JP2003073102A - Apparatus for generating or storing hydrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase efficiency of a hydrogen additive reaction or a dehydrogenation reaction for storing or supplying hydrogen. SOLUTION: An apparatus for generating or storing hydrogen generates or stores hydrogen utilizing for the dehydrogenation reaction or the hydrogen addition reaction between a hydrogen generating substance which changes to an aromatic compound by discharging hydrogen and a hydrogen storing substance which consists of an aromatic compound to store hydrogen by reacting with hydrogen. A reaction part 141 in which a cavity 141(a) is filled with a catalyst 143 for the dehydrogenation reaction or the hydrogen addition reaction is installed. The dehydrogenation reaction or the hydrogen addition reaction is caused by spraying or coating of the hydrogen generating substance or the hydrogen storing substance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen generating / storing device for generating or storing hydrogen as an energy source for fuel cells and the like.

[0002]

2. Description of the Related Art The amount of energy consumed is increasing year by year, and problems such as the power supply from power plants becoming unable to keep up, especially in urban areas, are occurring. Currently, about half of Japanese electric power depends on thermal power generation, about 30% to 40% on nuclear power, and the rest on hydroelectric power, wind power, and the like.

However, petroleum, which is a fuel for thermal power generation, is a fossil fuel and its supply is limited. Further, exhaust gas such as carbon dioxide and NOX generated after burning oil is a cause of deterioration of global environment including global warming. In addition, nuclear power is regarded as a problem in the treatment of radioactive waste or accidents at power plants.

However, in order to maintain and maintain a comfortable life, Japan is the only one who has to rely on thermal power generation and nuclear power generation while keeping an eye on some environmental problems and the risk of radiation generation. It is the current state of the world. In addition, hydroelectric power generation has problems such as unstable power supply depending on the season, deforestation associated with construction of a power plant, and low power generation efficiency.
It is declining as a power supply method. In addition, wind power generation and geothermal power generation are still costly,
It remains small.

On the other hand, turning to automobile fuels, hydrocarbon fuels such as gasoline, light oil and propane gas are mainly used at present. Recently, "environmentally friendly" has become a catchphrase, and hybrid vehicles that can switch between electricity and gasoline have been put into practical use in order to suppress exhaust gas as much as possible.
However, even in the case of hybrid vehicles, hydrocarbon fuels such as gasoline still have to be used.

From the current state of power generation and automobile development,
Recently, hydrogen fuel has been drawing attention. Hydrogen can be generated by electrolysis of water. Therefore, considering the electrolysis of seawater or river water, hydrogen fuel is inexhaustibly present. Further, hydrogen is a clean energy source that does not generate carbon dioxide after combustion. Due to these advantages, hydrogen is drawing attention as an alternative fuel for hydrocarbon fuels such as gasoline and petroleum.

[0007] However, since hydrogen is a gas at room temperature, it is more difficult to store and transport it than liquid or solid. Moreover, hydrogen is a flammable substance and explodes at a predetermined mixing ratio with air even in the presence of a slight electric spark. Therefore, hydrogen is a fuel that requires extremely careful handling. It is possible to store hydrogen in a high-pressure cylinder in a gas state, but the storage amount is limited and high-pressure encapsulation is costly.

As a technique for solving such a problem, as disclosed in Japanese Patent Laid-Open No. 7-192746, there is known a method of reacting hydrogen with a hydrogen storage alloy and storing it.
However, the hydrogen storage alloys such as La-Ni type and Ti-Fe type are heavy and have a problem as a portable hydrogen storage device. In addition, existing hydrogen storage alloys can store a maximum amount of hydrogen of only about 3% by weight, and there is also a demand for increasing the amount of hydrogen stored. Another problem is that the hydrogen storage alloy is expensive.

Therefore, hydrocarbons such as benzene and cyclohexane are attracting attention as a hydrogen storage method which is excellent in safety, transportability, storage capacity and cost reduction. Since these hydrocarbons are liquid at room temperature, they are excellent in transportability.

Benzene and cyclohexane are cyclic hydrocarbons having the same carbon number. Benzene is an unsaturated hydrocarbon having a double bond between carbons, whereas cyclohexane is a saturated hydrocarbon having no double bond. It is a hydrocarbon. Cyclohexane is obtained by the hydrogenation reaction of benzene, and benzene is obtained by the dehydrogenation reaction of cyclohexane. That is, it is possible to store or generate hydrogen by utilizing the hydrogenation / dehydrogenation reaction of these hydrocarbons.

[0011]

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

The present invention has been made in view of the above circumstances, and it is an object of the present invention to enhance the reaction efficiency of a raw material required for hydrogen generation or storage.

[0013]

In order to achieve the above object, the present invention provides a hydrogen generator which releases hydrogen to be converted into an aromatic compound, and an aromatic compound which reacts with hydrogen to store the hydrogen. A hydrogen generating / storing device for generating or storing hydrogen by utilizing a dehydrogenation reaction or a hydrogen addition reaction with a hydrogen storage body, which comprises a hydrogen generator or a hydrogen storage body. A dehydrogenation reaction or a hydrogen addition reaction is characterized by providing a reaction member in which a catalyst for reaction is arranged in the cavity, and spraying or applying a hydrogen generator or a hydrogen storage body into the cavity.

According to the above-mentioned invention, the catalyst for the dehydrogenation reaction or the hydrogenation reaction is arranged in the cavity of the reaction member, and the hydrogen generator or the hydrogen storage body is sprayed into the cavity. The dehydrogenation reaction or the hydrogenation reaction is caused by. Therefore, the hydrogen generator or the like sprayed into the narrow cavity is surely brought into contact with the catalyst to cause the dehydrogenation reaction or the hydrogenation reaction. Therefore, the member provided with the catalyst can have a simple structure, and the reaction efficiency is high.

Another aspect of the present invention is characterized in that the hydrogen generating / storing apparatus described above is provided with a lotus root-shaped cylindrical member having a plurality of cavities and serving as the reaction member. Therefore, if the hydrogen generator or the hydrogen storage is sprayed on the end surface of the cylindrical member, the catalysts arranged in the plurality of cavities come into contact with each other to cause a dehydrogenation reaction or a hydrogen addition reaction. For this reason, the member provided with the catalyst can have a simple structure in which spraying or the like can be easily performed, and the reaction efficiency is high.

Further, another invention is characterized in that, in the above-mentioned hydrogen generating / storing apparatus, the reaction member is constituted by bundling a plurality of tubular members each having at least one cavity. Therefore, it becomes possible to easily process the reaction member including the catalyst for causing the dehydrogenation reaction or the hydrogen addition reaction.

In another aspect of the present invention, in the above hydrogen generating / storing device, a heating device for heating the catalyst to a predetermined temperature for causing a dehydrogenation reaction or a hydrogenation reaction is arranged outside the reaction member. It is characterized by having done. Therefore, when the catalyst heated by the heating device to a predetermined temperature comes into contact with the hydrogen generating body or the hydrogen storing body, the hydrogen reaction is surely caused.

In another aspect of the present invention, in the hydrogen generating / storing apparatus described above, heating is performed by heating the catalyst to a predetermined temperature in each gap between the plurality of cylindrical members in order to cause a dehydrogenation reaction or a hydrogen addition reaction. The feature is that the device is arranged. In this way, when the heating device is arranged at a position close to the catalyst, that is, in each gap of the plurality of cylindrical members in which the catalyst is arranged, the temperature control of the catalyst in the cavity becomes easier, and further An efficient dehydrogenation reaction or hydrogen addition reaction can occur.

Another aspect of the present invention is a hydrogen generating / storing device as described above, wherein a catalyst is provided outside the reaction member and in each of the gaps between the plurality of tubular members so as to cause a dehydrogenation reaction or a hydrogen addition reaction. It is characterized by arranging a heating device for heating up to the temperature. In this way, by disposing the heating device in the outer side of the reaction member and in the respective gaps of the tubular member, heating of the catalyst becomes more sufficient.

Another aspect of the present invention is, in the above hydrogen generating / storing apparatus, a heating device for heating a catalyst to a predetermined temperature on the outer periphery of each tubular member to cause a dehydrogenation reaction or a hydrogen addition reaction. The feature is that they are arranged so as to be wrapped around. In this way, if each tubular member provided with the catalyst in the inner cavity is heated independently, the temperature control of the catalyst in each tubular member can be individually performed. Therefore, in each tubular member, the catalyst and the hydrogen generator or hydrogen storage can be reacted more efficiently.

Another aspect of the present invention is the above-described hydrogen generating / storing device, wherein a heating device for heating the catalyst to a predetermined temperature on the inner circumference of each tubular member to cause a dehydrogenation reaction or a hydrogen addition reaction. Is arranged to heat the catalyst from the outside and the inside of each tubular member. Therefore, it is possible to more sufficiently heat the catalyst arranged in the cavity inside each tubular member.

Another aspect of the present invention is characterized in that, in the hydrogen generating / storing apparatus described above, the cavity is meandered from one end side to the other end side. In this way, if the cavity with the catalyst is configured to meander rather than linearly, the hydrogen generator or hydrogen storage atomized in the cavity will pass through the cavity without touching the catalyst in the cavity. Very unlikely. As a result, the hydrogen generating body or the hydrogen storing body surely comes into contact with the catalyst in the cavity to cause a dehydrogenation reaction or a hydrogen addition reaction.

A hydrogen generating / storing device of another invention is
A hydrogen generator that releases hydrogen and changes to an aromatic compound,
Hydrogen generation or storage that utilizes the dehydrogenation reaction or hydrogen addition reaction between a hydrogen storage that is made of an aromatic compound that reacts with hydrogen and stores that hydrogen.
A storage device, a reaction member in which a catalyst for performing a dehydrogenation reaction or a hydrogen addition reaction of a hydrogen generator or a hydrogen storage member is arranged in a cavity, and a reaction container including the reaction member therein, Pre-reaction substance tank for storing hydrogen generator or hydrogen storage body before hydrogen reaction, and reaction substance supply section for sucking up or spraying hydrogen generation body or hydrogen storage body from this pre-reaction tank to the reaction container, for reaction It has a cooler for cooling and liquefying the substance after the reaction of the dehydrogenation reaction or the hydrogenation reaction by the reaction member in the container, and a post-reaction substance recovery tank for recovering the liquefied substance after the reaction. It has a feature.

In the above-mentioned invention, the dehydrogenation reaction or the hydrogen is produced by spraying the hydrogen generator or the hydrogen storage body on the reaction member having the catalyst for the dehydrogenation reaction or the hydrogenation reaction arranged in the cavity. It is designed to generate an addition reaction. Therefore, the hydrogen generator or the like sprayed in the narrow cavity surely comes into contact with the catalyst and the dehydrogenation reaction or the hydrogenation reaction surely occurs. A hydrogen generating / storing device capable of reliably reacting a catalyst with a hydrogen generating body or a hydrogen storing body by utilizing a catalyst reaction member having such a characteristic, that is, a catalyst reaction member having a cavity provided with the catalyst. Can be

Another aspect of the present invention is that, in each of the above hydrogen generating / storing devices, an aromatic compound is added to benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenathrene, and alkyl-substituted products thereof. It is characterized in that any one of the above or a plurality of any one of them is mixed.

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

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of a hydrogen generating / storing device according to the present invention will be described below with reference to the drawings.

FIG. 1 is a diagram for explaining a mechanism common to each of the embodiments described below. In particular,
It is a figure which shows the principle which stores or supplies hydrogen using the hydrogenation reaction of an aromatic compound, and the dehydrogenation reaction of the compound (henceforth a chemical hydride) produced | generated by the hydrogenation reaction of the aromatic compound.

The aromatic compound 1 such as benzene undergoes a hydrogenation reaction with hydrogen 2 produced by electrolysis of water to become a chemical hydride 3 such as cyclohexane. Specifically, hydrogen 2 is added to the carbon-carbon double bond of the aromatic compound 1. That is, hydrogen 2 is chemical hydride 3
Will be stored in the form of.

Further, the chemical hydride 3 becomes an aromatic compound 1 and hydrogen 2 by the dehydrogenation reaction. The hydrogen 2 thus generated is supplied to the fuel cell 5 together with the oxygen 4. This fuel cell 5 produces electricity by the reverse principle of electrolysis of water.

As described above, the aromatic compound 1 functions as a hydrogen storage body capable of storing hydrogen 2, and the chemical hydride 3 functions as a hydrogen generator generating hydrogen 2. Therefore, it is possible to form a hydrogen generation / storage system using the cycle of the aromatic compound 1 and the chemical hydride 3.

Next, an example of the hydrogen generation / storage system using the principle shown in FIG. 1 will be described with reference to FIG. In the following, the raw materials such as chemical hydride will not be numbered. Further, the hydrogen generation / storage device 14 which is a part of the hydrogen generation / storage system shown in FIG. 2 is the device of the first embodiment of the present invention.

FIG. 2 is a diagram schematically showing a hydrogen storage / supply system, which is an example of energy self-sustaining home power generation for home use. The hydrogen generation / storage device of the present invention functions as a part of this system.

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

The hydrogen generating / storing device 14 generates hydrogen by utilizing the dehydrogenation reaction of chemical hydride represented by cyclohexane, which is a hydrogen generating substance which releases hydrogen and changes to an aromatic compound, and generates this hydrogen. It can be sent to the outside of the hydrogen generation / storage device 14. Further, the hydrogen generation / storage device 14 is capable of causing an aromatic compound represented by benzene to react with hydrogen and storing hydrogen in the hydrogen generation / storage device 14.

The hydrogen generating / storing device 14 has a catalyst 143 (see FIG. 3) for dehydrogenating or hydrogenating a chemical hydride which becomes a hydrogen generator or an aromatic compound which becomes a hydrogen store in a cavity 141a. It has a reaction container 142 having therein a reaction member 141 to be arranged. In addition, the hydrogen generation / storing device 14 includes a reaction material supply unit 16 for supplying a hydrogen generator or a hydrogen storage material into the reaction container 142, and a material after reacting by touching a catalyst from the reaction container 142. The post-reaction substance recovery unit 17 for recovery is provided.

The reaction container 142 is a container having a space hermetically sealed from the outside. One side of a charging pipe 166 forming a part of the reactant supply unit 16 is inserted into the reaction container 142. This input pipe 166
Is a delivery pipe for supplying the hydrogen generating body or the hydrogen storage body from the reactant supply unit 16 to the reaction container 142. An injection nozzle 164 is provided in a portion of the charging pipe 166 that protrudes toward the inside of the reaction container 142.

Further, the reaction container 142 has a hydrogen inlet (not shown) for introducing hydrogen when hydrogenating an aromatic compound such as benzene with hydrogen.
A hydrogen supply pipe 144 connected to the electrolyzer 13 is connected to the hydrogen inlet. This hydrogen supply pipe 14
4 is a valve 1 for preventing hydrogen from entering the reaction container 142 from the electrolyzer 13 side when it is not necessary to input hydrogen.
45 are provided.

Further, the reaction container 142 is connected to a substance discharge pipe 146 connected to a cooler 171 which constitutes a part of the post-reaction substance recovery section 17. The substance discharge pipe 146 stores the hydrogen generator or the hydrogen store and hydrogen generated by the dehydrogenation reaction or the hydrogenation reaction occurring in the reaction member 141 in the reaction container 142, and the reaction container 1
It is for sending from 42 to the cooler 171.
The cooler 171 has a pipe 171a for sending a substance liquefied after being cooled by the cooler 171 to a post-reaction substance recovery tank 172, and hydrogen separated from a hydrogen storage body by a dehydrogenation reaction in a fuel cell. Pipe 17 for feeding to 15
1b is connected. In the tube 171b, the fuel cell 15
A valve 175 is provided to close the delivery path from the cooler 171 to the fuel cell 15 when hydrogen is not supplied to the fuel cell 15.

In the reaction container 142, the reaction member 14
1 is arranged. That is, immediately below the injection nozzle 164 inside the reaction container 142, the reaction member 141 made of a metal material having high heat conduction efficiency such as aluminum or copper.
Are arranged. As shown in FIG. 3, the reaction member 14
Reference numeral 1 is a columnar member having a lotus-like appearance and having a plurality of cavities 141a. When the hydrogen generating body or the hydrogen storage body is sprayed from the injection nozzle 164, the sprayed hydrogen generating body or the hydrogen storage body penetrates into the cavity 141a through the inlet of the cavity 141a of the reaction member 141. In this embodiment, the hydrogen generating body or the hydrogen storage body is sprayed from the injection nozzle 164, but it may be sprayed instead of spraying.

In the cavity 141a, a catalyst 143 for dehydrogenation reaction or hydrogen addition reaction of the hydrogen generator or hydrogen storage atomized by the injection nozzle 164 is arranged. As the catalyst 143, an active carbon material on which a platinum catalyst is supported is used. The hydrogen generator or hydrogen store causes a dehydrogenation reaction or a hydrogen addition reaction by contacting the surface of the catalyst 143 in a liquid film state.

The catalyst 143 is set to a predetermined constant temperature suitable for the dehydrogenation reaction or the hydrogenation reaction by being heated by a heating device (not shown). Normally, this temperature is 250 ° C to 400 ° C. When the sprayed hydrogen generator or hydrogen storage comes into contact with the heated catalyst 143, a dehydrogenation reaction or a hydrogen addition reaction occurs. The above-mentioned cylindrical reaction member 141 is formed by bundling a plurality of cylindrical members 141b having a cavity 141a shown in the enlarged view of FIG.

In this embodiment, the reaction member 141 is configured as described above, but the tubular members 141b need not be bundled. For example, the cavity 141a may be directly provided in the cylindrical reaction member 141.
Further, in the present embodiment, each tubular member 141b has one cavity 141a, but it may have two or more cavities.

A method of heating the above-mentioned catalyst 143,
That is, the arrangement of the heating device and the reaction member 141 accompanying it.
There are several possible configurations. Each of these examples will be described below, but the method for heating the catalyst, the arrangement of the heating device, and the configuration of the reaction member associated therewith in the present invention are not limited to the following examples.

In the first example, a flat plate-shaped heater serving as a heating device is arranged on the outer periphery of a cylindrical reaction member 141.
Thereby, from the outer peripheral side of the cylindrical reaction member 141,
The heat is gradually transferred to the inside of the reaction member 141, and the catalyst 143 arranged in the cavity 141a of the reaction member 141.
Is heated. The heater is equipped with a temperature control device to control the temperature of the catalyst 143. When the heating method of the first example is adopted, it is not necessary for the reaction member 141 to have a configuration in which a plurality of tubular members 141b are bundled as in the present embodiment, and a plurality of reaction members 141 can be used. Alternatively, the cavity 141b may be directly provided.

In the second example, a rod-shaped heater serving as a heating device is arranged in the gap between the tubular members 141b constituting the reaction member 141 described above. More specifically, a plurality of cylindrical members 141b are arranged in a predetermined shape, rod-shaped heaters are arranged in gaps formed at this time, and insert molding is performed in this state.
1 and a plurality of rod-shaped heaters are integrated to form a reaction member 14
It becomes 1. With such a configuration, the reaction member 141
A heater is arranged inside of, and in the immediate vicinity of each cylindrical member 141b provided with the catalyst 143 on the inner circumference,
The heating efficiency is improved. Also, the temperature control of the catalyst becomes easy.

In the third example, a flat plate-shaped heater serving as a heating device is arranged on the outer periphery of the cylindrical reaction member 141, and a heater is also arranged inside the cylindrical reaction member 141. The position of the heater arranged inside is set in each cavity 1.
It may be inside 41a or may be a gap formed between the tubular members 141b as in the second example described above. With such a configuration, the entire reaction member 141 is uniformly heated, and the catalysts 143 arranged in the respective cavities 141a are uniformly heated. Therefore, the catalyst 143 can be surely heated to a predetermined temperature without unevenness, and the reaction between the catalyst 143 and the hydrogen generator or the hydrogen storage can be surely caused.

Finally, the fourth example will be described. The fourth example is each tubular member 1 that constitutes the above-mentioned reaction member 141.
A heater serving as a heating device is wound around the outer circumference of 41b, and a heater is also arranged on the inner circumference of each tubular member 141b. As a result, the catalyst 143 arranged in each tubular member 141b is heated from both the outer periphery and the inner periphery of each tubular member 141b. Therefore, the catalyst 143 can be surely heated to a predetermined temperature without unevenness, and the catalyst 143 can be heated.
It is possible to reliably cause a reaction between the hydrogen generator and the hydrogen generator.

The reactant supply unit 16 for sending the hydrogen generating body or the hydrogen storage body into the above-mentioned reaction container 142 is a tank for the pre-reaction material storing the hydrogen generating body or the hydrogen storage body before the hydrogen reaction. 161 and this pre-reaction tank 1
A pump 162 for sucking up the hydrogen generator or hydrogen store from 61, a chamber 163 for pressurizing the sucked up hydrogen generator or hydrogen store, and this chamber 1
The reaction member 141 in the reaction container 142 that is connected to 63.
Of the injection nozzle 164 disposed directly above the chamber 1
Valve 16 disposed between the nozzle 63 and the injection nozzle 164.
It consists of 5.

Further, the post-reaction substance recovery unit 17 for storing the substance after the dehydrogenation reaction or the hydrogenation reaction in the reaction container 142 is vaporized after the reaction by the dehydrogenation reaction or the hydrogenation reaction. It is composed of a cooler 171 for cooling and liquefying the liquefied substance, and a recovery tank 172 for recovering the liquefied substance.

Hereinafter, an operation example when hydrogen is generated by the hydrogen generating / storing device 14 will be described.

First, the hydrogen inlet of the reaction vessel 142 is
It is closed by the valve 145 of the hydrogen supply pipe 144 connected to the hydrogen inlet. Next, the hydrogen generating element composed of chemical hydride such as cyclohexane or decalin contained in the pre-reaction substance tank 161 of the reaction substance supply unit 16 is sucked up by the pump 162 and pressurized in the chamber 163. Next, the valve 165 is opened to open the injection nozzle 1 arranged in the reaction container 142.
From 64, a hydrogen generator is sprayed into the reaction container 142. As a result, the atomized hydrogen generator penetrates into the cavity 141a of the reaction member 141 and touches the catalyst 143,
Dehydrogenation reaction occurs. The temperature of the catalyst 143 is controlled to a constant temperature between 250 ° C. and 400 ° C. as described above.

Hydrogen generators such as cyclohexane and decalin that come into contact with the heated catalyst 143 become benzene and hydrogen in the case of cyclohexane and naphthalene and hydrogen in the case of decalin. That is, the hydrogen generator becomes an aromatic compound that is a hydrogen storage body while generating hydrogen. Aromatic compounds such as benzene and naphthalene and hydrogen are sent to the cooler 171 through the substance discharge pipe 146. Here, the aromatic compound is cooled, liquefied, and stored in the recovery tank 172 through the pipe 171a. On the other hand, hydrogen is discharged from the cooler 171 and sent to the fuel cell 15 through the pipe 171b.

Next, an operation example when hydrogen is stored by the hydrogen generation / storage device 14 will be described.

First, the hydrogen storage is put in the pre-reaction substance tank 161. Next, the pipe 171b for supplying hydrogen to the fuel cell 15 connected to the cooler 171 is closed by the valve 175, while the valve 145 provided for the hydrogen supply pipe 144 connected to the hydrogen inlet is opened. The hydrogen supply pipe 144 allows the electrolysis device 13 and the reaction container 1 to be connected.
42 and the communication state. Further, the reactant supply unit 16
The pre-reaction substance tank 161 of the above-mentioned hydrogen storage body composed of an aromatic compound such as benzene or naphthalene is sucked up by the pump 162, and the chamber 163
Pressurize with. Next, by opening the valve 165, the hydrogen storage body is sprayed into the reaction container 142 from the injection nozzle 164 arranged in the reaction container 142. In addition to this, hydrogen is introduced from the hydrogen inlet of the reaction container 142. As a result, the sprayed hydrogen storage material penetrates into the cavity 141a of the reaction member 141, touches the catalyst 143, and a hydrogen addition reaction (exothermic reaction) occurs. The catalyst 143 is kept at a constant temperature between 250 ° C. and 400 ° C. as described above.

The hydrogen storage material such as benzene and naphthalene, which is applied to the catalyst 143 thus heated, becomes cyclohexane in the case of benzene and hydrogen and decalin in the case of naphthalene and hydrogen by the reaction with hydrogen. . In other words, the hydrogen storage body becomes a hydrogen generator composed of chemical hydride such as cyclohexane or decalin by the hydrogen addition reaction. This hydrogen generator is sent to the cooler 171 through the substance discharge pipe 146. Here, the chemical hydride as a hydrogen generator is cooled, liquefied, and stored in the recovery tank 172 through the pipe 171a.

Next, an energy self-sustaining home-use private power generation system using the hydrogen generation / storage system using the hydrogen generation / storage device 14 will be described.

As shown in FIG. 2, electricity generated by the solar cell 11 or the wind power generator 12 is supplied to the inverter 24.
Is converted to alternating current via. The converted electricity is used for household electric appliances 25, or when the electric appliances 25 are not used, the converted electricity is electrolyzed.
Is supplied to. In the electrolyzer 13, hydrogen (H2) and oxygen (O2) are generated by electrolysis of water. The generated hydrogen is stored in the hydrogen generation / storage device 1 via the hydrogen supply pipe 144.
4 is sent to the reaction container 142 side.

It should be noted that hydrogen is generated by utilizing the hydrogen addition reaction.
When hydrogen is stored in the storage device 14, the valve 14 is used.
5 is opened to introduce hydrogen into the reaction container 142 through the inlet, and the valve 175 of the pipe 171b connected to the cooler 171 is closed to close the hydrogen outlet. On the other hand, when hydrogen is generated in the hydrogen generation / storage device 14 using the dehydrogenation reaction, the above-mentioned inlet-side valve 145 for supplying hydrogen is closed, and the inside of the reaction container 142 is closed. The pipe 171 connected to the cooler 171 was not charged with hydrogen.
The valve 175 of b is opened. As a result, the hydrogen generation / storage device 14 and the fuel cell 15 are brought into communication with each other.

Even when the electricity produced by the solar cell 11 or the wind power generator 12 is excessive, that is, when the electricity generated is more than the electricity used by the household electric appliance 25, the extra electricity is generated. It is sent to the electrolysis device 13. Then, the hydrogen generated in the electrolysis device 13 is sent to the reaction container 142 of the hydrogen generation / storage device 14. In addition,
Also in this case, when hydrogen is stored, the valve 145 is opened and the hydrogen is generated and stored in the reaction container 14 of the hydrogen generating / storing device 14.
2, but when performing dehydrogenation reaction, valve 1
Since 45 is closed, hydrogen is not introduced into the reaction container 142.

When hydrogen is sent from the electrolyzer 13 to the hydrogen generating / storing device 14 and hydrogen is stored in the hydrogen generating / storing device 14 by a hydrogen addition reaction, an aromatic compound represented by benzene sucked from the reactant supply unit 16 A hydrogen storage made of a compound is sprayed into the reaction container 142. On the other hand, hydrogen is introduced from the hydrogen inlet of the reaction container 142.

Then, an exothermic reaction starts, hydrogen is added to the hydrogen storage body, and the hydrogen storage body is changed to a hydrogen generation body composed of chemical hydride represented by cyclohexane. The hydrogen generator passes through the cooler 171 and is liquefied to recover the recovery tank 1
Stored at 72. That is, in the hydrogen storage body, hydrogen is added to cause a hydrogen addition reaction to become a hydrogen generation body, which is stored in the recovery tank 172.

Further, the solar cell 11 or the wind power generator 12
In the case where the electric power generated by the electric equipment 25 cannot cover the electric power of the electric device 25, the hydrogen generator stored in the recovery tank 172 by the hydrogen addition reaction is transferred to the pre-reaction substance tank 161 in advance. . Then, the hydrogen generator stored in the pre-reaction substance tank 161 is sucked and pressurized as described above and supplied to the reaction container 142.
As a result, a dehydrogenation reaction occurs in the reaction vessel,
The hydrogen produced by this dehydrogenation reaction is the fuel cell 1
5 is supplied. In addition, the supply of the hydrogen generator and the hydrogen storage body to the pre-reaction substance tank 161 is performed by the recovery tank 161.
It is preferable that after they have been stored, they are sorted and stored in a storage tank (not shown) and automatically supplied to the pre-reaction substance tank 161 when needed.

That is, when hydrogen is generated by the hydrogen generation / storage device 14, the hydrogen supply pipe 144 connected to the hydrogen inlet is closed by the valve 145. Then, in this state, the hydrogen generating body is sprayed onto the reaction container 142.

Then, the hydrogen generating body touches the catalyst 143 set to a predetermined temperature by the heating device, and the catalyst 1
The surface of 43 becomes a liquid film state. That is, the dehydrogenation reaction is likely to occur. Therefore, the hydrogen generator changes to hydrogen and a hydrogen storage body composed of an aromatic compound represented by benzene. The hydrogen storage body is sent to the cooler 171 through the substance discharge pipe 146. Then, the hydrogen storage body is cooled by the cooler 171, liquefied, and stored in the recovery tank 172.

In the fuel cell 15, the hydrogen generating / storing device 1
Electricity is produced by the reaction between hydrogen sent from No. 4 and oxygen supplied from the air. The electricity thus generated is used not only for household electric appliances 25 but also for powering an electric vehicle 26. In this way, the hydrogen generation / storage device 14 stores energy in the form of a hydrogen generator such as cyclohexane, or produces energy from the hydrogen generator by a dehydrogenation reaction, according to the demand for electric power at home. .

In the hydrogen generation / storage device 14 which is a part of the hydrogen storage / supply system of FIG. 2, the hydrogen storage body is not benzene or naphthalene but toluene, xylene, mesitylene, methylnaphthalene, anthracene, biphenyl, Any one or a plurality of phenalenes and their alkyl-substituted compounds may be used in combination.

Next, a control unit for performing various controls of the hydrogen generation / storage device 14 of the above-described embodiment will be described.

As shown in FIG. 4, the control unit 60 mainly
A control panel 61, a CRT monitor 62, an operation unit 63 such as a keyboard and a mouse, a personal computer body 64, a P
The CI expansion unit 65 is provided to perform various controls.

The control panel 61 has a power switch 70 for a 100V power source, a power switch 71 for a 200V power source for a pump, a flow meter 72 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 73 for measuring, a temperature controller 74 for controlling the temperature in the reaction container 142, an alarm section 81 by a buzzer, and an operation switch 8
2 and a status indicator lamp 83 for displaying the operating status.

The control unit 60 is turned on by the temperature of the catalyst 143, the temperature in the reaction vessel 142, the temperature of the surface of the heater serving as a heating device, the temperature of each raw material, each temperature of the inlet and outlet of the cooler 171. Controls the temperature of hydrogen. Further, the control unit 60 measures the flow rate of generated hydrogen and the flow rate of hydrogen introduced into the device.

Further, the control unit 60 detects the hydrogen pressure after cooling and the pressure of hydrogen introduced into the apparatus. Further, the control unit 60 is configured to be able to set the upper and lower limits of the liquid level of the pre-reaction substance tank 161, and also has a mechanism for notifying when there is no liquid level between the upper and lower limits.

The personal computer main body 64 is a part for setting and controlling the temperature, pressure and the like in various components such as the reaction container 142, and at the same time, can analyze hydrogen with the analysis software of the installed gas chromatography. .

Next, the result of grasping the operating conditions by the lab scale device before the operation of the hydrogen generation / storage device 14 will be explained.

FIG. 5 is a graph showing the results of examining the reaction temperature dependence of the dehydrogenation reaction of cyclohexane. The horizontal axis is the reaction temperature, and the vertical axis is the hydrogen generation rate per minute. As shown in FIG. 5, when the reaction temperature is 523 K (= 250 ° C.),
It can be seen that the amount of hydrogen generated is the largest. Moreover, when the reaction temperature is too high, the amount of hydrogen generated decreases. It is considered that this is because the volatile content of the raw material increases and it becomes difficult to form a liquid film of the raw material on the surface of the catalyst 143.

FIG. 6 is a graph showing the results of examining the group mass dependence of the dehydrogenation reaction of cyclohexane. The horizontal axis is the basic mass, and the vertical axis is the hydrogen generation amount per minute. Here, the base mass is the supply amount of cyclohexane. Catalyst 1
For 43, 0.5 g of platinum was used. The reaction temperature is 5
23K.

As shown in FIG. 6, it is understood that the hydrogen generation amount is the largest when the cyclohexane supply amount is 1.7 ml. It is considered that the increase in the amount of cyclohexane supplied decreases the amount of hydrogen generation because the catalyst 143 was applied with more cyclohexane than necessary and an appropriate liquid film could not be formed on the catalyst surface.

The above is the result of the experiment conducted for investigating the dehydrogenation reaction condition of cyclohexane, but chemical hydride such as decalin can be used in addition to cyclohexane. Next, the lab-scale experimental results using decalin will be described.

FIG. 7 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. Even when decalin is used, only hydrogen can be generated without breaking the carbon skeleton, as in the case of using cyclohexane. Therefore, decalin can be a clean energy source that can prevent global warming associated with carbon dioxide emission.

FIG. 8 is a graph showing the results of examining the group mass dependence of the dehydrogenation dehydrogenation reaction. The horizontal axis is the basic mass, and the vertical axis is the hydrogen generation amount per minute. Here, the base mass is the supply amount of decalin. As the catalyst 143, 0.5 g of platinum was used. The reaction temperature was 523K.

As shown in FIG. 8, it is understood that the hydrogen generation amount decreases as the supply amount of decalin increases from 1.4 to 1.75 ml. It is considered that the reason why the hydrogen generation amount decreases when the supply amount of decalin increases is that the catalyst 143 was applied with more decalin than necessary and a proper liquid film could not be formed on the catalyst surface.

FIG. 9 is a graph showing the results of comparing the amount of hydrogen generated by changing the type of chemical hydride.
In the figure, open triangles indicate the case where only decalin was used. The black diamonds show the case of using a mixed solution of decalin and methylcyclohexane, and the black squares show the case of using a mixed solution of decalin and cyclohexane.
The amount of hydrogen gas generated is shown as a cumulative value for each hour. The reaction temperature was 573K, and the amount of raw material supplied was 1.
It was set to 75 ml / min.

As a result, it was found that hydrogen gas was extremely generated when only decalin was dehydrogenated. It was also found that the hydrogen gas generation amount was the smallest in the case of a mixed liquid of decalin and methylcyclohexane. It should be noted that naphthalene produced by dehydrogenation of decalin has a high melting point (about 80 ° C.) and is difficult to use at room temperature. Therefore, it is preferable to use cyclohexane rather than decalin.

[0084]

[Table 1]

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

However, in terms of the ease of use of the raw material after releasing hydrogen, decalin which produces naphthalene is inferior to cyclohexane. This is because naphthalene becomes solid at room temperature and sublimates without liquefying at 80 ° C or higher. Further, 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., which is an easy-to-use raw material like cyclohexane having almost the same boiling point. Therefore, cyclohexane is the most suitable raw material from the viewpoint of ease of use including hydrogen release and safety.

However, raw materials other than cyclohexane can be used by improving the safety and changing the use conditions. For example, a chemical hydride that becomes xylene, mesitylene, methylnaphthalene, anthracene, biphenyl, or phenathrene after releasing hydrogen can be used.

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

The present invention is not limited to the above embodiment. For example, in the above-described embodiment, the system and the apparatus including both the hydrogenation reaction and the dehydrogenation reaction have been described, but the apparatus and the system that perform only one of the reactions and the apparatus that performs the other reaction are described. The system may be configured as another system. In the case of an apparatus that performs either one, it is not necessary to provide an unnecessary one of the hydrogen inlet and the hydrogen outlet that is closed by the valve as described above. That is, when the device is used only for the operation of generating hydrogen, it is configured so that the discharge port is provided and the input port is not provided, and when the device is used only for the operation of storing hydrogen, the input port is provided. The discharge port may not be provided.

Further, in the above-described embodiment, hydrogen generation /
Although the reaction member 141 arranged in the reaction container 142 of the storage device 14 is formed of a cylindrical member, it may have another shape such as a prismatic shape. Further, in the above-described embodiment, the cavity 141a of the reaction member 141 is a straight insertion hole, but it may be a cavity that meanders in a zigzag shape or the like. The cavity 141a may be a bottomed hole instead of the insertion hole. Furthermore, the cavity 141 of the reaction member 141
Instead of a plurality of a, only one may be provided.

Further, in the above-mentioned embodiment, an example in which hydrogen is supplied to the fuel cell has been described, but a power generation device other than the fuel cell may be adopted. For example, hydrogen may be burned to boil water, and a turbine may be rotated to generate electricity by rotating a generator. Further, this hydrogen storage / supply system may be used in combination with an electric power supply system such as a conventional thermal power plant or nuclear power plant.

[0092]

EFFECTS OF THE INVENTION According to the present invention, since the catalyst is arranged in the narrow cylindrical hole, the hydrogen generating body or the hydrogen storing body is surely brought into contact with the catalyst. The reaction efficiency of the reaction can be increased.

[Brief description of drawings]

FIG. 1 is a diagram showing a principle underlying a hydrogen storage / supply system using a hydrogen generation / storage device of the present invention, which is produced by a hydrogenation reaction of an aromatic compound and a hydrogenation reaction of the aromatic compound. It is a figure which shows the flow which stores or produces | generates hydrogen using the dehydrogenation reaction of a compound (chemical hydride).

FIG. 2 is a diagram showing a hydrogen storage / supply system using the hydrogen generation / storage device according to the embodiment of the present invention, and is a diagram showing a hydrogen storage / supply system using energy self-sustaining home-use private power generation as an example. is there.

FIG. 3 is a perspective view of a reaction member of the hydrogen generation / storage device of FIG. 2 and an enlarged perspective view of a tubular member constituting the reaction member.

4 is a diagram showing a control unit that performs various controls of the hydrogen generation / supply device of FIG.

FIG. 5 is a graph showing the results of examining the reaction temperature dependence of the dehydrogenation reaction of cyclohexane used in the present invention.

FIG. 6 is a graph showing the results of examining the group mass dependence of the dehydrogenation reaction of cyclohexane used in the present invention.

FIG. 7 is a diagram showing a reaction formula in which naphthalene and hydrogen are produced by the dehydrogenation reaction of decalin that can be used in the present invention, and conversely, decalin is produced by the hydrogenation reaction of naphthalene.

FIG. 8 is a graph showing the results of examining the group mass dependence of the dehydrogenation reaction of decalin usable in the present invention.

FIG. 9 is a graph showing the results of comparing the amount of hydrogen generated by changing the type of chemical hydride usable in the present invention.

[Explanation of symbols]

14 Hydrogen generation / storage device 16 Reactant supply unit 17 Post-reaction material recovery section 141 Reaction Member (Cylindrical Member) 141a cavity 141b tubular member 142 Reaction container 143 catalyst 161 Pre-reaction material tank 162 pump (a part of reactant supply part) 163 chamber (a part of reactant supply part) 164 injection nozzle (a part of reactant supply part) 165 valve 171 cooler 172 Post-reaction material recovery tank

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C22C 5/04 C22C 5/04 F17C 11/00 F17C 11/00 C H01M 8/04 H01M 8/04 J 8 / 06 8/06 RZ F term (reference) 3E072 EA10 4G040 AA42 4H006 AA04 AA05 AC11 AC12 BA60 BA61 5H027 AA02 BA01 BA13

Claims (11)

[Claims] 1. A dehydrogenation reaction or hydrogen between a hydrogen generator that releases hydrogen to be converted into an aromatic compound and a hydrogen storage material that reacts with the hydrogen to store the hydrogen and is composed of the aromatic compound. A hydrogen generating / storing device for generating or storing hydrogen by using an addition reaction, wherein a catalyst for causing the dehydrogenation reaction or the hydrogen addition reaction of the hydrogen generator or the hydrogen storage body is arranged in a cavity. The hydrogen generating / storing device, wherein the dehydrogenation reaction or the hydrogen addition reaction is carried out by providing the reaction member and spraying or applying the hydrogen generator or the hydrogen storage into the cavity. 2. The hydrogen generating / storing device according to claim 1, further comprising a lotus root-shaped cylindrical member having a plurality of said cavities and serving as said reaction member. 3. The hydrogen generating / storing device according to claim 1, wherein the reaction member is configured by bundling a plurality of tubular members each having at least one cavity. 4. A heating device for heating the catalyst to a predetermined temperature in order to cause the dehydrogenation reaction or the hydrogenation reaction is arranged outside the reaction member. The hydrogen generation / storage device according to 2 or 3. 5. A heating device for heating the catalyst to a predetermined temperature for causing the dehydrogenation reaction or the hydrogenation reaction is arranged in each gap of the plurality of cylindrical members. Item 3. The hydrogen generation / storage device according to item 3. 6. A heating device for heating the catalyst to a predetermined temperature in order to cause the dehydrogenation reaction or the hydrogenation reaction to be provided outside the reaction member and in each gap between the plurality of cylindrical members, respectively. The hydrogen generating / storing device according to claim 3, wherein the hydrogen generating / storing device is arranged. 7. A heating device for heating the catalyst to a predetermined temperature for causing the dehydrogenation reaction or the hydrogenation reaction is wound around the outer periphery of each of the cylindrical members. The hydrogen generating / storing device according to claim 3. 8. A heating device that heats the catalyst to a predetermined temperature in order to cause the dehydrogenation reaction or the hydrogenation reaction is arranged on the inner circumference of each of the tubular members. 8. It is configured to heat the catalyst from the outside and the inside.
The described hydrogen generation / storage device. 9. The hydrogen generating / storing device according to claim 1, wherein the cavity is configured to meander from one end side to the other end side. 10. A dehydrogenation reaction or hydrogen between a hydrogen generator which releases hydrogen to be converted into an aromatic compound and a hydrogen store which is made of the aromatic compound and reacts with the hydrogen to store the hydrogen. A hydrogen generating / storing device for generating or storing hydrogen by using an addition reaction, wherein a catalyst for performing the dehydrogenation reaction or the hydrogen addition reaction of the hydrogen generator or the hydrogen store is arranged in a cavity. Member for reaction, a reaction container equipped with the reaction member therein, a tank for a pre-reaction substance that stores the hydrogen generator or the hydrogen storage body before the hydrogen reaction, and the hydrogen from the pre-reaction tank The dehydrogenation reaction or the hydrogenation reaction is performed by the reaction material supply unit that sucks up the generator or the hydrogen storage body and sprays or applies it to the reaction container, and the reaction member in the reaction container. Hydrogen generation and storage device, characterized in that it comprises and material after the reaction was cooled and cooler for liquefying and the on reacted material recovery tank for collecting the liquefied material after the reaction. 11. A mixture of any one or more of the above aromatic compounds selected from benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenthrene and alkyl-substituted compounds thereof. The hydrogen generating / storing device according to any one of claims 1 to 10, wherein: