JP2002187702A - Hydrogen storage/supply system and hydrogen storage/ supply apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the reaction efficiency of hydrogen addition reaction or dehydrogenation reaction utilized for the storage or the supply of hydrogen. SOLUTION: The hydrogen storage/supply apparatus 30 is provided with 1st liquid vessels 31 and 32 each housing a hydrogen storage body or 2nd liquid vessels 31 and 32 each housing a hydrogen supply body, a reaction furnace 35, where the hydrogen addition reaction or the dehydrogenation reaction is performed and a catalyst 42 used for the hydrogen addition reaction or the dehydrogenation reaction is included, a jetting structure part having a jetting nozzle 44 for jetting the hydrogen storage body or the hydrogen supply body to be supplied to the reaction furnace 35 mistily toward the catalyst 42 and a cooling vessel 36 for cooling the hydrogen storage body or the hydrogen supply body generated in the reaction furnace 35.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

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

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

[0005] On the other hand, in the case of 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 a hybrid vehicle that can be switched by using both electricity and gasoline has been put to practical use in order to suppress exhaust gas as much as possible.
However, even in the case of a hybrid vehicle, a hydrocarbon fuel such as gasoline must still be used.

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

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

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

Accordingly, hydrocarbons such as benzene and naphthalene have been attracting attention as a hydrogen storage method excellent in safety, transportability, storage capacity, and cost reduction. These hydrocarbons have the advantage of being excellent in transportability.

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

[0011]

However, in order to make hydrogen storage or supply practical by utilizing a hydrogen addition reaction or a dehydrogenation reaction represented by a reaction between benzene and cyclohexane, the reaction efficiency must be further increased. It needs to be raised. In particular, there is a problem of the action of the catalyst with a liquid raw material such as benzene or cyclohexane.

The present invention has been made in view of the above circumstances, and has as its object to increase the reactivity of a raw material necessary for storing or supplying hydrogen.

[0013]

In order to achieve the above object, the present invention provides a hydrogen storage comprising an aromatic compound which stores hydrogen by reacting with hydrogen, A hydrogen storage / supply system for storing and supplying hydrogen using a hydrogen addition reaction and a dehydrogenation reaction with a hydrogen supplier that is converted into a compound, wherein at least one of a hydrogen addition reaction and a dehydrogenation reaction is provided. A hydrogen reactor having an injection nozzle for injecting a hydrogen storage or a hydrogen supplier in a mist state into a catalyst used for one hydrogen reaction, and hydrogen supplying hydrogen for a hydrogen addition reaction in the hydrogen reactor The hydrogen storage / supply system includes a supply device and a power generation device that generates power using hydrogen generated by the dehydrogenation reaction in the hydrogen reactor.

For this reason, in the hydrogen reactor, a hydrogen storage unit or a hydrogen supply unit (hereinafter referred to as “raw material”) covers the catalyst surface in a uniform and appropriate amount of liquid film state, and the hydrogen storage or supply efficiency is reduced. Extremely high. As a result, hydrogen generated when refining or reforming natural gas or petroleum can be efficiently stored. In addition, hydrogen discharged from the hydrogen reaction device can be guided to a fuel cell and used for private power generation for home use or hospital use, or can be used supplementarily according to fluctuations in power supply from a power plant. Furthermore, a hydrogen supply can also be manufactured by adding hydrogen from the outside to the hydrogen storage. Therefore, an independent energy conversion system can be constructed at home or factory.

Further, another invention is directed to a hydrogen storage device comprising an aromatic compound which reacts with hydrogen to store the hydrogen, and a hydrogen supply device which releases hydrogen to convert the compound into an aromatic compound. A hydrogen storage / supply system for storing and supplying hydrogen using an addition reaction and a dehydrogenation reaction, wherein the heater heats a catalyst used for at least one of the hydrogen addition reaction and the dehydrogenation reaction A hydrogen reaction device having a hydrogen supply device for supplying hydrogen for a hydrogen addition reaction in the hydrogen reaction device, and a power generation device for generating power using hydrogen generated by the dehydrogenation reaction in the hydrogen reaction device. A hydrogen storage and supply system equipped with

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

Another aspect of the present invention is to provide an aromatic compound according to the above-mentioned invention, wherein benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene,
A hydrogen storage / supply system in which one or a plurality of any of biphenyl, phenathrene, and their alkyl-substituted products are mixed is provided.

These raw materials store hydrogen by adding hydrogen to a double bond between carbon atoms. After hydrogenation, the hydrogen supplier releases hydrogen and returns to the original hydrogen storage.
That is, the above-mentioned raw material is a raw material suitable for recycling hydrogen. On the other hand, catalysts used for the hydrogenation reaction of the above-mentioned raw materials have been researched and developed and are well known. For this reason, the use of the above-described raw materials makes it possible to reduce development costs in practical use.

Further, another invention is directed to a hydrogen storage device comprising an aromatic compound which reacts with hydrogen to store the hydrogen, and a hydrogen supply device which releases hydrogen to convert to an aromatic compound. A hydrogen storage and supply device that performs storage and supply of hydrogen using an addition reaction and a dehydrogenation reaction,
A hydrogen addition reaction or a dehydrogenation reaction is performed with at least one of the first liquid tank containing the hydrogen storage material or the second liquid tank containing the hydrogen supply material, and is used for the hydrogen addition reaction. A reaction furnace equipped with a catalyst, a hydrogen storage unit or a hydrogen supply unit to be supplied to the reaction furnace, an injection mechanism having an injection nozzle for injecting a mist toward the catalyst, and a hydrogen storage unit generated in the reaction furnace or The hydrogen storage / supply device includes a cooling tank for cooling the hydrogen supply body.

For this reason, the raw material covers the catalyst surface in a state of a uniform and appropriate liquid film, and the efficiency of hydrogen storage or supply becomes extremely high. Therefore, the present invention can be introduced to a system including a hydrogen supply device such as an oil refinery plant and a power generation device such as a home power generation system using a fuel cell.

Another aspect of the present invention is a hydrogen storage / supply device in which the injection mechanism in the above-described invention performs pulse injection for injecting a hydrogen storage or a hydrogen supply at a predetermined cycle. For this reason, it is easy to create a situation where the raw material forms a uniform and appropriate liquid film on the surface of the catalyst. This is because in the continuous injection, the supply amount is too large and spills from the catalyst surface, and conversely, the supply amount is too small and the hydrogen generation amount or the hydrogen storage amount is easily suppressed.

Another aspect of the present invention is a hydrogen storage / supply device in which the pulse injection in the above-described invention is repeated between injection and stop at predetermined time intervals in a range of 0.5 to 30 seconds. Therefore, an optimal liquid film can be formed on the catalyst surface. Therefore, the amount of generated hydrogen or the amount of stored hydrogen can be increased.

Further, another invention is directed to a hydrogen storage device comprising an aromatic compound which reacts with hydrogen to store the hydrogen, and a hydrogen supply device which releases hydrogen to convert to an aromatic compound. A hydrogen storage and supply device that stores or supplies hydrogen using an addition reaction or a dehydrogenation reaction,
At least one of a first liquid tank containing a hydrogen storage or a second liquid tank containing a hydrogen supply, and a hydrogen addition reaction or a hydrogen supply of the hydrogen storage sent from the liquid tank. A reaction furnace having at least one of the dehydrogenation reactions and a catalyst used for the hydrogen reaction, and a catalyst having a temperature of 60 degrees to 12 degrees during the hydrogenation reaction.
A heater that heats the catalyst to a temperature in the range of 0 degrees and a temperature in the range of 200 to 400 degrees when performing the dehydrogenation reaction; and a hydrogen storage or hydrogen supply generated in the reaction furnace. The hydrogen storage / supply device has a cooling tank for cooling.

For this reason, in the hydrogen reactor, there is no danger that the reaction rate between the raw material and the catalyst is reduced due to a decrease in the temperature of the catalyst, and the efficiency of hydrogen storage or supply is extremely high. As a result, hydrogen generated when refining or reforming natural gas or petroleum can be efficiently stored. In particular, when benzene is used as the hydrogen storage, optimal hydrogen storage becomes possible, and also when cyclohexane is used as the hydrogen supplier, optimal hydrogen supply becomes possible.

In another aspect, the present invention provides an aromatic compound according to the above-mentioned invention, wherein the aromatic compound is benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene,
A hydrogen storage / supply device is provided in which any one or a mixture of any one of biphenyl, phenathrene and their alkyl-substituted products is used.

These raw materials store hydrogen by adding hydrogen to a double bond between carbon atoms. After hydrogenation, the hydrogen supplier releases hydrogen and returns to the original hydrogen storage.
That is, the above-mentioned raw material is a raw material suitable for recycling hydrogen. On the other hand, catalysts used for the hydrogenation reaction of the above-mentioned raw materials have been researched and developed and are well known. For this reason, the use of the above-described raw materials makes it possible to reduce development costs in practical use.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of a hydrogen storage / supply system and a hydrogen storage / supply device according to the present invention will be described below with reference to the drawings.

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

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

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

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

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

FIG. 2 is a diagram schematically showing a hydrogen storage / supply system using an energy self-contained home power generation as an example. The hydrogen storage and supply system provided in the house 10
Mainly, solar cell 11 installed on roof etc. and wind power generator 1
2, an electrolysis device 13, a hydrogen reaction device 14, and a fuel cell 15.

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

The reaction furnace 18 is provided with a catalyst 21 required for a hydrogenation reaction and a dehydrogenation reaction. The catalyst 21 is provided with a heater 22 for heating the catalyst. Further, the reaction furnace 18 is provided with an injection nozzle 23 for injecting a liquid raw material called a hydrogen storage or a hydrogen supply.

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

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

Then, hydrogen is added to the hydrogen storage material, and the hydrogen storage material is changed to a hydrogen supplier represented by cyclohexane. Here, the catalyst 21 is heated to 60 to 120 ° C. by the heater 22. As a result, the rate of generation of the hydrogen supplier by the hydrogenation reaction becomes very high.

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

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

Then, a dehydrogenation reaction of the hydrogen supplier occurs, and hydrogen is generated with a hydrogen storage material such as benzene. Here, the catalyst 21 is heated to 220 to 400 by the heater 22.
Heated to ° C. For this reason, the generation rate of the hydrogen storage material by such a dehydrogenation reaction becomes very high. When the efficiency of the dehydrogenation reaction is taken into consideration, the temperature of the catalyst 21 is 250 to 300 ° C.
It is more preferable to heat the heater 22 such that

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

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

In the hydrogen storage / supply system of FIG. 2, instead of benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene,
Any one or any of anthracene, biphenyl, phenathrene and an alkyl-substituted product thereof may be used in combination.

Next, the structure of the hydrogen storage / supply device of the present invention will be described with reference to FIG.

FIG. 3 is a diagram schematically showing a configuration of a hydrogen storage / supply device capable of performing either one of storage and supply of hydrogen. The hydrogen storage / supply device 30 mainly includes raw material supply tanks 31, 32, a pressurized tank 33, a pump 34, a reaction furnace 35, and a cooling tank 36.

The raw material supply tank 32 plays a role of a buffer of the raw material supply tank 31. In the raw material supply tanks 31, 32,
The same type of raw material is charged, and benzene as a hydrogen storage material or cyclohexane as a hydrogen supply material is charged.

The pressurized tank 33 includes raw material supply tanks 31, 32
This is a component for applying pressure for injecting the raw material to the reaction furnace 35 to benzene or cyclohexane derived from the reactor. Benzene or cyclohexane is supplied to pressurized tank 3
It is sent to a pressurized tank 33 by a pump 34 arranged between the feed tank 3 and the raw material supply tank 32. The pressurized tank 72
A pressure gauge 40 is attached to a nearby pipe, and when the pressure becomes equal to or higher than a predetermined pressure, the pressure is detected and the pressure tank 33 is detected.
The raw material inside is returned to the raw material supply tank 32 by opening the valve 41. This is to prevent damage to the device due to an abnormal rise in pressure.

The reactor 35 is a component for injecting benzene or cyclohexane into the catalyst 42 to cause a hydrogen addition reaction or a dehydrogenation reaction. The injection of benzene or cyclohexane is performed from the injection nozzle 44 by opening the valve 43. By injecting the raw material from the injection nozzle 44, a liquid film of the raw material is easily formed on the surface of the catalyst 42 in the reaction furnace. Further, a thermometer 42a following the thermocouple in contact with the catalyst 42 is provided in the reaction furnace 35.
Is provided. This is because the temperature of the catalyst 42 is monitored by the thermometer 42a. A pressure gauge 44a is provided in the vicinity of a pipe entering the reaction furnace 35. This pressure gauge 44
The injection pressure can be measured by a.

The valve 43 is a valve that enables instantaneous injection of the raw material, that is, pulse injection, by controlling the opening and closing time. The time of injection can be varied in the range of 0.5 to 30 seconds. Further, the time during which the injection is stopped can be varied in the range of 0.0 to 30 seconds. However, during normal operation, the injection time is set so that the upper limit is 5.0 seconds.

The injection nozzle 44 has an injection range angle X for the raw material.
Is designed to be 50 degrees at a pressure of 0.3 MPa. The injection amount of the raw material is 5.0 to 4 by continuous injection for one second.
It can be adjusted within the range of 0.0 ml.

As the catalyst 42, a catalyst in which a platinum catalyst is supported on an activated carbon material is used. The weight of the catalyst 88 is 1
The weight and size are not limited to 00 g.

The reaction furnace 35 is provided with a heater 45 for heating the catalyst 42. The heater 45 is connected to the catalyst 4
2 is housed in the heater storage section 46 in which the heater 2 is placed. The energization of the heater 45 can be controlled by the temperature controller 47. This is because the temperature of the catalyst 42 can be changed depending on a difference in production conditions such as a raw material used.

The heater 45 can heat up to a maximum of 600 ° C., and can be controlled in a range of 100 to 600 ° C. When generating cyclohexane by the hydrogenation reaction of benzene, it is heated to about 60 to 120 ° C.
Considering the conversion efficiency, it is preferable to heat to 95 to 105 ° C.

When producing benzene by the dehydrogenation of cyclohexane, the mixture is heated to about 220 to 400 ° C. Similarly, considering the conversion efficiency, preferably, 2
It is preferable to heat to 50 to 300 ° C. This is because the hydrogenation reaction is an exothermic reaction and the dehydrogenation reaction is an endothermic reaction, and the latter reaction requires thermal energy.

The reactor 35 is provided with a valve 48 for supplying hydrogen into the reactor and a drain valve 49 for removing the raw material in the reactor 35. Valve 48
Is a valve for introducing hydrogen from the hydrogen cylinder 50 into the reaction furnace 35. In addition, hydrogen cylinder 50 and valve 4
8, a three-way valve 51 is provided. The three-way valve 51 is a valve that switches between nitrogen from the nitrogen cylinder 52 and hydrogen from the hydrogen cylinder 50.

The nitrogen from the nitrogen cylinder 52 is sent to the raw material supply tank 31 via the pipe 53 and the valve 54 by opening the three-way valve 51. This is for setting the raw material supply system to a nitrogen atmosphere before sending benzene or cyclohexane to the reaction furnace 35.

The drain valve 49 is connected to the reaction furnace 35.
This is a valve for putting the raw material therein into the reactant storage tank 55. When a hydrogenation reaction occurs between hydrogen and benzene in the reaction furnace 35, a reactant called cyclohexane is generated. Further, when a dehydrogenation reaction of cyclohexane occurs, a reactant called benzene and hydrogen are generated. These reactants are gases at the time of the reaction, but liquefy when cooled in the cooling bath 36. The liquefied cyclohexane or benzene returns from the cooling bath 36 into the reaction furnace 35.
When the drain valve 49 is opened, the liquefied cyclohexane or benzene is sent from the reaction furnace 35 to the reactant storage tank 55.

The cooling tank 36 is a water-cooled circulation type cooling device. The cooling tank 36 is provided to completely liquefy benzene or cyclohexane sent from the reaction furnace 35 and separate it from hydrogen. Cooling is performed at 10-20 ° C and can be varied in 1 ° C units.

The benzene or cyclohexane liquefied in the cooling tank 36 returns to the reaction furnace 35, while unreacted hydrogen or hydrogen generated by the reaction is exhausted to the outside via a valve 57 and a three-way valve 58. Can be. The three-way valve 58 is connected to a generated gas amount measuring device 59 so that the generated gas can be analyzed.

Bubblers 60, 61, and 62 are provided outside the three-way valve 58, at a point branched from the hydrogen cylinder 50 and the nitrogen cylinder 52 to the valve 48, and outside the raw material supply tank 31. Is provided. These bubblers 60, 61 and 62 are provided mainly for the purpose of mixing air from outside and releasing pressure when the internal pressure rises.

Here, a procedure for storing hydrogen by a hydrogen addition reaction of benzene using the hydrogen storage / supply device 30;
An example of a procedure for supplying hydrogen to the outside by a dehydrogenation reaction of cyclohexane will be briefly described with reference to FIG.

When storing hydrogen from the outside, first, the nitrogen cylinder 52, the three-way valve 51, and the valve 54 are opened to make the inside of the raw material supply tank 31 a nitrogen atmosphere. next,
By switching the three-way valve 51, the hydrogen cylinder 50 and the valve 48 are opened, and hydrogen is supplied into the reaction furnace 35. next,
The heater 45 of the reaction furnace 35 is energized to adjust the temperature of the catalyst 42 to around 100 ° C. Next, the pump 34 is operated to supply the benzene in the raw material supply tank 32 into the pressurized tank 33. When the amount of benzene in the raw material supply tank 32 decreases, the valve 65 is opened, and benzene is supplied from the raw material supply tank 31.

Next, the temperature of the cooling water in the cooling tank 36 is set to 10 ° C.
Adjust to Then, benzene is pulse-injected toward the catalyst 42 of the reaction furnace 35 while pulse-controlling the valve 43. As a condition of pulse injection, a method of repeating injection for 1.0 second and stopping for 1.0 second is optimal.

The cyclohexane produced by the reaction is cooled in the cooling bath 36 and returns to the reaction furnace 35. When the drain valve 49 is opened, the reactant storage tank 55
Cyclohexane accumulates. On the other hand, unreacted hydrogen moves to the outside via the cooling tank 36, the three-way valve 58, and the bubbler 60.

On the other hand, when supplying hydrogen to the outside, first, the nitrogen cylinder 52, the three-way valve 51, and the valve 54 are opened to make the inside of the raw material supply tank 31 a nitrogen atmosphere. next,
By switching the three-way valve 51, the hydrogen cylinder 50 and the valve 48 are opened, and hydrogen is supplied into the reaction furnace 35. next,
The heater 45 of the reaction furnace 35 is energized to adjust the temperature of the catalyst 42. Next, the pump 34 is operated to supply the raw material supply tank 3.
2 is supplied into the pressurized tank 33.

Next, the temperature of the cooling water in the cooling tank 36 is set to 10 ° C.
Adjust to Then, the pulse of cyclohexane is injected toward the catalyst 42 of the reaction furnace 35 while the valve 43 is pulse-controlled. As a condition of pulse injection, a method of repeating injection for 1.0 second and stopping for 1.0 second is optimal.

The benzene produced by the reaction is supplied to the cooling bath 3
After cooling at 6, the process returns to the reaction furnace 35. Then, when the drain valve 49 is opened, benzene is stored in the reactant storage tank 55. On the other hand, hydrogen generated by the reaction moves to the outside via the cooling tank 36, the three-way valve 58, and the bubbler 60.

Next, a description will be given of a result obtained by ascertaining the operating conditions with a lab-scale device before the operation of the hydrogen storage / supply device 30.

FIG. 4 is a graph showing the result of examining the reaction temperature dependence of the dehydrogenation of cyclohexane. The horizontal axis is the reaction temperature, and the vertical axis is the amount of hydrogen generated per minute. As shown in FIG. 4, when the reaction temperature is 523 K (= 250 ° C.),
It can be seen that the amount of generated hydrogen is the largest. If the reaction temperature is too high, the amount of generated hydrogen decreases. This is considered to be 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 42.

FIG. 5 is a graph showing the results obtained by examining the dependence of the dehydrogenation reaction of cyclohexane on the group mass. The horizontal axis is the base mass, and the vertical axis is the amount of hydrogen generated per minute. Here, the base mass refers to the supply amount of cyclohexane. Catalyst 4
For 0.5, 0.5 g of platinum was used. The reaction temperature is 52
3K.

As shown in FIG. 5, when the supply amount of cyclohexane is 1.7 ml, the amount of generated hydrogen is the largest. It is considered that the reason why the amount of generated hydrogen decreases when the supply amount of cyclohexane increases is that excess cyclohexane is applied to the catalyst 42 and an appropriate liquid film cannot be formed on the surface of the catalyst 42.

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

FIG. 6 is a diagram showing a reversible reaction formula in which naphthalene and hydrogen are produced by the dehydrogenation of decalin and conversely, decalin is produced by the hydrogenation of naphthalene. In the case of using decalin, as in the case of using cyclohexane, only hydrogen can be generated without breaking the carbon skeleton. Therefore, decalin can be a clean energy source that can prevent global warming accompanying the release of carbon dioxide.

FIG. 7 is a graph showing the results obtained by examining the dependence of the dehydrogenation reaction of decalin on the base mass. The horizontal axis is the base mass, and the vertical axis is the amount of hydrogen generated per minute. Here, the base mass refers to the supply amount of decalin. The catalyst 42 contains 0.
5 g of platinum was used. The reaction temperature was 523K.

As shown in FIG. 7, it can be seen that as the supply amount of decalin increases from 1.4 to 1.75 ml, the amount of generated hydrogen decreases. It is considered that the reason why the amount of generated hydrogen decreases when the supply amount of decalin increases is that excess decalin was applied to the catalyst 42 and a proper liquid film could not be formed on the surface of the catalyst 42.

FIG. 8 is a graph showing the result of comparing the amount of generated hydrogen by changing the type of chemical hydride.
In the figure, open triangles indicate the case where only decalin was used. Black diamonds indicate the case where a mixed solution of decalin and methylcyclohexane was used, and black squares indicate the case where a mixed solution of decalin and cyclohexane was used.
The amount of generated hydrogen gas is shown as a cumulative value for each time. The reaction temperature was 573K, and the supply amounts of the raw materials were 1.
It was 75 ml / min.

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

[0079]

[Table 1]

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

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

However, raw materials other than cyclohexane can be used if safety is improved and use conditions are changed. For example, a chemical hydride which becomes at least one of xylene, mesitylene, methylnaphthalene, anthracene, biphenyl, phenathrene, and an alkyl-substituted product thereof after hydrogen release can be used.

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

[0084]

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

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

Table 2 shows the results.

[0087]

[Table 2]

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

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

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

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

The present invention is not limited to the above embodiments and examples. Various modified embodiments as described below may be adopted. For example, in the above embodiment,
The system that includes both the hydrogenation reaction and the dehydrogenation reaction has been described. Is also good.

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

[0094]

According to the present invention, the reaction efficiency of a hydrogenation reaction or a dehydrogenation reaction can be increased.

[Brief description of the drawings]

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

FIG. 2 is a view showing an embodiment of a hydrogen storage / supply system of the present invention, and is a view showing a hydrogen storage / supply system in which an energy self-contained home power generation system is used as an example.

FIG. 3 is a diagram showing an embodiment of the hydrogen storage / supply device of the present invention, and is a diagram schematically showing a hydrogen storage / supply device capable of storing or supplying hydrogen.

FIG. 4 is a graph showing the results of examining the reaction temperature dependence of the dehydrogenation of cyclohexane used in the present invention.

FIG. 5 is a graph showing the results obtained by examining the dependence of the dehydrogenation of cyclohexane used in the present invention on the base mass.

FIG. 6 is a diagram showing a reaction formula in which naphthalene and hydrogen are produced by a dehydrogenation reaction of decalin and conversely, decalin is produced by a hydrogenation reaction of naphthalene which can be used in the present invention.

FIG. 7 is a graph showing the results obtained by examining the dependence of the dehydrogenation reaction of decalin on the base mass, which can be used in the present invention.

FIG. 8 is a graph showing the results of comparing the amount of generated hydrogen with different types of chemical hydrides usable in the present invention.

[Explanation of symbols]

 Reference Signs List 13 hydrogen supply device 14 hydrogen reaction device 15 power generation device 16 hydrogen storage container (first liquid tank) 17 hydrogen supply container (second liquid tank) 18 reaction furnace 21 catalyst 22 heater 23 injection nozzle 30 hydrogen storage / supply device ( (Hydrogen reactor) 31, 32 Raw material supply tank (first liquid tank, second liquid tank) 33 Pressurized tank (part of injection mechanism) 34 Pump (part of injection mechanism) 35 Reaction furnace 36 Cooling tank 42 Catalyst 44 Injection nozzle (part of injection mechanism) 45 Heater

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masaru Ichikawa 4-22-22, Hachiken 3-Jo Nishi, Nishi-ku, Sapporo, Hokkaido (72) Inventor Yasunori Sugai 1-2-1, Shimotoro Techno Park, Atsubetsu-ku, Sapporo, Hokkaido Shares (72) Inventor Tadashi Utagawa 1-2-1 Shimonopporo Techno Park, Atsetsu-ku, Sapporo, Hokkaido In-service Electric Corporation (72) Inventor Tadashi Sakuramoto 1-2-1, Shimotoro Techno Park, Atsubetsu-ku, Sapporo, Hokkaido Within the control system (72) Inventor Kazuhiro Fukaya 32 Wadai, Tsukuba, Ibaraki Sekisui Chemical Co., Ltd.Tsukuba Research Laboratories (72) Inventor Kazuo Tsuchiyama 32 Wadai, Tsukuba, Ibaraki Sekisui Chemical Co., Ltd. Terms (reference) 3E072 EA10 4G040 AA12 AA42 4G140 AA12 AA42 5H027 AA02 BA13 DD00 DD01

Claims (8)

[Claims] 1. A hydrogen addition reaction and dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen to store the hydrogen, and a hydrogen supplier which releases hydrogen to be converted to the aromatic compound. A hydrogen storage / supply system for storing and supplying hydrogen by using an elementary reaction, wherein the catalyst used for at least one of a hydrogen addition reaction and a dehydrogenation reaction includes A hydrogen reactor having an injection nozzle for injecting the hydrogen supplier in a mist state, a hydrogen supplier for supplying hydrogen for a hydrogen addition reaction in the hydrogen reactor, a dehydrogenation reaction in the hydrogen reactor A power generation device that generates power using the hydrogen generated by the hydrogen storage and supply system. 2. A hydrogen addition reaction and a dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen and stores the hydrogen, and a hydrogen supplier which releases hydrogen to be converted to the aromatic compound. A hydrogen storage / supply system for storing and supplying hydrogen using an elementary reaction, comprising a heater for heating a catalyst used in at least one of the hydrogen addition reaction and the dehydrogenation reaction. A hydrogen reaction device, a hydrogen supply device for supplying hydrogen for a hydrogen addition reaction in the hydrogen reaction device, and a power generation device for generating power using hydrogen generated by a dehydrogenation reaction in the hydrogen reaction device. , A hydrogen storage and supply system. 3. An aromatic compound obtained by mixing one or more of benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenathrene, and an alkyl-substituted product thereof. The hydrogen storage / supply system according to claim 1 or 2, wherein: 4. A hydrogen addition reaction or dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen and stores the hydrogen, and a hydrogen supplier which releases hydrogen and converts it to the aromatic compound. A hydrogen storage / supply device for storing or supplying hydrogen using an elementary reaction, wherein at least one of a first liquid tank containing the hydrogen storage material or a second liquid tank containing the hydrogen supply material Performing one of the liquid tanks and the hydrogenation reaction or the dehydrogenation reaction,
A reaction furnace having a catalyst used for the hydrogenation reaction, and an injection mechanism portion having an injection nozzle for spraying the hydrogen storage or the hydrogen supply to be supplied to the reaction furnace toward the catalyst in a mist state. And a cooling tank for cooling the hydrogen storage body or the hydrogen supply body generated in the reaction furnace. 5. The hydrogen storage / supply device according to claim 4, wherein the injection mechanism performs pulse injection for injecting the hydrogen storage body or the hydrogen supply body at a predetermined cycle. 6. The hydrogen storage / supply device according to claim 5, wherein the pulse injection repeats injection and stop at predetermined time intervals in a range of 0.5 to 30 seconds. 7. A hydrogen addition reaction or dehydration reaction between a hydrogen storage made of an aromatic compound which reacts with hydrogen to store the hydrogen, and a hydrogen supplier which releases hydrogen to be converted to the aromatic compound. A hydrogen storage / supply device for storing or supplying hydrogen using an elementary reaction, wherein at least one of a first liquid tank containing the hydrogen storage material or a second liquid tank containing the hydrogen supply material One liquid tank and at least one of a hydrogen addition reaction of the hydrogen storage material sent from the liquid tank and a dehydrogenation reaction of the hydrogen supplier are used for the hydrogen reaction. A reaction furnace equipped with a catalyst;
A heater for heating the catalyst to a temperature in the range of 200 degrees to 400 degrees when the dehydrogenation reaction is performed; and a hydrogen storage unit generated in the reaction furnace. A hydrogen storage / supply device, comprising: a cooling tank that cools the hydrogen supply body. 8. An aromatic compound obtained by mixing one or more of benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenathrene, and an alkyl-substituted product thereof. The hydrogen storage / supply device according to any one of claims 4 to 7, wherein: