use of the catalyst-integrated heaters 155 and 156 is a particularly effective means.
As shown in FIG. 12, a catalyst-integrated heater 157 in which a heater 92 is embedded in a fixed catalyst 88 such as a cube, a rectangular parallelepiped, or a column may be used.

Next, a control section for performing various controls of the hydrogen storage / supply device 70 will be described. As shown in FIG.
The control unit 160 mainly includes a control panel 161, a CRT monitor 162, and an operation unit 16 such as a keyboard and a mouse.
3, the PC body 164, and the PCI expansion unit 16
5 is provided.

The control panel 161 has a power switch 170 of a 100 V power supply, a power switch 171 of a 200 V power supply for a pump, a flow meter 172 for measuring the flow rate of hydrogen discharged to the outside, and a flow rate of hydrogen taken in from the outside. A flow meter 173 for measurement, a temperature controller 174 of the reaction furnace 74,
A temperature controller 175 for the benzene tank 79, a temperature controller 176 for the cyclohexane tank 80, a valve controller 177,
Injection time setting timers 178 and 179 for setting the injection time and the injection stop time, a changeover switch 180 for switching operation between hydrogen addition and dehydrogenation, and a buzzer alarm unit 18
1, an operation switch 182, and a state indicator 183 for displaying an operation state.

The controller 160 controls the temperature of the catalyst 88, the temperature in the reactor 74, the temperature of the surface of the heater 92, the temperature of each raw material, the temperatures of the inlet and outlet of the cooling tank 75, the temperature of the injected raw material, Each control of the temperature of the hydrogen supplied to is performed. The control unit 160 measures the flow rate of the generated hydrogen and the flow rate of the hydrogen supplied to the inside of the reaction furnace 74.

In the control section 160, the pressure inside the reaction furnace 74, the pressure in the raw material supply tank 71, the pressure in the pressurized tank 72, the hydrogen pressure after cooling, the injection pressure of the raw material, and the supply The pressure of the generated hydrogen is detected. Further, an upper limit and a lower limit of the liquid level in the benzene tank 79 and the cyclohexane tank 80 can be set. If there is no liquid level between the upper limit and the lower limit, a mechanism for notifying the user is provided. The control unit 16
At 0, the opening and closing of the valve and the operation of the pumps 73 and 77 are controlled.

The personal computer main body 164 is a part for setting and controlling the temperature and pressure in various components such as the reaction furnace 74, and at the same time, it can also analyze hydrogen using installed gas chromatography analysis software.

Next, a description will be given of a result obtained by ascertaining the operating conditions with a lab-scale device before the operation of the hydrogen storage / supply device 70.

FIG. 14 is a graph showing the results of examining the reaction temperature dependence of the dehydrogenation of cyclohexane. The horizontal axis is the reaction temperature, and the vertical axis is the amount of hydrogen generated per minute. FIG.
As shown in the graph, when the reaction temperature is 523 K (= 250 ° C.), the amount of generated hydrogen is the largest. On the other hand, if the reaction temperature is too high, the amount of generated hydrogen decreases. this is,
It is considered that this is because the volatile matter of the raw material increases, and it becomes difficult to form a liquid film of the raw material on the surface of the catalyst 88.

FIG. 15 is a graph showing the result of examining the dependence of the dehydrogenation reaction of cyclohexane on the base mass. The horizontal axis is the base mass, and the vertical axis is the amount of hydrogen generated per minute. Here, the base mass refers to the supply amount of cyclohexane. 0.5 g of platinum was used for the catalyst 88. The reaction temperature is 5
23K.

As shown in FIG. 15, when the supply amount of cyclohexane is 1.7 ml, the amount of generated hydrogen is the largest. It is considered that the reason why the amount of hydrogen generated decreases when the supply amount of cyclohexane increases is that excess cyclohexane is applied to the catalyst 88 and an appropriate liquid film cannot be formed on the catalyst surface.

The above are the results of an experiment conducted to examine the conditions for the dehydrogenation of cyclohexane. However, other than cyclohexane, a chemical hydride such as decalin can be used. Next, the results of a laboratory-scale experiment using decalin will be described.

FIG. 16 is a diagram showing a reversible reaction formula in which naphthalene and hydrogen are produced by the dehydrogenation reaction of decalin, and conversely, decalin is produced by the hydrogenation reaction of naphthalene. In the case of using decalin, as in the case of using cyclohexane, only hydrogen can be generated without breaking the carbon skeleton. Therefore, decalin can be a clean energy source that can prevent global warming accompanying the release of carbon dioxide.

FIG. 17 is a graph showing the results obtained by examining the dependence of the dehydrogenation reaction of decalin on the base mass. The horizontal axis is the base mass, and the vertical axis is the amount of hydrogen generated per minute. Here, the base mass refers to the supply amount of decalin. The catalyst 88 has 0.
5 g of platinum was used. The reaction temperature was 523K.

As shown in FIG. 17, it can be seen that as the supply amount of decalin increases from 1.4 to 1.75 ml, the amount of generated hydrogen decreases. It is considered that the reason why the amount of generated hydrogen decreases when the supply amount of decalin increases is that excessive decalin is applied to the catalyst 88 and an appropriate liquid film cannot be formed on the catalyst surface.

FIG. 18 is a graph showing the result of comparing the amount of generated hydrogen by changing the type of chemical hydride. In the figure, open triangles indicate the case where only decalin was used. Black diamonds indicate the case where a mixed solution of decalin and methylcyclohexane was used, and black squares indicate the case where a mixed solution of decalin and cyclohexane was used. The amount of generated hydrogen gas is shown as a cumulative value for each time. The reaction temperature was 573 K, and the supply amounts of the raw materials were 1.75 ml / min for all three types.

As a result, it was found that when only decalin was dehydrogenated, generation of hydrogen gas was extremely increased. Further, it was found that in the case of a mixed solution of decalin and methylcyclohexane, the generation amount of hydrogen gas was the least. Naphthalene produced by the dehydrogenation of decalin has a high melting point (about 80 ° C.) and is difficult to use at room temperature. For this reason, it is preferable to use cyclohexane rather than decalin.

[0127]

[Table 1]

Table 1 shows the results of hydrogen release using various chemical hydrides. As the chemical hydride, methylcyclohexane can be used in addition to cyclohexane or decalin. Further, as other compounds containing hydrogen, methanol, lithium hydride, and calcium hydride can also be used. Judging from only the amount of hydrogen generated (= weight of hydrogen generated for the same weight of raw material), lithium hydride, decalin, and cyclohexane are superior as raw materials.

However, in terms of ease of use of the raw material after releasing hydrogen, decalin which produces naphthalene is inferior to cyclohexane. This is because naphthalene becomes a solid at room temperature and sublimates at 80 ° C. or higher without liquefaction. Lithium hydride is inferior to cyclohexane in terms of handling danger. Cyclohexane becomes benzene after the dehydrogenation reaction. Benzene has a boiling point of 80.1 ° C. and is an easy-to-use raw material, like cyclohexane having almost the same boiling point. Therefore, from the viewpoint of ease of use including the amount of released hydrogen and safety, cyclohexane is the most suitable raw material.

However, raw materials other than cyclohexane can be used if safety is improved and use conditions are changed. For example, a chemical hydride that becomes xylene, mesitylene, methylnaphthalene, anthracene, biphenyl or phenathrene after releasing hydrogen can be used.

[0131] The type of catalyst used in the reaction was also examined. Specifically, platinum mixed with 4.5 wt% tungsten and platinum mixed with 1.9 wt% rhodium were examined. As a result, it was found that when a platinum catalyst mixed with 4.5% by weight of tungsten was used, the amount of generated hydrogen was the largest.

[0132]

Next, the results of examining changes in the amount of hydrogen generated when the injection conditions for pulse injection of cyclohexane to the catalyst were changed in the following examples will be described.

The catalyst used was 0.5% by weight of alumina.
Was used. A cylindrical granule carrying platinum was used. The amount of the catalyst was 20 g. The catalyst temperature is 240-270 ° C
It was. The cooling temperature was 13 to 15 ° C. The injection time of cyclohexane was 1 second, and the injection intervals in which injection was stopped were changed to 10, 20, and 30 seconds, and each injection interval was compared with the amount of generated hydrogen.

Table 2 shows the results.

[0135]

[Table 2]

As shown in Table 2, in the case of the injection interval of 10 seconds, the hydrogen generation rate measured at 17 minutes after the injection was 11.1 hours.
0 ml / sec, and the hydrogen gas generation efficiency determined from the accumulated hydrogen generation amount for 17 minutes from the start of the experiment was about 8
1.7%. The hydrogen gas generation efficiency refers to the ratio (%) to the theoretical hydrogen gas generation amount.

When the injection interval is 20 seconds, the measured hydrogen generation rate 82 minutes after the injection is 9.6 ml / sec.
c, and the hydrogen gas generation efficiency determined from the accumulated hydrogen generation amount for 82 minutes from the start of the experiment was about 82.3%.

When the injection interval was 30 seconds, the hydrogen generation rate measured at 48 minutes after the injection was 12.3 ml / s.
ec, and the hydrogen gas generation efficiency determined from the accumulated hydrogen generation amount for 48 minutes from the start of the experiment was about 83.3%.

The hydrogen generation rate cannot be compared because it decreases with the passage of time from the start of the experiment. However, when the hydrogen gas generation efficiency is compared, within the range of the injection interval in this experiment, it does not depend on the injection interval. , 80% or more of hydrogen was generated with high efficiency.

The present invention is not limited to the above embodiments and examples. Various modified embodiments as described below may be adopted. For example, in the above embodiment,
The system that includes both the hydrogenation reaction and the dehydrogenation reaction has been described.However, a device or system that performs only one of the reactions is configured, and a device or system that performs the other reaction is configured as another system. Is also good.

Depending on the selection of the raw materials, it is not necessary to heat only the raw materials and not the catalyst. Also, the heating of the raw material may be performed by heating only the hydrogen supply body and not heating the hydrogen storage body. Furthermore, it is not necessary to heat only the catalyst and heat the raw material. Further, regarding the injection of the raw material, only the hydrogen storage may be injected, or only the hydrogen supply may be injected.

Further, as the catalyst-integrated heater, the shape of the heater is not limited to the lattice type or the spiral type, but may be various shapes. Further, benzene and cyclohexane may be put in separate containers instead of being put in one container. Also,
A pump for discharging hydrogen and a pump for supplying hydrogen may be separated.

Further, a power generator other than the fuel cell may be employed. For example, electricity may be generated by burning hydrogen to boil water, rotating a turbine, and rotating a generator. Further, a conventional electric power supply system such as a thermal power plant or a nuclear power plant may be used in combination with the hydrogen storage / supply system.

[0144]

According to the present invention, the reaction efficiency of a hydrogenation reaction or a dehydrogenation reaction can be increased. Further, according to another aspect of the present invention, it is possible to prevent the hydrogen storage and the hydrogen supply from being mixed with each other, and to allow an appropriate amount of each raw material to be used for supply or storage of hydrogen at any time. According to another aspect of the present invention, hydrogen and a liquid raw material can be efficiently separated.

[Brief description of the drawings]

FIG. 1 is a diagram showing the principle underlying a hydrogen storage / supply system of the present invention, in which a hydrogenation reaction of an aromatic compound and a compound produced by the hydrogenation reaction of the aromatic compound (hereinafter, referred to as “hydrogenation reaction”);
FIG. 3 is a diagram showing a flow of storing or supplying hydrogen using a dehydrogenation reaction of a chemical hydride).

FIG. 2 is a diagram illustrating a hydrogen storage and supply system according to an embodiment of the present invention, and is a diagram illustrating a hydrogen storage and supply system as an example of an energy self-contained home power generation system for home use;

FIG. 3 is a diagram showing a hydrogen storage / supply system according to an embodiment of the present invention. FIG. 3 shows a dedicated regional station for converting a hydrogen storage such as benzene into a hydrogen supplier such as cyclohexane, and hydrogen from the regional station. It is a figure which shows the hydrogen storage / supply system which consists of the fuel station for homes, factories, or vehicles which receive supply of a supply body.

FIG. 4 is a diagram illustrating a hydrogen storage / supply system according to an embodiment of the present invention, and is a diagram schematically illustrating a hydrogen storage / supply device that can perform both storage and supply of hydrogen.

FIG. 5 is an external view of a hydrogen storage / supply device schematically shown in FIG.

6 is a diagram showing a hydrogen tank which can be attached to the hydrogen storage / supply device of FIG. 4, and piping around the hydrogen tank.

FIG. 7 is a diagram showing the appearance and internal structure of a raw material supply tank provided in the hydrogen storage / supply device of FIG.

8 is a diagram showing a pressurized tank provided in the hydrogen storage / supply device of FIG. 4 and piping around the pressurized tank.

9A and 9B are views showing the appearance and the internal structure of the reaction furnace and the like of the hydrogen storage / supply device in FIG. 4, wherein FIG. 9A shows the appearance and the internal structure of the reaction furnace, and FIG. The injection nozzle,
Shown respectively.

10A and 10B are diagrams for explaining the form of a catalyst used in the hydrogen storage / supply device of FIG. 4, in which (A) shows a cross section inside the reaction furnace, and (B) shows an upper surface and a side surface of the catalyst, respectively. .

11A and 11B are diagrams showing a catalyst in a form other than the catalyst shown in FIG. 10; FIG. 11A shows a catalyst-integrated heater in which a catalyst is attached to a mesh-shaped heater surface; FIG. 11B shows a spiral heater surface; FIG. 3 is a diagram illustrating a catalyst-integrated heater in which a catalyst is attached to a heater.

FIG. 12 is a view showing a catalyst in a form other than the catalysts shown in FIGS. 10 and 11, and is a view showing a catalyst-integrated heater in which a heater is embedded inside a fixed catalyst.

13 is a diagram illustrating a control unit that performs various controls of the hydrogen storage / supply device of FIG.

FIG. 14 is a graph showing the results of examining the reaction temperature dependence of the dehydrogenation of cyclohexane used in the present invention.

FIG. 15 is a graph showing the results obtained by examining the dependence of the dehydrogenation of cyclohexane used in the present invention on the base mass.

FIG. 16 is a diagram showing a reaction formula in which naphthalene and hydrogen are produced by a dehydrogenation reaction of decalin and conversely, decalin is produced by a hydrogenation reaction of naphthalene which can be used in the present invention.

FIG. 17 is a graph showing the results obtained by examining the dependence of the dehydrogenation reaction of decalin on the base mass that can be used in the present invention.

FIG. 18 is a graph showing the results of comparing the amount of generated hydrogen with different types of chemical hydrides usable in the present invention.

[Explanation of symbols]

 13 Hydrogen Supply Device 14 Hydrogen Reactor 15 Power Generator 16 Hydrogen Storage Container (First Liquid Tank) 17 Hydrogen Supply Container (Second Liquid Tank) 18 Reactor 20 Heater 21 Catalyst 22 Heater 23 Injection Nozzle 32 Regional Station (Hydrogen) Supply device manufacturing device) 33 Hydrogen storage container (first liquid tank) 34 Reactor 42 Catalyst 43 Heater 44 Hydrogen production device 45 Reaction furnace 46 Hydrogen storage container 47 Fuel cell (power generation device) 48 Injection nozzle 49 Catalyst 50 Heater 51 Hydrogen production device 55 Hydrogen production device 56 Reactor 57 Hydrogen storage container 58 Fuel cell (power generation device) 59 Injection nozzle 60 Catalyst 61 Heater 70 Hydrogen storage / supply device (hydrogen reaction device) 71 Raw material supply tank (container) 72 Pressurization Tank (part of injection mechanism) 73 Pump (part of injection mechanism) 74 Reactor 75 Cooling tank 7 Filter 77 Pump 79 Benzene tank (first liquid tank) 80 Cyclohexane tank (second liquid tank) 81 Heater (heater for heating raw material) 82 Heater (heater for heating raw material) 83 Valve 88 Catalyst 91 Injection nozzle (one of injection mechanism section) Part) 91b injection hole 92 heater (catalyst heating heater) 155 lattice catalyst heater (catalyst integrated heater) 156 spiral catalyst heater (catalyst integrated heater) 157 embedded catalyst heater (catalyst integrated heater) 160 controller

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[Procedure amendment]

[Submission Date] October 10, 2001 (2001.10.
10)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

[0015]

In order to achieve the above object, the present invention provides a hydrogen storage comprising an aromatic compound which reacts with hydrogen to store the hydrogen, and an aromatic compound which releases hydrogen to release the hydrogen. A hydrogen storage / supply system that stores and supplies hydrogen by utilizing a hydrogen addition reaction and a dehydrogenation reaction with a hydrogen supply that changes to a hydrogen supply, wherein the hydrogen storage or the hydrogen supply Before or before the dehydrogenation reaction, a hydrogen reactor equipped with a heater for heating to a temperature below the boiling point and near the boiling point, and a hydrogen supply device for supplying hydrogen for a hydrogen addition reaction in the hydrogen reactor A hydrogen storage / supply system including a power generation device that generates power using hydrogen generated by the dehydrogenation reaction in the hydrogen reaction device.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

Another aspect of the present invention relates to a hydrogen storage device comprising an aromatic compound which reacts with hydrogen to store the hydrogen and a hydrogen supply device which releases hydrogen to convert the compound into an aromatic compound. A hydrogen storage and supply device that stores or supplies hydrogen using an addition reaction or a dehydrogenation reaction,
At least one of the first liquid tank containing the hydrogen storage or the second liquid tank containing the hydrogen supply, and the hydrogen addition reaction or the hydrogen supply of the hydrogen storage sent from the liquid tank. A reaction furnace having at least one of the hydrogen reactions of the dehydrogenation reaction and a catalyst used for the hydrogen reaction, and a hydrogen storage material or a hydrogen supply material which is a raw material for the hydrogen reaction and is supplied to the reaction furnace An injection mechanism portion having an injection nozzle for injecting mist from a plurality of injection holes toward the catalyst, and a cooling tank for cooling a hydrogen storage body or a hydrogen supply body generated in the reaction furnace, the injection mechanism section The hydrogen storage and hydrogen supply
Equipped with a common injection path for injecting
When the injection of the storage or hydrogen supply is stopped,
Release the pressure in the whirlpool and the hydrogen storage or hydrogen
The hydrogen storage / supply device is designed to prevent dripping into the reactor .

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

Also, after the raw material is supplied, the residual
It is not necessary to supply the surplus raw material existing in the reactor. Special
Then, when switching between the hydrogen storage and the hydrogen supply,
The possibility that the previous raw material is mixed is reduced. Therefore, water
The amount of element generated or the amount of hydrogen stored can be increased.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

Further , another invention is directed to the water in the above invention.
Control unit that controls the injection conditions of the hydrogen storage unit or hydrogen supply unit
As a hydrogen storage and supply device
I have.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

Therefore, when another raw material is used,
Also, depending on how the liquid film is formed on the catalyst surface of the raw material,
Injection conditions can be controlled appropriately. Therefore, what
High-efficiency hydrogen storage or hydrogen supply corresponding to raw materials
Wear.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0027

[Correction method] Change

[Correction contents]

Further, another invention is directed to a hydrogen storage device comprising an aromatic compound which reacts with hydrogen to store the hydrogen and a hydrogen supply device which releases hydrogen to convert the compound into an aromatic compound. A hydrogen storage and supply device that stores or supplies hydrogen using an addition reaction or a dehydrogenation reaction,
At least one of the first liquid tank containing the hydrogen storage or the second liquid tank containing the hydrogen supply, and the hydrogen addition reaction or the hydrogen supply of the hydrogen storage sent from the liquid tank. of dehydrogenation reaction, performs at least one of the hydrogen reaction, a reactor equipped with a catalyst for use in hydrogenation reactions, prior to hydrogenation reaction the hydrogen reservoir or a hydrogen donor, its
And a cooling tank for cooling the hydrogen storage or hydrogen supply generated in the reaction furnace.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

Further , by raising the temperature of the raw material to slightly lower than the boiling point of the raw material, the reaction between the raw material and the catalyst can be further enhanced. Specifically, the boiling point is 1 to 5
It is preferred to heat to a temperature lower by ° C.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasunori Sugai 1-2-1, Shimonopporo Techno Park, Atsubetsu-ku, Sapporo, Hokkaido In-house Corporation (72) Inventor Tadashi Utagawa 1-2-1, Shimonopporo Techno Park, Atsubetsu-ku, Sapporo, Hokkaido Densei Co., Ltd. (72) Inventor Tadashi Sakuramoto 1-2-1, Shimonopporo Techno Park, Atsubetsu-ku, Sapporo, Hokkaido F-term (reference) 3E072 EA10 4G040 AA12 AA31 4G140 AA12 AA31 5H027 AA02 BA13

Claims (19)

[Claims] 1. A hydrogen addition reaction and dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen to store the hydrogen, and a hydrogen supplier which releases hydrogen to be converted into the aromatic compound. A hydrogen storage / supply system for storing and supplying hydrogen using an elementary reaction, wherein the heater heats the hydrogen storage body or the hydrogen supply body before the hydrogenation reaction or before the dehydrogenation reaction. A hydrogen supply device that supplies hydrogen for a hydrogen addition reaction in the hydrogen reaction device, and a power generation device that uses the hydrogen generated by the dehydrogenation reaction in the hydrogen reaction device to generate power And a hydrogen storage / supply system. 2. A hydrogen addition reaction and a dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen to store the hydrogen, and a hydrogen supplier which releases hydrogen to be converted to the aromatic compound. A hydrogen storage / supply system for storing and supplying hydrogen by using an elementary reaction, comprising: a first liquid tank containing the hydrogen storage, and a reaction between the hydrogen storage and hydrogen to produce the hydrogen supply. A hydrogen supplier manufacturing apparatus having a reaction furnace for generating hydrogen, and the hydrogen supplier supplied from the hydrogen supplier manufacturing apparatus is dehydrogenated using the catalyst, and decomposed into hydrogen and the hydrogen storage body. A hydrogen production apparatus having a reaction furnace and a power generation apparatus that generates power using hydrogen generated by decomposition thereof,
For heating at least one of the hydrogen storage device or the hydrogen supply device in the hydrogen supply device or the hydrogen production device before reacting in the reaction furnace. A hydrogen storage / supply system comprising: a heater; 3. The heater according to claim 1, wherein the heater can be energized according to the type of the aromatic compound.
Or the hydrogen storage / supply system according to 2. 4. An aromatic compound obtained by mixing one or more of benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenathrene, and an alkyl-substituted product thereof. The hydrogen storage and supply system according to any one of claims 1 to 3, wherein: 5. A hydrogen addition reaction or dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen and stores the hydrogen, and a hydrogen supplier which releases hydrogen to convert to the aromatic compound. A hydrogen storage / supply device for storing or supplying hydrogen using an elementary reaction, wherein at least one of a first liquid tank containing the hydrogen storage material or a second liquid tank containing the hydrogen supply material A catalyst for performing at least one of a hydrogen addition reaction of the hydrogen storage unit and a dehydrogenation reaction of the hydrogen supply unit sent from the liquid tank with one liquid tank and utilizing the hydrogen reaction A hydrogen storage material or a hydrogen supply material, which is a raw material for the hydrogen reaction and is supplied to the reaction furnace, is sprayed from a plurality of injection holes toward the catalyst in a mist state. With injection nozzle A morphism mechanism, hydrogen storage and supply device, characterized in that it comprises a cooling tank for cooling the hydrogen storage material or the hydrogen donor which is generated in the reactor. 6. The injection mechanism has a common injection path for injecting the hydrogen storage medium and the hydrogen supply medium into the reaction furnace, and stops injection of the hydrogen storage medium or the hydrogen supply medium. 6. The hydrogen storage / supply device according to claim 5, wherein the pressure in the injection nozzle is released to prevent the hydrogen storage or the hydrogen supply from dripping into the reaction furnace. . 7. The hydrogen storage / supply device according to claim 5, further comprising a control unit for controlling an injection condition of the hydrogen storage unit or the hydrogen supply unit. 8. A hydrogen addition reaction or dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen and stores the hydrogen, and a hydrogen supplier which releases hydrogen and converts it to the aromatic compound. A hydrogen storage / supply device for storing or supplying hydrogen using an elementary reaction, wherein at least one of a first liquid tank containing the hydrogen storage material or a second liquid tank containing the hydrogen supply material One liquid tank and at least one of a hydrogen addition reaction and a dehydrogenation reaction of the hydrogen supply sent from the liquid tank are used for the hydrogen reaction. A reaction furnace having a catalyst, a heater for heating the hydrogen storage body or the hydrogen supply body before the hydrogen reaction, and a cooling tank for cooling the hydrogen storage body or the hydrogen supply body generated in the reaction furnace. , Be prepared A hydrogen storage / supply device characterized in that: 9. The hydrogen storage / supply device according to claim 8, wherein said heater is a heater capable of heating up to a boiling point of said hydrogen storage material or said hydrogen supply material. 10. A hydrogen addition reaction or dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen to store the hydrogen, and a hydrogen supplier which releases hydrogen to convert the hydrogen into an aromatic compound. A hydrogen storage / supply device for storing or supplying hydrogen using an elementary reaction, wherein at least one of a first liquid tank containing the hydrogen storage material or a second liquid tank containing the hydrogen supply material One liquid tank and at least one of a hydrogen addition reaction of the hydrogen storage material sent from the liquid tank and a dehydrogenation reaction of the hydrogen supplier are used for the hydrogen reaction. A reaction furnace having a catalyst, a heater for heating the catalyst, a catalyst-integrated heater having the heater attached to the surface of the heater, and the hydrogen storage or the hydrogen supply generated in the reaction furnace body And a cooling tank for cooling the hydrogen. 11. The catalyst-integrated heater includes a grid-shaped catalyst heater having a catalyst attached to a grid-shaped heater surface, a spiral catalyst heater having a catalyst attached to a spiral heater surface,
The hydrogen storage / supply device according to claim 10, wherein the catalyst is an embedded catalyst heater in which a heater is embedded in a catalyst or an enclosed catalyst heater in which a catalyst is enclosed by a cylindrical heater. 12. The apparatus according to claim 8, further comprising a control unit for controlling a heating condition by said heater.
The hydrogen storage / supply device according to any one of the preceding claims. 13. A path for discharging hydrogen from the reaction furnace, wherein a filter is provided outside the cooling tank, and the filter heats the hydrogen storage unit or the hydrogen supply unit attached to the filter. 13. The hydrogen storage / supply device according to claim 5, further comprising a filter heater for volatilizing the gas. 14. The hydrogen storage body or the hydrogen supply body is provided in the reaction furnace by switching the valve of the container by arranging the first liquid tank and the second liquid tank adjacent to each other in one container. The hydrogen storage and supply device according to any one of claims 5 to 13, wherein the hydrogen storage and supply device is configured to be able to supply hydrogen. 15. Supplying hydrogen flowing into the reactor,
The hydrogen storage / supply apparatus according to any one of claims 5 to 14, further comprising one common pump for discharging hydrogen from the reaction furnace. 16. The hydrogen storage / supply device according to claim 5, wherein the catalyst is a honeycomb-shaped catalyst or a catalyst supported on felt. 17. An aromatic compound obtained by mixing one or more of benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenathrene and their alkyl-substituted products. The hydrogen storage / supply device according to any one of claims 5 to 16, wherein: 18. A hydrogenation reaction or dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen and stores the hydrogen, and a hydrogen supplier which releases hydrogen to convert the aromatic compound into the aromatic compound. A hydrogen storage / supply catalyst for use in elementary reactions, wherein the catalyst is attached to the surface of a heater for heating the catalyst, and the catalyst and the heater are integrally configured. . 19. The heater includes a lattice catalyst heater having the catalyst adhered to a lattice heater surface, a spiral catalyst heater having the catalyst adhered to a spiral heater surface, and a heater embedded in the catalyst. 19. The hydrogen storage / supply catalyst according to claim 18, wherein the catalyst is an embedded catalyst heater or an enclosed catalyst heater in which the catalyst is surrounded by a cylindrical heater.