JP2003035400A - Hydrogen generating and storing equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the reaction coefficient of hydrogenation or dehydrogenation used for the storage or supply of hydrogen. SOLUTION: In the hydrogenation and dehydrogenation equipment for generating or storing hydrogen by using hydrogenation or dehydrogenation between hydrogen generating body releasing hydrogen and changing into aromatic compound and hydrogen storing body consisting of aromatic compound reacting with hydrogen and storing the hydrogen, a catalyst part 21 provided with a catalyst for dehydrogenation or hydrogenation of the hydrogen generating body or the hydrogen storing body and a cooling part 18 for cooling and liquefying the vaporized hydrogen generating body or the hydrogen storing body are alternatively arranged.

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. It is characterized in that a catalyst portion provided with a catalyst for reaction and a cooling portion for cooling and liquefying the vaporized hydrogen generating body or hydrogen storage body are alternately arranged.

According to the above-mentioned invention, the catalyst section for carrying out the dehydrogenation reaction or the hydrogenation reaction and the cooling section for cooling and liquefying the hydrogen generator or the hydrogen storage body are arranged alternately. Therefore, the substance that has not completely reacted in the catalyst part is liquefied in the adjacent cooling part and returns to the catalyst part, so that it can be reacted again in the catalyst part. Therefore, the reaction efficiency of the vaporized substance is high.

Another aspect of the present invention is dehydrogenation between a hydrogen generator that releases hydrogen to be converted to an aromatic compound and a hydrogen storage body made of an aromatic compound that reacts with hydrogen to store the hydrogen. A hydrogen generating / storing device for generating or storing hydrogen by using a reaction or a hydrogen addition reaction, the hydrogen storing body after storing the hydrogen generating body or the hydrogen storing body and dehydrogenating the hydrogen generating body. Alternatively, a storage unit for collecting and storing the hydrogen generator after the hydrogen addition reaction to the hydrogen storage unit and a main unit for heating the hydrogen generator or the hydrogen storage unit in the storage unit to vaporize the hydrogen generation unit or the hydrogen storage unit. The heater, the cooling unit that liquefies and drops by cooling the vaporized and rising hydrogen generator or hydrogen store, and the dehydrogenation reaction of the hydrogen generator or hydrogen store that has fallen from this cooling unit. Or a catalyst part having a catalyst and a heater for a hydrogen addition reaction, an outlet for discharging hydrogen generated by the dehydrogenation reaction, and at least one of a charging port for charging hydrogen for the hydrogen addition reaction. It is characterized by that.

According to the above-mentioned invention, the hydrogen generating element or the hydrogen storage element which is heated by the main heater and vaporized is liquefied and drops in the cooling section, and the falling material is reacted with hydrogen in the catalyst section. ing. Therefore, the hydrogen generator or the hydrogen store is efficiently supplied to the catalyst section, and the reaction efficiency with hydrogen becomes good. In addition, the storage unit for storing the substance before the hydrogen reaction and the storage unit for collecting and storing the substance after the reaction can be used together, so that the entire apparatus can be made compact.

Another aspect of the present invention is dehydrogenation between a hydrogen generator which releases hydrogen to be converted into an aromatic compound and a hydrogen store which is made of an aromatic compound which reacts with hydrogen to store the hydrogen. A hydrogen generating / storing device for generating or storing hydrogen by utilizing a reaction or a hydrogen addition reaction, in which a hydrogen generator or a hydrogen store is dehydrogenated or hydrogen-added on the upper surface of a corrugated metal material having irregularities. In addition to providing a catalyst for the reaction, a passage portion for passing the vaporized hydrogen generating body or hydrogen storage body is provided in one or both of a part of the metal material or a concave portion or a convex portion between the metal materials.

Therefore, the hydrogen generator or the hydrogen store efficiently reacts with hydrogen on the upper surface of the metal material. in addition,
The generated hydrogen and the like can efficiently move through the passage.

Further, in another invention, in each of the above hydrogen generating / storing devices, the catalyst part and the cooling part are respectively formed in layers, and the catalyst part is formed in a layered structure and the cooling part is formed in a layered cooling layer. Is characterized in that each of them is provided with a passage portion for passing the vaporized substance, and that the passage portion of the catalyst layer and the passage portion of the cooling layer are formed at positions where they do not overlap each other in the vertical direction. for that reason,
The vaporized substance that rises through the catalyst layer hits the cooling layer, is cooled, and falls. Therefore, it returns to the catalyst layer again and reacts with hydrogen in the catalyst layer. As a result, a device having a high reaction efficiency with hydrogen can be obtained.

In another aspect of the present invention, in the above hydrogen generator / storage device, the catalyst layer and the cooling layer are arranged in a tilted state, and the liquefied substance is not accumulated in each layer by utilizing this tilting. It is characterized by being configured to fall. Therefore, liquid is not accumulated in the catalyst layer and the cooling layer, and the liquid drops efficiently downward. As a result, the hydrogen generator or the hydrogen storage can be reliably reacted with hydrogen in the catalyst layer, and a device with high reaction efficiency can be obtained.

Another aspect of the present invention is characterized in that, in each of the above hydrogen generating / storing devices, a plurality of cooling layers and a plurality of catalyst layers are provided. Therefore, a substance that has been heated in the catalyst layer and vaporized and cannot be completely separated from the hydrogen by reaction is liquefied again in another cooling layer and drops into another catalyst layer, where it reacts with hydrogen. Since the cooling layer and the catalyst layer are composed of a plurality of layers in this way, a substance that has not completely reacted and is vaporized can be reacted again with hydrogen in the catalyst layer, and a device with high reaction efficiency can be provided. can do.

Further, another invention is characterized in that each of the hydrogen generating / storing devices described above has a hydrogen reaction layer having an integral structure in which the cooling portion is on the lower surface side and the catalyst portion is on the upper surface side. Therefore, the entire device becomes compact in the vertical direction.

Another aspect of the present invention is characterized in that, in the above hydrogen generating / storing apparatus, the cooling section and the catalyst section are made to function on both sides of the Peltier element, respectively. Therefore, the vertical direction of the device can be made compact by utilizing the characteristics of the Peltier device.

Another aspect of the present invention is characterized in that, in the hydrogen generating / storing apparatus described above, an insulating layer, a heater, and a heat conducting material are arranged in this order from the cooling section side between the cooling section and the catalyst section. There is. If the cooling unit and the catalyst unit are integrally formed on the front and back without using the Peltier element as described above, a compact and low-cost device can be obtained.

Another aspect of the present invention is the hydrogen generating / storing apparatus described above, wherein the aromatic compound is benzene, toluene,
It is characterized in that any one of xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthrene, and alkyl-substituted compounds thereof or a mixture of a plurality 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 prismatic hydrogen generating / storing device 14 is
A tank 16 serving as a storage unit for storing a hydrogen generating body or a hydrogen storing body, a main heater 17 for heating and vaporizing the hydrogen generating body or the hydrogen storing body in the tank 16, a hydrogen generating body vaporized and rising, or A cooling layer 18 for cooling and liquefying and dropping the hydrogen storage body, and this cooling layer 18
It has a catalyst layer 21 provided with a catalyst 21a and a heater 21b for performing a dehydrogenation reaction or a hydrogen addition reaction of a hydrogen generator or a hydrogen storage body that has fallen from the.

The tank 16 is a container for alternately storing benzene, which is a hydrogen storage body, or cyclohexane, which is a hydrogen generation body, depending on the situation. The tank 16 is provided with a main heater 17 for heating each raw material. The main heater 17 is provided to heat and vaporize each raw material.

The boiling points of benzene and cyclohexane are 80.1 ° C. and 80.9 ° C., respectively. Therefore, the main heater 17 is controlled to have a temperature equal to or higher than each of the above boiling points so that each raw material can boil and vaporize.

The cooling layer 18 is composed of a water-cooled circulation type cooling device. That is, the hydrogen generator or the hydrogen store is cooled by circulating the refrigerant in the thin pipe. A mixed solution of 30% by weight of ethylene glycol and 70% by weight of water is used as the refrigerant. The cooling layer 18 has an elongated through hole 18 which serves as a passage portion through which a gas or a liquid can pass vertically.
a is formed at a predetermined position. Therefore, the main heater 1
Gaseous hydrogen generators or hydrogen stores vaporized in 7 and not liquefied in the cooling layer 18, hydrogen in the dehydrogenation reaction or the hydrogenation reaction, and the like pass through the through holes 18a. In addition, you may make it cool with cold air instead of water.

The catalyst layer 21 has a catalyst 21a provided on the upper surface of a bellows-shaped material such as stainless steel, and a flat heater 21b attached on the lower surface thereof. The catalyst 21a is
A plane-shaped activated carbon material carrying a platinum catalyst is used. The catalyst layer 21 has an elongated through hole 21c serving as a passage portion through which a gas or a liquid can pass vertically.
Are formed at predetermined positions. Therefore, the main heater 17
Gaseous hydrogen generators or hydrogen storages that have been vaporized in the above and have not been liquefied in the cooling layer 18, hydrogen in the dehydrogenation reaction or hydrogen addition reaction, etc. will pass through the through holes 21c.

The through hole 21c of the catalyst layer 21 and the through hole 18a of the cooling layer 18 are preferably arranged at positions that do not overlap each other in the vertical direction. The vaporized substance is the catalyst layer 2
This is because when the liquid passes through the first through hole 21c and rises, it easily collides with the refrigerant layer 18 above it and is easily liquefied.
Further, the through holes 18a and 21c may have a circular shape instead of the elongated shape, and the periphery of the through holes 18a and 21c may be rounded up.

The hydrogen generating / storing device 14 supplies the hydrogen generating / storing device 14 with an inlet 14a for charging hydrogen into the hydrogen generating / storing device 14 and the hydrogen generated in the hydrogen generating / storing device 14 to the outside. It has a discharge port 14b for.
The discharge port 14b is provided with an activated carbon filter 14c for preventing the hydrogen generator or the hydrogen storage body from being discharged from the discharge port 14b to the outside.

That is, the activated carbon filter 14c is provided for trapping benzene or cyclohexane mixed with hydrogen and discharging only hydrogen to the outside. The activated carbon filter 14c is not shown,
It can be heated by a heater. This is because the activated carbon filter 14c is heated periodically to forcibly volatilize the trapped benzene and cyclohexane, thereby prolonging the life of the activated carbon filter 14c.

Electricity generated by the solar cell 11 or the wind power generator 12 is converted into alternating current via the inverter 24. The converted electricity is used for the household electric device 25, or when the electric device 25 is not used, the converted electricity is supplied to the electrolysis device 13. In the electrolyzer 13, hydrogen (H2) and oxygen (O2) are generated by electrolysis of water. The generated hydrogen is sent to the hydrogen generation / storage device 14. When hydrogen is stored in the hydrogen generation / storage device 14 using the hydrogen addition reaction,
A valve (not shown) is opened to supply hydrogen from the input port 14a to the hydrogen generation / storage device 14 and close the discharge port 14b. On the other hand, when hydrogen is generated in the hydrogen generation / storage device 14 by utilizing the dehydrogenation reaction, the above-mentioned valve is closed, hydrogen is not charged into the hydrogen generation / storage device 14, and the discharge port 14b is used. Can be opened.

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 hydrogen generation / storage device 14. In this case also, in the case of storing hydrogen, the valve is opened to supply hydrogen to the hydrogen generation / storage device 14, but in the case of performing the dehydrogenation reaction,
Hydrogen is generated and stored in the hydrogen storage device 14 because the valve is closed.
Is not thrown inside.

When hydrogen is sent from the electrolysis device 13 to the hydrogen generating / storing device 14 and stored in the hydrogen generating / storing device 14, the tank 1 in the hydrogen generating / storing device 14 is previously stored.
The hydrogen storage body made of an aromatic compound represented by benzene and stored in 6 is heated by the main heater 17. As a result, the hydrogen storage is vaporized and rises in the device 14. Then, the hydrogen storage body is cooled in the cooling layer 18 and liquefied, and the catalyst layer 2 disposed below the cooling layer 18 is liquefied.
It falls to 1.

Then, 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. This hydrogen generator is a liquid, and finally falls into the tank 16 and is stored in the tank 16. That is, in the hydrogen storage body, hydrogen is added to cause a hydrogen addition reaction to become a hydrogen generating body, which is stored in the tank 16. In addition, when the cooling layer 18 is flat, it may be assumed that the hydrogen generator does not drop into the tank 16 as intended and may accumulate on the surface of the cooling layer 18. When such a liquid pool occurs, the cooling layer 18 may be inclined as in the second and third embodiments (see FIGS. 3 and 4) described later.

Here, the hydrogen storage body originally stored in the tank 16 is heated by the main heater 17 to a temperature above the boiling point of 80 ° C. Therefore, all of the hydrogen storage is surely vaporized and rises, is liquefied in the cooling layer 18, and falls into the catalyst layer 21. As a result, the proportion of hydrogen storage bodies participating in the hydrogenation reaction increases. In addition, the catalyst 21a is 60 to 60% by the heater 21b.
It is heated to 120 ° C. As a result, the production rate of hydrogen generators due to the hydrogenation reaction becomes very high.

When the hydrogen storage body that has been liquefied and dropped is heated by the heater 21b of the catalyst layer 21 for hydrogen reaction, there is a portion where it vaporizes and rises again without hydrogen addition reaction. . In the present embodiment, there are three combinations of the cooling layer 18 on the upper side and the catalyst layer 21 on the lower side, that is, the catalyst layer 21, the cooling layer 18, the catalyst layer 21, and the cooling layer 18 are alternately arranged from the tank 16 side. Has been done. Therefore, even if the hydrogen storage body that has vaporized and further rises passes through the cooling layer 18 at the bottom and the second catalyst layer 21 above it, it is cooled in the second cooling layer 18 and liquefied. It is designed to fall onto the second catalyst layer 21 below the lever. Since the three-layer structure is used as described above, the hydrogen storage body is surely liquefied and falls, and the rate of becoming a hydrogen generation body in the catalyst layer 21 is increased.

Further, the solar cell 11 or the wind power generator 12
When the electricity generated by the above cannot supply the electric power of the electric device 25, the hydrogen generator stored in the tank 16 is heated to cause a dehydrogenation reaction. As a result, hydrogen is generated by the hydrogen generation / supply device 14 and supplied to the fuel cell 15.

That is, when hydrogen is generated in the hydrogen generation / storage device 14, the inlet 14a is closed by a valve. Then, the hydrogen generator stored in advance in the tank 16 in the hydrogen generation / storage device 14 is connected to the main heater 17
Heating by. This vaporizes the hydrogen generator,
It rises in the hydrogen generation / storage device 14. Then, the hydrogen generator is cooled in the cooling layer 18 and liquefied, and the cooling layer 1
It falls to the catalyst layer 21 arranged in the lower part of 8.

Then, the hydrogen generator undergoes a dehydrogenation reaction to be converted into a hydrogen storage body composed of hydrogen and an aromatic compound represented by benzene. Hydrogen is discharged to the outside from the discharge port 14b. The hydrogen store is a liquid and eventually tank 1
6 and is stored in the tank 16. That is, the hydrogen generator becomes hydrogen and a hydrogen storage body by the dehydrogenation reaction, the hydrogen is discharged, and the hydrogen storage body is stored in the tank 16.

The hydrogen generator previously stored in the tank 16 is heated by the main heater 17 at a temperature of 80 ° C. or higher, that is, a boiling point or higher. For this reason, all of the hydrogen generating elements are surely vaporized and risen, and the cooling layer 18
It will be liquefied and fall into the catalyst layer 21. This increases the proportion of hydrogen generators involved in the dehydrogenation reaction. In addition, the catalyst 21a is 60 to 60
It is heated to 120 ° C. As a result, the production rate of hydrogen storage by the dehydrogenation reaction becomes very high.

The catalyst 21a is heated to 250 to 400 ° C. by the heater 21b. As a result, the generation rate of hydrogen due to the dehydrogenation reaction becomes extremely high. Since the dehydrogenation reaction is an endothermic reaction, a large amount of heat energy is required as compared with the above hydrogenation reaction.
In consideration of the efficiency of the dehydrogenation reaction, the catalyst 21a is
It is more preferable to heat by the heater 21b so that the temperature becomes about 50 ° C.

There is also a portion where when the hydrogen generating body which has been liquefied and dropped is heated by the heater 21b, it is vaporized again without undergoing a dehydrogenation reaction and rises. In the present embodiment, the cooling layer 18 and the catalyst layer 21 are formed as described above.
Because of the layered structure, even if the vaporized hydrogen generator further passes through the cooling layer 18 at the bottom and the second catalyst layer 21 above it, it is cooled in the second cooling layer 18. It is designed to be liquefied and fall into the second catalyst layer 21 below it. Since the three-layer structure is used as described above, the hydrogen generating body is surely liquefied and falls, and the rate of becoming the hydrogen storage body in the catalyst layer 21 is increased. The hydrogen generated by the dehydrogenation reaction is sent to the fuel cell 15 through the outlet 14b.

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 supplier such as cyclohexane or produces energy from the hydrogen supplier by a dehydrogenation reaction in accordance with 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 is not benzene but toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, Any one or a plurality of phenalenes and their alkyl-substituted compounds may be used in combination.

The structure of the hydrogen generating / storing device according to the second embodiment of the present invention will be described below with reference to FIG. The hydrogen generating / storing device described below is functionally similar to the hydrogen generating / storing device of the first embodiment described above, and should be incorporated as a part of the system shown in FIG. It is a device that can

The hydrogen generating / storing device 34 of the second embodiment of the present invention shown in FIG. 3 has a prismatic shape as a whole, and is a tank 36 serving as a hydrogen generator or a storage unit for storing the hydrogen store.
A main heater 37 for heating and vaporizing the hydrogen generating body or hydrogen storage body in the tank 36; and a cooling layer 38 for cooling, liquefying and dropping the vaporized and rising hydrogen generating body or hydrogen storage body. And a catalyst 41a and a heater 4 for performing a dehydrogenation reaction or a hydrogen addition reaction on the hydrogen generating body or hydrogen storage body that has fallen from the cooling layer 38.
It has a catalyst layer 41 with 1b. The cooling layers 38 and the catalyst layers 41 are alternately arranged in the order of the catalyst layers 41, the cooling layers 38, the catalyst layers 41, and the cooling layers 38 from the main heater 37 side upward.

In each cooling layer 38, a plurality of cooling parts 38a for cooling the hydrogen generators or hydrogen storage bodies are provided on a substantially same plane within a predetermined width by circulating cold water or cold air in a thin metal pipe. It is arranged in layers. An elongated gap 38b serving as a passage portion through which a gas or a liquid can pass is provided between the cooling portions 38a in the vertical direction. Therefore, a gaseous hydrogen generator or hydrogen storage that has been vaporized by the main heater 37 and has not been liquefied by the cooling layer 38, hydrogen in the dehydrogenation reaction or hydrogen addition reaction, and the like pass through the gap 38b. Become.

In the catalyst layer 41, a catalyst portion 41c having a flat heater 41b attached to the lower surface of the catalyst 41a is arranged in layers on a substantially same plane within a plurality of predetermined widths. A long gap 41d serving as a passage portion through which a gas or a liquid can pass vertically is provided between the catalyst portions 41c so as not to overlap the gap 38b in the vertical direction. Therefore, a gaseous hydrogen generator or hydrogen storage which is vaporized by the main heater 37 and is not liquefied by the cooling layer 38,
Hydrogen or the like during the dehydrogenation reaction or the hydrogen addition reaction will pass through the gap 41d.

Incidentally, each cooling section 38a and each catalyst section 41
a is a hydrogen generating / storing device 3 in a tilted state.
It is installed in 4. Therefore, the liquid hydrogen generator or hydrogen storage that has been liquefied in the cooling layer 38 and dropped from above does not cause liquid pools on the upper surfaces of the cooling parts 38a and the catalyst parts 41a, and smoothly flows along the slope. It is designed to fall. For this reason, the storage efficiency of the substance that drops as a hydrogen generator due to the addition of hydrogen and the storage efficiency of the hydrogen store that separates and falls from hydrogen by the dehydrogenation reaction increase.

The hydrogen generating / storing device 34 has an inlet 34a for introducing hydrogen into the device 34 and an outlet 34b for supplying hydrogen generated in the device 34 to the outside. ing. The discharge port 34b is provided with an activated carbon filter 34c for preventing the hydrogen generator or the hydrogen storage body from being discharged from the discharge port 34b to the outside.

As described above, each catalyst portion 41a which constitutes the catalyst layer 41 and each cooling portion 38 which constitutes the cooling layer 38.
By tilting a and mounting it in the apparatus, it is possible to prevent a phenomenon in which a liquid pool is generated on the upper surface of each catalyst portion 41a and each cooling portion 38a and a sufficient hydrogen reaction cannot be performed.
That is, the substance before the reaction can be surely dropped into each of the catalyst portions 41a for hydrogen reaction, and the substance after the hydrogen reaction can be smoothly dropped and stored in the tank 36 without fail.

Next, the structure of the hydrogen generating / storing device according to the third embodiment of the present invention will be described with reference to FIG.
The hydrogen generating / storing device described below is functionally the same as the hydrogen generating / storing device of the first and second embodiments described above, and is a part of the system shown in FIG. It is a device that can be incorporated as.

The hydrogen generating / storing device 54 of the third embodiment of the present invention shown in FIG. 4 includes a tank 56 which serves as a hydrogen generator or a storage unit for storing the hydrogen storage member, and a tank 56.
6, a main heater 57 for heating and vaporizing the hydrogen generator or hydrogen storage body, a cooling layer 58 for cooling, liquefying and dropping the vaporized and rising hydrogen generator or hydrogen storage body, and this cooling It has a catalyst layer 61 provided with a catalyst 61a and a heater 61b for performing a dehydrogenation reaction or a hydrogen addition reaction of a hydrogen generating body or a hydrogen storage body that has fallen from the layer 58. The cooling layer 58 and the catalyst layer 61 are formed by assembling the catalyst layer 61 and the cooling layer 5 from the main heater 57 side upward.
8, the catalyst layers 61, and the cooling layers 58 are alternately arranged in this order.

Each cooling layer 58 is formed of one large flat plate-shaped thin pipe, and the refrigerant circulates inside the thin pipe. The cooling layer 58 is attached inside the apparatus in a state of being inclined at a predetermined angle. And
Between one end of each cooling layer 58 and the inner wall of the device, there is provided a gap 58b serving as a passage portion through which gas or liquid can pass in the vertical direction. Therefore, a gaseous hydrogen generator or hydrogen storage that has been vaporized in the main heater 57 and not liquefied in the cooling layer 58, hydrogen in the dehydrogenation reaction or hydrogen addition reaction, and the like pass through the gap 58b. Become. The end on the side of the gap 58b is a sloped slope portion,
A drain port 59 for collecting the liquefied substance on the upper surface of the refrigerant layer 58 and sending the liquefied substance to the tank 56 arranged below is provided at the other end (the sloped portion).

The catalyst layer 61 is a flat plate-shaped catalyst 61a.
A flat-plate heater 61b is attached to the lower surface of the. The catalyst layer 61 is attached inside the apparatus in a state of being inclined at a predetermined angle. Then, each catalyst layer 61
Between one end of the device and the inner wall of the device, there is provided a gap 61d serving as a passage through which a gas or a liquid can pass in the vertical direction. Therefore, a gaseous hydrogen generator or hydrogen storage which is vaporized by the main heater 57 and not liquefied by the cooling layer 58,
Hydrogen or the like during the dehydrogenation reaction or the hydrogen addition reaction will pass through the gap 61d.

Incidentally, each cooling layer 58 and each catalyst layer 61.
Are hydrogen generating / storing devices 54 in a tilted state.
It is installed inside. Therefore, the liquid hydrogen generating body or hydrogen storage body that has been liquefied in the cooling layer 58 and dropped from above does not cause liquid pools on the upper surfaces of the cooling layers 58 and the catalyst layers 61, and smoothly flows along the slope. It is designed to fall. Moreover, since the drain port 59 is formed in the sloped portion of the inclined surface of the refrigerant layer 58, the liquid descending along the inclination of the refrigerant layer 58 is smoothly sent to the tank 56. For this reason, the storage efficiency of the substance that drops as a hydrogen generator due to the addition of hydrogen and the storage efficiency of the hydrogen store that separates and falls from hydrogen by the dehydrogenation reaction increase.

Further, the hydrogen generating / storing device 54 has a charging port 54a for charging hydrogen into the device 54 and a discharging port 54b for supplying hydrogen generated in the device 54 to the outside. ing. The discharge port 54b is provided with an activated carbon filter 54c for preventing the hydrogen generator or the hydrogen storage body from being discharged to the outside from the discharge port 54b.

As described above, by tilting the catalyst layer 61 and the cooling layer 58 and mounting them in the apparatus, a liquid pool is generated on the upper surface of each catalyst layer 61 and each cooling layer 58, and a sufficient hydrogen reaction cannot be performed. The phenomenon can be prevented. That is, the substance before the reaction can be surely dropped into each catalyst layer 61 for hydrogen reaction, and the substance after the hydrogen reaction can be smoothly dropped and stored in the tank 56 without fail.

Next, the structure of the hydrogen generating / storing device according to the fourth embodiment of the present invention will be described with reference to FIGS. In addition, the hydrogen generation and storage device described below,
The hydrogen generation / storage device of the first, second, and third embodiments described above is functionally similar to the hydrogen generation / storage device, and can be incorporated as a part of the system shown in FIG. ing.

The hydrogen generating / storing device 74 according to the fourth embodiment of the present invention shown in FIG. 5 includes a tank 76 which serves as a hydrogen generator or a storage unit for storing the hydrogen storing body, and the tank 76.
6, a main heater 77 for heating and vaporizing the hydrogen generator or hydrogen store in 6, a cooling layer 78 for cooling, liquefying and dropping the vaporized and rising hydrogen generator or hydrogen store, and a cooling layer A circulation pump system 80 that circulates cold water serving as a refrigerant in 78, and a catalyst layer 81 for performing a dehydrogenation reaction or a hydrogen addition reaction of a hydrogen generator or a hydrogen storage body that has dropped from the cooling layer 78. The cooling layer 78 and the catalyst layer 81 are the catalyst layer 81, the cooling layer 78, the catalyst layer 81, and the cooling layer 78.
・ Alternatively arranged in the order of.

FIG. 6 is a perspective view showing each cooling layer 78. The cooling layer 78 is composed of a hollow member having a substantially columnar shape and having a predetermined height in the vertical direction. Cooling water serving as a refrigerant is circulated inside the cooling layer 78 by the action of the circulation pump system 80. The cooling layer 78 is formed with a plurality of cylindrical insertion holes 78a that are vertically inserted. These insertion holes 78a are passage portions for passing gas or liquid in the vertical direction. Therefore, a gaseous hydrogen generator or hydrogen storage that has been vaporized by the heating of the main heater 77 and not liquefied in the cooling layer 78, hydrogen during a dehydrogenation reaction or a hydrogen addition reaction, passes through the insertion hole 78a. Will be done.

FIG. 7 is a perspective view showing each catalyst layer 81. The catalyst layer 81 has a honeycomb structure. That is, the catalyst layer 81 is formed by bundling a plurality of catalysts 81a made of a hexagonal columnar tubular catalyst material in a cylindrical shape such that the outer peripheral surfaces of the adjacent catalysts 81a are brought into contact with each other. The space inside each cylindrical catalyst 81a is a passage portion for passing gas or liquid in the vertical direction.
The gaseous hydrogen generator or hydrogen storage that has been vaporized by the heating of the main heater 77 and has not been liquefied in the cooling layer 78, hydrogen in the dehydrogenation reaction or hydrogen addition reaction, etc.
It will pass through the hole inside each prism-shaped catalyst 81a. The catalyst layer 81 causes a hydrogen reaction by being heated by a heater. Various heating methods can be considered as follows.

For example, a flat-plate heater may be attached to the outer peripheral portion of the columnar shape, that is, the outer periphery of the catalyst layer 81 to heat the inside of the cylinder from the outer periphery of the catalyst layer 81. Further, for example, rod-shaped or planar heaters may be arranged in the gaps between the catalysts 81a adjacent to each other, and the catalysts 81a may be heated by these heaters.

Further, for example, heaters are provided at the outer peripheral portion (outer peripheral portion of the catalyst layer 81) and the central portion (central portion of the catalyst layer 81), respectively, which are bundled into a cylindrical shape, You may make it heat each catalyst 81a from both the outer side and the center side of the catalyst layer 81. Further, for example, a heater may be directly wound around each of the hexagonal cylindrical tubular catalysts 81a for heating, or a heater may be arranged inside each of the tubular catalysts 81a for heating.

The hydrogen generating / storing device 74 has an inlet 74a for supplying hydrogen into the device 74 and an outlet for supplying hydrogen generated in the hydrogen generating / storing device 74 to the outside. It has 74b. The discharge port 74b is provided with an activated carbon filter 74c for preventing the hydrogen generator or the hydrogen storage body from being discharged to the outside from the discharge port 74b.

As described above, by arranging the catalyst layers 81 and the cooling layers 78 alternately in the vertical direction, it is possible to surely drop the substance before the hydrogen reaction into each catalyst layer 81 to cause the hydrogen reaction. The substance after the hydrogen reaction can be dropped smoothly and can be reliably stored in the tank 76.

Next, the structure of the hydrogen generating / storing device according to the fifth embodiment of the present invention will be described with reference to FIG.
The hydrogen generating / storing device described below is functionally the same as the hydrogen generating / storing device of each of the first to fourth embodiments described above, and a part of the system shown in FIG. It is a device that can be incorporated as. But,
The fifth embodiment is common to the above-described first to fourth embodiments in that the catalyst layers and the cooling layers are alternately arranged in the vertical direction, but the configuration of the other parts. Is different. Therefore, different parts will be described in detail.

As shown in FIG. 8, the hydrogen generating / storing apparatus 100 of the fifth embodiment has a hydrogen reactor 101 and a reaction for supplying a hydrogen generator or a hydrogen store to the hydrogen reactor 101. It is composed of a substance supply device 110.

The hydrogen reactor 101 is a storage tank 1 for storing a substance (such as benzene or cyclohexane) after the hydrogen reaction in the hydrogen reactor 101.
02 and cooling layers 10 alternately arranged in the vertical direction.
3 and the catalyst layer 104, and the hydrogen generator or hydrogen storage body sent from the reactant supply device 110.
4 is equipped with a spray nozzle 105 for spraying.
The outlet of the injection nozzle 105 is the uppermost cooling layer 10
3 and the catalyst layer 104 arranged below the space 3a. Also, this hydrogen reactor 1
01 is an inlet 106 for supplying hydrogen to the inside of the apparatus during a hydrogen addition reaction, and an outlet 107 for supplying the hydrogen to the outside when hydrogen is generated by a dehydrogenation reaction inside the apparatus. And have. The outlet 107
Is provided with an activated carbon filter 108.

The reactant supply device 110 includes a storage tank 111 in which a hydrogen generator or a hydrogen store to be supplied to the hydrogen reactor 101 is stored, and a pump 112 for sucking up the hydrogen generator or the hydrogen store in the storage tank 111. When,
Chamber 113 for pressurizing the sucked up hydrogen generator or hydrogen storage, chamber 113 and hydrogen reactor 10
No. 1 valve 114 provided between the injection nozzle 105 and
It consists of

Below, an explanation will be given of an operation example in the case where hydrogen is generated by the hydrogen generating / storing apparatus 100 of the fifth embodiment described above.

First, the charging port 106 is closed by a valve (not shown). Since the storage tank 111 contains a hydrogen generator composed of chemical hydride such as cyclohexane or decalin, the hydrogen generator is sucked up by the pump 112 and pressurized in the chamber 113. Next, by opening the valve 114, the hydrogen generator is sprayed into the hydrogen reaction device 101 from the injection nozzle 105 of the hydrogen reaction device 101. As a result, the atomized hydrogen generator comes into contact with the catalyst in the catalyst layer 104 to cause a dehydrogenation reaction. The catalyst is the same as in the above-described embodiments.
The temperature is controlled to be constant between 250 ° C and 400 ° C.

Cyclohexane or decalin thus applied to the heated catalyst becomes 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 are used in the multi-stage cooling layer 10
The hydrogen reactor 10 is cooled and liquefied by any one of 3
It is stored in one storage tank 102. On the other hand, hydrogen is discharged from the discharge port 107.

Next, an example of operation when hydrogen is stored by the hydrogen generating / storing device 100 of the fifth embodiment will be described.

First, the outlet 107 is closed by a valve (not shown), while the inlet 106 is opened by operating a valve (not shown). Since the storage tank 111 contains a hydrogen storage material composed of an aromatic compound such as benzene or naphthalene, the hydrogen storage material is sucked up by the pump 112 and pressurized in the chamber 113. next,
By opening the valve 114, the hydrogen storage device is moved from the injection nozzle 105 of the hydrogen reactor 101 to the hydrogen reactor 1 concerned.
Sprayed in 01. In addition to this, hydrogen is introduced from the inlet 106. As a result, the sprayed hydrogen storage material comes into contact with the catalyst in the catalyst layer 104, and the hydrogen addition reaction (exothermic reaction) occurs.
Happens. The catalyst is the same as in the above-described embodiments.
The temperature is controlled to be constant between 250 ° C and 400 ° C.

By the reaction with hydrogen, benzene and naphthalene which are applied to the catalyst thus heated become cyclohexane in the case of benzene and hydrogen, and decalin in the case of naphthalene and 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 liquefied by being cooled in any of the multiple cooling layers 103, and stored in the storage tank 102 of the hydrogen reactor 101.

In each of the above-described embodiments, the catalyst layer and the refrigerant layer are separated, but the catalyst layer and the cooling layer may be integrated. FIG. 9 is a schematic diagram showing an example thereof. Note that FIG. 9 is a diagram showing only the hydrogen reaction layer 120 in which the catalyst layer and the refrigerant layer mounted inside the hydrogen generation / storage device are integrated into the front and back. The other parts have the same configurations as those of the first to fourth embodiments described above, and thus the description thereof will be omitted.

The hydrogen reaction layer 120 includes a Peltier element 121 composed of a heat-absorbing ceramic substrate 121a, a heat-dissipating ceramic substrate 121b, and p-type and n-type semiconductors 121c sandwiched between the two ceramic substrates 121a and 121b.
And the ceramic substrate 121 for heat dissipation of the Peltier element 121
A metal member arranged on the b side with good heat conduction efficiency (for example,
(Stainless steel or aluminum plate) 122 and this metal member 12
2 is composed of a catalyst 123 attached to the upper surface. A plurality of hydrogen reaction layers 120 having such a configuration are attached in the hydrogen generation / storage device at predetermined intervals in the vertical direction.

The Peltier element 121 can be cooled on one surface and heated on the other surface. That is, the endothermic ceramic substrate 121a is for cooling and liquefying the hydrogen generating body or the hydrogen storing body which is heated and vaporized in the tank of the hydrogen generating / storing device. Further, the heat-dissipating ceramic substrate 121b, which is attached to the surface opposite to the surface on which the heat-absorbing ceramic substrate 121a is attached with the semiconductor 121c interposed therebetween, plays the role of a heater for heating the catalyst 123.

As described above, the Peltier element 121 is integrally provided with the refrigerant layer in each of the above-described embodiments and the heater provided in the catalyst layer on the front and back sides. In addition, the catalyst 123 is heated by arranging the catalyst 123 on the heat dissipation ceramic substrate 121b, which serves as a heater, with the metal member 122 having good heat conductivity interposed therebetween. With this configuration, the catalyst layer and the cooling layer can be integrally formed on the front and back sides as a whole. In the example of FIG. 9, the catalyst 123 is directly attached to the upper surface of the metal member 122, but a heater is attached between the metal member 122 and the catalyst 123 to further raise the temperature of the catalyst 123. Is also good.

As a modification of FIG. 9, as shown in FIG. 10, a hydrogen reaction layer may be used in which the catalyst layer and the cooling layer are integrated into the front and back without using the Peltier element. That is, in the hydrogen reaction layer 130 shown in FIG. 10, the cooling layer 13 is formed between the cooling layer 131 and the catalyst layer 132 each including a cooling pipe.
Insulating layer 133 composed of a heat insulating agent from one side, catalyst 13
It is composed of a heater 134 for heating 2 and a metal member 135 with high thermal conductivity efficiency for transmitting heat of the heater 134 to the catalyst layer 132. Note that the insulating layer 133
Is for preventing the heat for heating the catalyst 132 from being transferred to the cooling layer 131 side. With this configuration, the catalyst layer 132 and the cooling layer 131 can be integrally formed on the front and back sides without using the Peltier element 121.

Next, a control unit for performing various controls of the hydrogen generation / storage device 14 of the first embodiment described above will be described. The hydrogen generating / storing devices of the second to fourth embodiments can also perform various controls described below.

As shown in FIG. 11, the control unit 160 mainly includes a control panel 161, a CRT monitor 162, an operating unit 163 such as a keyboard and a mouse, a personal computer main body 164, and a PCI expansion unit 165. ing.

The control panel 161 includes a power switch 170 for a 100V power source, a power switch 171 for a 200V power source 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 for controlling the temperature of the tank 16, an alarm unit 181, a buzzer, an operation switch 182, and a status indicator lamp 183 for displaying an operation status are provided.

In the control unit 160, the temperature of the catalyst 21a, the temperature in the tank 16, the temperature of the surface of the main heater 17, the temperature of each raw material, the temperatures of the inlet and the outlet of the cooling layer 18, and the temperature of the charged hydrogen are controlled. Each control is performed. In addition, the control unit 1
At 60, the flow rate of generated hydrogen and the flow rate of hydrogen introduced into the apparatus are measured.

Further, the control unit 160 detects the hydrogen pressure after cooling and the pressure of hydrogen introduced into the apparatus. Further, a mechanism is provided which can set an upper limit and a lower limit of the liquid level of the tank 16 and informs the liquid level when there is no liquid level between the upper limit and the lower limit.

The personal computer main body 164 is a portion for setting and controlling temperature, pressure and the like in various components such as the tank 16, and at the same time, can analyze hydrogen by the installed analysis software of gas chromatography.

Next, the result of grasping the operating conditions with a lab-scale device before the operation of the hydrogen generation / storage device 14 will be described.

FIG. 12 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. 12
As shown in, the hydrogen generation amount is the largest when the reaction temperature is 523 K (= 250 ° C.). Moreover, when the reaction temperature is too high, the amount of hydrogen generated decreases. this is,
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 21a.

FIG. 13 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. 0.5 g of platinum was used for the catalyst 21a. The reaction temperature was 523K.

As shown in FIG. 13, 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 reason why the hydrogen generation amount decreases when the supply amount of cyclohexane increases is that the catalyst 21a 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. 14 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. 15 is a graph showing the results of examining the group mass dependence of decalin 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. 0.5 g of platinum was used for the catalyst 21a. The reaction temperature was 523K.

As shown in FIG. 15, as the supply amount of decalin increases from 1.4 to 1.75 ml, the hydrogen generation amount decreases. It is considered that the reason why the hydrogen generation amount decreases when the supply amount of decalin increases is that the catalyst 21a was applied with more decalin than necessary and a proper liquid film could not be formed on the catalyst surface.

FIG. 16 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 573 K, and the feed rates of the three raw materials were 1.75 ml / min.

As a result, it was found that hydrogen gas was significantly 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.

[0111]

[Table 1]

Table 1 is a table showing the hydrogen release results 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 hydrogen release, 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 embodiments. The following various modified embodiments may be adopted. 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 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 each of the above-mentioned embodiments, a plurality of pairs of catalyst portions and cooling portions are arranged alternately in the vertical direction.
It may be a pair only. Further, two or more cooling sections may be provided for one catalyst section.

Further, depending on the selection of the raw material, it is not necessary to heat the catalyst by heating only the raw material. Further, the raw material may be heated by heating only the hydrogen supply body and not by heating the hydrogen storage body. Further, it is not necessary to heat the raw material by heating only the catalyst. Further, regarding the heating of the raw material, only the hydrogen storage body may be heated, or only the hydrogen supply body may be heated and raised, and then cooled to be liquefied and brought into contact with the catalyst.

Further, a power generator 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.

[0120]

According to the present invention, the reaction efficiency of hydrogen addition reaction or dehydrogenation reaction can be increased. Further, according to another aspect of the present invention, the hydrogen storage body and the hydrogen supply body can be collected in the same container without preparing separate containers. Therefore,
An apparatus capable of performing both hydrogen addition reaction and dehydrogenation reaction can be compactly configured.

[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 (henceforth chemical hydride).

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

FIG. 3 is a diagram showing a hydrogen generation / storage device according to a second embodiment of the present invention.

FIG. 4 is a diagram showing a hydrogen generation / storage device according to a third embodiment of the present invention.

FIG. 5 is a diagram showing a hydrogen generation / storage device according to a fourth embodiment of the present invention.

FIG. 6 is a perspective view showing a cooling layer of the hydrogen generation / storage device of FIG.

FIG. 7 is a perspective view showing a catalyst layer of the hydrogen generation / storage device of FIG.

FIG. 8 is a diagram showing a hydrogen generation / storage device according to a fifth embodiment of the present invention.

FIG. 9 is a diagram showing a main part of a modified example of the first to fourth embodiments of the present invention.

FIG. 10 is a diagram showing a main part of another modification of the first to fourth embodiments of the present invention.

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

FIG. 12 is a graph showing the results of examining the reaction temperature dependence of the dehydrogenation reaction of cyclohexane used in the present invention.

FIG. 13 is a graph showing the results of examining the group mass dependence of the dehydrogenation reaction of cyclohexane used in the present invention.

FIG. 14 is a diagram showing a reaction formula in which naphthalene and hydrogen are produced by a dehydrogenation reaction of decalin which can be used in the present invention, and conversely decalin is produced by a hydrogenation reaction of naphthalene.

FIG. 15 is a graph showing the results of investigating the group mass dependence of the dehydrogenation reaction of decalin usable in the present invention.

FIG. 16 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 14a input port 14b outlet 16 tanks (storage section) 17 Main heater 18 cooling layer 18a Through hole (passing part) 20 heater 21 catalyst layer 21a catalyst 21b heater 21c Through hole (passing part) 34 Hydrogen generation / storage device 34a input port 34b outlet 36 tanks (storage) 37 Main heater 38 Cooling layer 38a cooling unit 38b Gap (passing part) 41 catalyst layer 41a catalyst 41b heater 41c catalyst part 54 Hydrogen generation / storage device 54a input port 54b outlet 56 tanks (storage) 57 Main heater 58 cooling layer 58b Gap (passing part) 61 catalyst layer 61a catalyst 61b heater 61d Gap (passing part) 74 Hydrogen generation / storage device 74a input port 74b outlet 76 tanks (storage) 77 Main heater 78 Cooling layer 78a insertion hole (passage part) 81 catalyst layer 81a catalyst 103 cooling layer 104 catalyst layer 121 Peltier element 123 catalyst

Claims (10)

[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, comprising a catalyst part for carrying out the dehydrogenation reaction or the hydrogen addition reaction of the hydrogen generator or the hydrogen storage body. And a cooling unit for cooling and liquefying the vaporized hydrogen generating body or the hydrogen storing body, which are alternately arranged. 2. 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 the hydrogen generating body or the hydrogen storing body before the hydrogen reaction is stored and the hydrogen generating body is dehydrogenated. Of hydrogen storage or a storage for collecting and storing the hydrogen generator after hydrogenation reaction to the hydrogen storage, and heating the hydrogen generator or the hydrogen storage in the storage, or the hydrogen generator or A main heater for vaporizing a hydrogen storage body, a cooling unit for liquefying and dropping the vaporized and rising hydrogen generator or the hydrogen storage body, and a cooling unit for dropping the hydrogen storage unit A catalyst part provided with a catalyst and a heater for performing the dehydrogenation reaction or the hydrogen addition reaction on the hydrogen generator or the hydrogen storage body, an outlet for discharging hydrogen generated by the dehydrogenation reaction, and the hydrogen addition reaction. A hydrogen generating / storing device comprising at least one of a charging port for charging hydrogen. 3. 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 generation / storage device for generating or storing hydrogen by using an addition reaction, wherein the hydrogen generator or the hydrogen storage body is provided on the upper surface of a corrugated metal material having irregularities, the dehydrogenation reaction or the hydrogen A catalyst for addition reaction is provided, and a passage portion for passing the vaporized hydrogen generating body or hydrogen storage body to one or both of a concave portion or a convex portion between the metal materials or the metal material is provided. A hydrogen generation and storage device characterized by 4. The catalyst portion and the cooling portion are formed in layers, respectively, and a catalyst layer formed by layering the catalyst portion and a cooling layer formed by layering the cooling portion are provided for passing vaporized substances, respectively. 4. The hydrogen according to claim 1, wherein the passage portion is provided, and the passage portion of the catalyst layer and the passage portion of the cooling layer are formed at positions that do not overlap each other in the vertical direction. Generator / storage device. 5. The catalyst layer and the cooling layer are arranged in a slanted state, respectively, and the slanted substance is used to drop the liquefied substance into the respective layers without delay. The hydrogen generating / storing device according to claim 4. 6. The hydrogen generating / storing device according to claim 4, wherein a plurality of cooling layers and a plurality of catalyst layers are provided in the same number. 7. The hydrogen generating / storing device according to claim 1, further comprising a hydrogen reaction layer having an integral structure in which the cooling unit is on the lower surface side and the catalyst unit is on the upper surface side. 8. The hydrogen generating / storing device according to claim 7, wherein the cooling unit and the catalyst unit are made to function on both sides of a Peltier element, respectively. 9. The hydrogen generating / storing device according to claim 7, wherein an insulating layer, a heater, and a heat conducting material are arranged in this order from the cooling section side between the cooling section and the catalyst section. . 10. The aromatic compound, wherein any one or a plurality of benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthrene, and their alkyl-substituted compounds are mixed. The hydrogen generating / storing device according to any one of claims 1 to 9, wherein: