JP2002274803A - Hydrogen storage and supply system - Google Patents

Abstract

(57) [Summary] (Modified) [Problem] To provide a low-cost, stable and efficient hydrogen storage / supply system for fuel cells. SOLUTION: A hydrogen storage / supply system utilizing at least one of a hydrogenation reaction of a hydrogen storage material made of an aromatic compound and a dehydrogenation reaction of a hydrogen supply material made of a hydrogenated derivative of the aromatic compound. (A) raw material storage means 2 for storing a hydrogen storage body and / or a hydrogen supply body; and (b) reactor 4 for housing a metal-supported catalyst for performing hydrogenation of the hydrogen storage body and / or dehydrogenation of the hydrogen supply body. (C) a heating means 11 for heating the metal-supported catalyst 11 (d) a raw material supply means 3 for supplying a hydrogen storage and / or a hydrogen supply in the raw material storage means to the reaction apparatus 3 (e) a gas produced from the reaction apparatus is condensed A gas-liquid separation means 5 (f) for separating the hydrogen into a hydrogen storage material and / or a hydrogen supply material; and a reactant recovery means 8 for collecting the separated hydrogen storage material and / or the hydrogen supply material.

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 more particularly, to a hydrogenation reaction of a hydrogen storage made of an aromatic compound and a hydrogen storage made of a hydrogenated derivative of the aromatic compound. The present invention relates to a low-cost, stable, and efficient hydrogen storage / supply system that stores and / or supplies hydrogen by utilizing at least one of a dehydrogenation reaction.

[0002]

2. Description of the Related Art In recent years, the deterioration of the global environment, for example, global warming, has become a problem. Hydrogen fuel has been used as a clean energy source instead of fossil fuel, and a fuel cell using hydrogen has been used as one of its uses. The system is in the spotlight. Since hydrogen can be produced by electrolysis of water, hydrogen fuel is inexhaustible if it is assumed that seawater or river water is electrolyzed. However, hydrogen is a gas and a flammable substance at normal temperature, so it is difficult to store and transport it, and handling it requires extreme care.

[0003] When considering a fuel cell system for a house or the like as a distributed power source, the form of hydrogen supply is important. However, the method of supplying hydrogen as it is to each home has only safety problems. In addition, there is a problem that it is necessary to prepare an infrastructure for supply. Currently, the following method is considered as a form of hydrogen supply that can be practically used. A. A method in which hydrogen is injected into cylinders and delivered to households. B. A method of obtaining hydrogen from existing infrastructure such as city gas and propane gas by steam reforming. C. A method of obtaining hydrogen by electrolyzing water with nighttime electricity. D. A method for obtaining hydrogen by electrolyzing water using electric energy obtained from a solar cell or the like. E. FIG. A method of obtaining hydrogen directly from light energy and water by a photocatalytic reaction. F. A method for obtaining hydrogen using photosynthetic bacteria, anaerobic hydrogen-producing bacteria, and the like.

Among these, A.I. Can be easily realized as a supply system, but since hydrogen gas is handled at home, there is a problem in safety and it is considered that the practicality is low. On the other hand, B. Although it is realistic in that gas already supplied to the home can be used, there is a problem that the reformer does not sufficiently respond to load fluctuations in the home. C.I. ~ F. However, since there is a time lag between the supply side and the demand side, there is a problem that it is not possible to follow load fluctuations in the home.

Accordingly, the above-mentioned B.I. ~
F. In order to realize the above method, a hydrogen storage / supply system for temporarily storing generated hydrogen and supplying hydrogen to the fuel cell system with good responsiveness as necessary has been studied. For example, Japanese Patent Application Laid-Open No. 7-192746 Japanese Patent Laid-Open Publication No. 5-27080 discloses a system using a hydrogen storage alloy.
No. 1 discloses fullerenes, carbon nanotubes,
A system using a carbon material such as carbon nanofiber is disclosed.

However, in the system using the hydrogen storage alloy, although a simple system capable of controlling the inflow and outflow of hydrogen by heat can be constructed, the amount of hydrogen stored per unit weight of the alloy is low, and a typical LaNi alloy is used. However, the amount of stored hydrogen is only about 3% by weight. In addition, since it is an alloy, it is heavy and lacks stability. further,
The high price of the alloy is also a serious problem in practical use.

In a system using a carbon material, a material capable of storing a large amount of hydrogen is being developed, but it is not sufficient. For example, a carbon nanotube has a large bulk density and a storage amount per unit volume. Low makes the system bulky. In addition, these materials are difficult to synthesize on an industrial scale, and none of them have been put to practical use.

Under these circumstances, the present applicant has proposed a low-cost, safe, transportable, and excellent storage capacity hydrogen storage / supply system such as benzene / cyclohexane or naphthalene / decalin / tetralin hydrocarbons. Pay attention to
Hydrogen storage for storing and / or supplying hydrogen by using at least one of a hydrogenation reaction of a hydrogen storage material made of an aromatic compound and a dehydrogenation reaction of a hydrogen supply material made of a hydrogenated derivative of the aromatic compound・ The supply system was developed. This hydrogen storage / supply system supplies saturated hydrocarbons such as cyclohexane and decalin to a metal-supported catalyst (a carrier such as activated carbon carrying a metal such as platinum) in a mist form using an injection nozzle. Hydrogen is generated, and benzene, naphthalene, and the like are similarly injected into a metal-supported catalyst in a reactor filled with hydrogen to store the hydrogen (Japanese Patent Application No. 2000-388043).

Although the above-mentioned hydrogen storage / supply system is inexpensive and excellent in safety, transportability and storage capacity,
Since the metal-supported catalyst is configured to be heated by the nichrome wire heater, particularly in the case of hydrogen generation, the catalyst heated to 200 to 350 ° C. by the low-temperature liquid raw material is cooled to lower the catalyst temperature. At the same time, the endothermic reaction accompanying the dehydrogenation reaction may cause the temperature of the catalyst to rapidly drop, and the reaction may be stopped halfway. In order to continue the dehydrogenation reaction while suppressing a decrease in the catalyst temperature, it is necessary to reduce the injection amount of the raw material. However, such a measure has a problem that a desired amount of generated hydrogen cannot be obtained. .

In addition, the nichrome wire heater is integrally incorporated in the aluminum storage part, and the catalyst is indirectly heated by heat conduction through the storage part, so that the contact area with the raw material is particularly large. When using a catalyst having a deformed shape such as a honeycomb shape or a catalyst having a foamed structure, the efficiency of heat conduction and the followability of heating are reduced, and it becomes difficult to perform uniform heating. Has not been able to supply efficiently and stably.

For this reason, there is a strong demand for developing a low-cost, stable and efficient hydrogen storage / supply system that enables a fuel cell system capable of promptly responding to fluctuations in household electric power load. Had been.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fuel cell system capable of quickly responding to a change in the load of electric power in a house in view of the above-mentioned problems of the prior art.
An object of the present invention is to provide a low-cost, stable and efficient hydrogen storage and supply system.

[0013]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a hydrogenation reaction of a hydrogen storage material composed of an aromatic compound and a hydrogenation reaction of a hydrogenated derivative of the aromatic compound are carried out. In a hydrogen storage / supply system for storing and / or supplying hydrogen by utilizing at least one of a dehydrogenation reaction of a hydrogen supplier, a raw material storage unit, a reaction device, a heating unit, a raw material supply unit, a gas-liquid separation unit, And a system consisting of reactant recovery means is constructed, and at this time, when the metal-supported catalyst is heated by a high-frequency electromagnetic induction heating means,
The inventor has found that the above-mentioned object is achieved, and has completed the present invention based on such findings.

That is, according to the first aspect of the present invention,
Hydrogen storage for storing and / or supplying hydrogen by using at least one of a hydrogenation reaction of a hydrogen storage material made of an aromatic compound and a dehydrogenation reaction of a hydrogen supply material made of a hydrogenated derivative of the aromatic compound A supply system, the system comprising: (a) a raw material storage means containing a hydrogen storage and / or a hydrogen supply; and (b) hydrogenation and / or hydrogen storage of the hydrogen storage.
A reaction device containing a metal-supported catalyst for performing a dehydrogenation reaction of a hydrogen supplier, (c) a heating unit for heating the metal-supported catalyst, and (d) a hydrogen storage unit and / or a hydrogen supply in a raw material storage unit. Raw material supply means for supplying the body to the reactor,
(E) gas-liquid separation means for condensing the gas produced from the reactor to separate it into hydrogen and a hydrogen storage and / or hydrogen supply; and (f) recovering the separated hydrogen storage and / or hydrogen supply. A hydrogen storage / supply system is provided, which comprises a reactant recovery means, and wherein the heating means is high-frequency induction heating by a high-frequency electromagnetic induction method.

Further, according to the second aspect of the present invention, the first aspect is provided.
In the invention of (1), there is provided a hydrogen storage / supply system, further comprising (g) control means for controlling conditions of a hydrogenation reaction and / or a dehydrogenation reaction in a reactor.

According to the third aspect of the present invention, the first aspect is provided.
Alternatively, in the second invention, the metal supported catalyst is such that the supported metal is nickel, palladium, platinum, rhodium, iridium,
A hydrogen storage / supply system is provided, which is at least one metal selected from the group consisting of ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, and iron.

According to the fourth aspect of the present invention, the third aspect
In the invention of the invention, the carrier carrying the supporting metal is a conductor,
Alternatively, there is provided a hydrogen storage / supply system comprising a conductor as a part.

Further, according to a fifth aspect of the present invention, in any one of the first to fourth aspects, the aromatic compound is
A hydrogen storage / supply system is provided, which is at least one compound selected from benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthrene, and an alkyl derivative thereof.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

1. Basic configuration of hydrogen storage / supply system The hydrogen storage / supply system of the present invention, as described above,
(A) a raw material storage means for storing a hydrogen storage material and / or a hydrogen supply material; and (b) a reaction device for storing a metal-supported catalyst for performing hydrogenation of the hydrogen storage material and / or dehydrogenation of the hydrogen supply material. (C) a heating means for heating the metal-supported catalyst, (d) a raw material supply means for supplying the hydrogen storage body and / or the hydrogen supply body in the raw material storage means to the reactor, and (e) a raw material supply means. Gas-liquid separation means for condensing the produced gas to separate hydrogen into hydrogen and a hydrogen storage and / or hydrogen supply; (f)
A reaction product recovery means for recovering the separated hydrogen storage material and / or hydrogen supply material, and further preferably (g) controlling the conditions of the hydrogenation reaction and / or the dehydrogenation reaction in the reactor. Embodiments of the hydrogen storage / supply system according to the present invention, including control means, will be described below in detail with reference to the drawings.

FIG. 1 is an explanatory view schematically showing the configuration of a hydrogen storage / supply system capable of storing and / or supplying hydrogen. Although the configuration of FIG. 1 shows a system capable of both storing and supplying hydrogen, an unnecessary device may be omitted and only one of them may be configured. The hydrogen storage / supply system 1 mainly includes a raw material storage means 2, a reaction device 4, a heating means (an electromagnetic induction coil) 11, a raw material supply means 3, a gas-liquid separation means 5, a reactant recovery means. 8 and, more preferably, control means 10.

The raw material storage means 2 is formed in a tank shape,
Benzene which is a hydrogen storage or cyclohexane which is a hydrogen supplier is stored. The raw material supply means 3 is a component for pressurizing benzene or cyclohexane introduced from the raw material storage means 2 and supplying the raw material to the reactor 4, and includes a compressor (pump) 31 and a valve 32 composed of an electromagnetic valve.
And is connected to the raw material storage means 2 by piping. The supply amount and supply time of the raw material supplied to the reactor 4 are controlled by the valve 32.

The reactor 4 is a component for injecting and supplying benzene or cyclohexane to the metal-supported catalyst to perform a hydrogen addition reaction or a dehydrogenation reaction. The reactor 4 is formed of a highly heat-resistant insulating container such as alumina or ceramic. A honeycomb sheet-shaped catalyst 41 is provided at the bottom of the inner surface thereof. Is provided with an injection nozzle 42 connected to the raw material supply means 3 by piping, facing the catalyst 41. Injection nozzle 4
2 is provided so that the raw material is uniformly injected onto the catalyst, and a uniform liquid film of the raw material is formed on the surface of the catalyst 41 in the reaction device 4 by injecting the raw material from the injection nozzle 42. You.

In the present embodiment, a catalyst in which platinum is supported on a honeycomb sheet-shaped activated carbon material is used as the catalyst 41, and the weight of the catalyst in the reactor is 100 g. Is a factor to be adjusted in accordance with the condition, and is not particularly limited.

The present invention is further characterized in that the metal-supported catalyst is heated by high-frequency electromagnetic induction. For this reason, below or beside the reactor 4,
A spiral electromagnetic induction coil 11 for heating the catalyst 41 is disposed opposite to the catalyst 41. The temperature of the catalyst is detected by a thermocouple 45 in contact with the catalyst 41, and a high-frequency current to the electromagnetic induction coil is adjusted. Thus, the temperature of the catalyst 41 is adjusted.
The high-frequency induction heating is for inductively heating a conductor at a high frequency generated by flowing a high-frequency current through an electromagnetic induction coil. An eddy current is generated in the conductor by electromagnetic induction, and the conductor is heated by Joule heat. It is overheated. The frequency of the high-frequency current applied to the electromagnetic induction coil depends on the impedance matching with the conductor to be heated, but generally 350 to 450 kHz is used.

As the shape of the electromagnetic induction coil, a spiral shape can be adopted in addition to a general coil shape. In the case of the coil shape, the conductor to be heated is located at the center of the coil, and in the case of the spiral shape, the conductor is arranged on the center line of the spiral,
It can be heated efficiently and with good response.

In the case of performing high-frequency induction heating, if a high-frequency current continues to flow through the electromagnetic induction coil, the conductor will continue to be heated, so that temperature control is generally required. As a method of controlling the temperature, various feedback controls for controlling the high-frequency current flowing through the electromagnetic induction coil by measuring the temperature of the conductor are possible.
At 500 ° C.), feedback control using a general thermocouple is sufficient. In addition, in order to balance the energy input for heating and the energy required for the reaction, it is also possible to determine the amount of heat per unit time required for the reaction and control the current (electric power) applied to the electromagnetic induction coil. It is possible. In order to obtain a hydrogen amount of 18 L / min generally required in a hydrogen fuel cell system by a dehydrogenation reaction from cyclohexane to benzene, 5 kW is required.
Is converted into about 1200 cal / s of thermal energy, so that 14.4 kcal / min of thermal energy, that is, 1 kW of electrical energy is required.

For more efficient and responsive heating, it is preferable to directly heat the metal-carrying catalyst by using a conductor such as carbon as the carrier of the metal-carrying catalyst and forming it in a shape that generates eddy currents. . When the carrier is a non-conductive material, the carrier and a general conductive material such as stainless steel are formed in a layered or blended state to impart conductivity to the carrier. In addition, in order to efficiently heat the conductor to be heated, one that is interposed between the electromagnetic induction coil and the conductor to be heated, for example, a container that stores the catalyst of the reactor,
It is preferable to use an insulator having high heat resistance such as alumina or ceramic.

The temperature of the catalyst 41 is heated to about 60 to 120 ° C. when the electromagnetic induction coil 11 generates cyclohexane by a hydrogenation reaction of benzene. Considering the conversion efficiency, it is preferable to heat to 95 to 105 ° C. When generating benzene by a dehydrogenation reaction of cyclohexane, it is heated to about 220 to 400 ° C. Similarly, considering the conversion efficiency, it is preferable to heat to 250 to 300 ° C. The reason for setting the latter catalyst temperature higher is that the hydrogen addition reaction is an exothermic reaction and the dehydrogenation reaction is an endothermic reaction, so that the latter requires more heat energy. In addition, the reaction device 4 is connected to the gas-liquid separation unit 5 via a valve 6 formed of an electromagnetic valve.
It is connected to a hydrogen supply means (not shown) via a valve 7 composed of an electromagnetic valve.

The valve 6 is used to guide the product in the reactor 4 to the gas-liquid separation means 5. In the reactor 4, cyclohexane is generated when a hydrogen addition reaction occurs between hydrogen and benzene, and benzene and hydrogen are generated when a dehydrogenation reaction of cyclohexane occurs. However, since these products are gases, The gas-liquid separation means 5 is provided to completely liquefy benzene or cyclohexane sent from the reactor 4 and separate it from hydrogen.
The valve 7 is a valve for introducing and controlling hydrogen from the hydrogen supply means into the reactor 4, and is used when cyclohexane is generated from benzene by a hydrogen addition reaction.

The gas-liquid separation means 5 is a heat exchanger 5 for cooling with cooling water, such as a helical thin tube or an alternating cooling pipe structure.
1a and a hydrogen separation unit 5 such as an activated carbon or a hydrogen separator membrane for separating droplets accompanying hydrogen.
And a hydrogen extraction unit 52 made of 2a. The condensing section 51 adjusts, for example, the cooling water temperature (for example, 5 to 20 ° C.) to optimize the gas-liquid separation of the generated hydrogen from the aromatic compound and the hydrogenated aromatic compound. It is preferable to aim.

The hydrogen extraction unit 52 can usually separate and purify hydrogen by manipulating various factors such as the contact area of the steam condensing unit 7, the temperature of the cooling water, and the rate of generated hydrogen. Not required, but higher purity (99.
(9% or more) of hydrogen is required, it is necessary to purify hydrogen using activated carbon or a conventional technique such as a silica separation membrane or a palladium / silver separation membrane as a hydrogen separator membrane. However, in the present embodiment, it is additionally provided.
In addition, a gas-liquid separation unit (not shown) filled with, for example, glass wool, wire mesh, or the like is provided between the reactant recovery unit 8 and the hydrogen extraction unit 52, and entrainment of droplets to the hydrogen extraction unit 52 The amount can also be reduced.

The reactant collecting means 8 is connected to the vapor condensing section 51 of the gas-liquid separating means 5 by a pipe. The cyclohexane or benzene cooled and liquefied by the vapor condensing section 51 is sent to the reactant collecting means 8. Collected. The reactant recovery means 8 is also connected to the hydrogen extraction part 52 of the gas-liquid separation means 5 by piping, and the generated hydrogen is temporarily removed from the vapor condensation part 51 together with the cyclohexane or benzene liquefied by the vapor condensation part 51. After entering the recovery means 8, the hydrogen extraction unit 5
2 and is separated and refined only by hydrogen gas having a low mass and a high diffusion rate by a hydrogen separation unit 52a made of activated carbon or a hydrogen separator membrane installed in the hydrogen extraction unit 52. The purified hydrogen is efficiently supplied to the outside, for example, a fuel cell system for a house, through a pipe 91 connected to the hydrogen extraction unit 52 and a hydrogen discharge side valve 92.

As described above, since the hydrogen extraction section 52 of the gas-liquid separation means 5 is usually unnecessary, the steam condensing section 51 of the gas-liquid separation means 5 and the outlet of the hydrogen extraction section 52 are directly connected by pipes, and hydrogen extraction is performed. The hydrogen may be sent to the pipe 91 by bypassing the section 52, and the liquid cyclohexane or benzene collected at the bottom of the vapor condensation section 51 may be collected by the reactant collection means 8. Further, since a sensor 93 for measuring the amount of generated gas is connected to the pipe 91, the amount of generated hydrogen can be measured by the sensor 93.

On the other hand, a compressor (pump) 31, valve 32, thermocouple 45, valve 6, valve 7, valve 9
2. The sensor 93 and the electromagnetic induction coil 11 are electrically connected to the control unit 10, respectively. Based on information from the thermocouple 45, the sensor 93, etc., a current applied to the electromagnetic induction coil 11, The operation of the (pump) 31 and the valves 6, 7, 92 is controlled.

FIG. 2 is an explanatory view showing another embodiment, in which an electromagnetic induction coil 11 is arranged so as to surround the outer periphery of the reactor 4 and an insulator having high heat resistance is provided near the center thereof. The catalyst 41 is installed via the installation table 46 of the. 42 is an injection nozzle, 45 is a thermocouple arranged in contact with the catalyst.

2. High Frequency Oscillator FIG. 3 shows an example of a high frequency oscillator for applying a high frequency current to the electromagnetic induction coil 11. The electromagnetic induction coil 11
A secondary circuit of the transformer coupling circuit 102 is connected in series with the resonance capacitor 101. A current transformer 103 is provided in a secondary circuit of the transformer coupling circuit 102. The primary circuit of the transformer coupling circuit 102 is provided with an inverter 105 having a full-bridge type semiconductor switching element 104. For example, an alternating current is amplified and input to the transformer coupling circuit 102. I have. The current transformer 103 provided in the secondary circuit of the transformer coupling circuit 102 and the inverter 105 provided in the primary circuit of the transformer coupling circuit 102 are controlled by a power control circuit 106.

3. Operation Method of Hydrogen Storage / Supply System The hydrogen storage / supply system of the present invention is configured as described above, and is characterized by heating the metal-supported catalyst by high-frequency electromagnetic induction. An example of a procedure for storing hydrogen by a hydrogenation reaction of benzene using the hydrogen storage / supply system of the present invention and a procedure for supplying hydrogen to the outside by a dehydrogenation reaction of cyclohexane will be briefly described with reference to FIG. .

When hydrogen is stored by the hydrogenation reaction of benzene, first, a high-frequency current is applied to the electromagnetic induction coil 11 and the catalyst 4 is controlled by feedback control by the thermocouple 45.
While adjusting the temperature of 1 to around 100 ° C., the valve 7 is opened, hydrogen is supplied to the reactor 4 from a hydrogen supply means (not shown), and hydrogen is charged into the reactor 4. Next, the valve 7 is closed, the valve 32 is opened, and the compressor (pump) 31 is operated to supply a predetermined amount of benzene in the raw material storage means 2 to the reaction device 4. Inject benzene.

At this time, gaseous cyclohexane is produced along with the hydrogenation reaction, and the produced cyclohexane is cooled by the vapor condensing part 51 of the gas-liquid separation means 5 to be in a liquid state. It moves and is stored in the reactant recovery means 8. On the other hand, the unreacted hydrogen once enters the reactant recovery means 8 and moves to the outside via the hydrogen extraction part 52 of the gas-liquid separation means 5, but is connected to the hydrogen supply means to be recovered and used for circulation. May be configured.

On the other hand, when hydrogen is supplied to the outside by the dehydrogenation reaction of cyclohexane, first, a high-frequency current is supplied to the electromagnetic induction coil 11 and the temperature of the catalyst 41 is adjusted to about 400 ° C. by feedback control by the thermocouple 45. While opening the valve 32, the compressor (pump)
By operating 31, a predetermined amount of cyclohexane in the raw material storage means 2 is supplied to the reactor 4, and cyclohexane is injected from the injection nozzle 42 toward the catalyst 41. After the injection is completed, the operation of the compressor (pump) 31 is stopped, and the valve 32 is closed.

At this time, gaseous benzene and hydrogen are produced along with the dehydrogenation reaction, and the produced benzene is cooled by the vapor condensing section 51 of the gas-liquid separation means 5 to become liquid, and the reaction product recovery device 8 and is stored in the reactant recovery means 8. On the other hand, the generated hydrogen once enters the reactant recovery means 8 and moves to the outside from the hydrogen extraction part 52 of the gas-liquid separation means 5 via the pipe 91 and the sensor 93.

Although the hydrogen storage / supply system of the present invention has been described above on the assumption that it is applied to a fuel cell, it goes without saying that the hydrogen storage / supply system of the present invention is applied to a power generator other than a fuel cell. Is also good. For example, steam may be generated by burning hydrogen, and a turbine may be rotated to generate electricity by 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 of the present invention.

4. Metal supported catalyst As the metal supported on the metal supported catalyst used in the present invention, nickel, palladium, platinum, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, and iron Noble metals and the like can be mentioned, and these may be used alone or in combination of two or more. Among them, platinum, tungsten, rhenium, molybdenum, rhodium, and vanadium are particularly preferable in terms of activity, stability, handleability, and the like.

The metal loading on the metal-supported catalyst is usually 0.1 to 50% by weight, preferably 0.5 to 50% by weight, based on the weight of the support.
-20% by weight. In the case of a composite metal catalyst using two or more metals, the amount of the additional metal M2 added to the main metal component M1 is 0.001 to 1 in terms of M2 / M1 atomic ratio.
It is preferably 0, particularly preferably 0.01 to 5. Note that M
1 and M2 are the metals shown below, respectively. M1: platinum, palladium, ruthenium M2: iridium, rhenium, nickel, molybdenum,
Tungsten, ruthenium, vanadium, osmium,
Chromium, cobalt, iron

The efficiency of hydrogen storage and hydrogen supply is determined by simultaneously or sequentially adding a carbonyl complex, acetylacetonate salt, cyclopentadienyl complex, or the like of the above metal to a platinum catalyst supported on carbon, which is a main catalyst metal. It is further improved by performing a hydrogen reduction treatment after thermal decomposition.

On the other hand, as a carrier for supporting an active metal,
For example, activated carbon, carbon nanotubes, molecular sieves, porous carriers such as zeolite, or silica gel, known carriers such as alumina can be used, as described above,
It is preferable that a metal-supported catalyst can be directly heated by using a conductive support such as carbon and forming it in a shape that generates an eddy current. When the carrier is a non-conductor, the carrier can be given conductivity by forming the carrier and a general conductor such as stainless steel in a layered or blended form. The conductive carrier refers to a porous body made of metal such as carbon, activated carbon, graphite, or Raney nickel, or a metal carbide such as molybdenum carbide, but does not exclude other conductors.

The shape of the metal-supported catalyst is not particularly limited, and is appropriately selected depending on the form of use, such as granule, sheet, woven, honeycomb, mesh, and porous.

5. Hydrogen supplier As the aromatic compound used in the present invention, benzene,
Toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, aromatic hydrocarbon compounds such as phenathrene, or alkyl derivatives thereof, among which benzene, toluene, xylene, naphthalene and the like are particularly preferable in terms of efficiency. It is preferably used.

[0050]

EXAMPLES Hereinafter, the hydrogen storage / supply system described in the embodiment of the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited by these examples. Not something.

(Example 1) As a metal-supported catalyst, a honeycomb sheet having 0.5% by weight of platinum supported on activated carbon was used. The amount of the catalyst was 100 g. Using this metal-supported catalyst, cyclohexane dehydrogenation and benzene hydrogenation were carried out in the following manner. [Hydrogen supply] A metal-supported catalyst is accommodated in a reactor, a high-frequency current is passed through an electromagnetic induction coil to directly heat the catalyst by electromagnetic induction heating, the catalyst temperature is set to 240 to 270 ° C, and 6 ml of cyclohexane is charged to the reactor. Was supplied for 1 second at intervals of 5 seconds. The hydrogen generation rate after 30 minutes was 36 l / min. The conversion of cyclohexane to benzene was 80%, and benzene was recovered in the reactant recovery means. [Hydrogen Storage] Next, an experiment of hydrogen storage was performed in the following manner, using the above-described apparatus and catalyst, and replacing the content of the raw material storage means 2 with benzene as a hydrogen storage body. As in the case of supplying hydrogen, the metal-supported catalyst was housed in the reactor, the temperature of the catalyst was set to 70 to 120 ° C., and 9 ml of benzene was supplied to the reactor at intervals of 5 seconds, one second at a time. 3
After 0 minutes, the conversion of benzene to cyclohexane is 50.
In%, the product was only cyclohexane.

Example 2 An experiment of hydrogen storage / hydrogen supply was performed according to Example 1 using a naphthalene / decalin system instead of a benzene / cyclohexane system. [Hydrogen supply] A hydrogen supply reaction was performed in the same manner as in Example 1 except that the catalyst temperature was set to 200 ° C. The hydrogen generation rate after 30 minutes was 30 l / min. The conversion of decalin into naphthalene was 80%, and naphthalene was recovered by the reaction product recovery means. [Hydrogen storage] A hydrogen storage reaction was performed in the same manner as in Example 1 except that the catalyst temperature was set to 300 ° C. After 30 minutes, the conversion of naphthalene to decalin was 85%. The product was only decalin.

(Comparative Example 1) Using the same metal-supported catalyst as in Example 1, an aluminum housing in which a nichrome wire was integrally housed was disposed at the bottom of the reactor in contact with the metal-supported catalyst. The reaction was carried out by using resistance heating with a nichrome wire in place of the high-frequency induction heating, especially for the hydrogen supply under the following conditions. [Hydrogen supply] A hydrogen supply reaction was performed in the same manner as in Example 1 except that a current was passed through the nichrome wire to indirectly heat the catalyst. After 30 minutes, the rate of hydrogen generation was 18 l / min, and the conversion of cyclohexane to benzene was 40%. In the reactant collecting means, a large amount of unreacted cyclohexane was recovered in addition to benzene.

[0054]

As described above, the hydrogen storage / supply system of the present invention can stably and efficiently supply hydrogen in a dehydrogenation reaction of a hydrogen supplier composed of a hydrogenated derivative of an aromatic compound. It can be carried out.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram schematically showing a configuration of a hydrogen storage / supply system of the present invention.

FIG. 2 is an explanatory view schematically showing another embodiment of the hydrogen storage / supply system of the present invention.

FIG. 3 is an explanatory diagram showing an example of a high-frequency oscillator for applying a high-frequency current to an electromagnetic induction coil of the hydrogen storage / supply system of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Hydrogen storage / supply system 2 Material storage means 3 Material supply means 31 Compressor (pump) 32 Valve 4 Reaction device 41 Catalyst 42 Injection nozzle 45 Thermocouple 5 Gas-liquid separation means 51 Steam condensing part 52 Hydrogen extraction part 6 Valve 7 Valve 8 Reactant recovery means 93 Sensor 10 Control means 11 Electromagnetic induction coil

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 15/04 C07C 15/04 F17C 11/00 F17C 11/00 C // C07B 61/00 300 C07B 61 / 00 300 (72) Inventor Masaru Ichikawa 4-22-22 Hachiken 3-Jo Nishi, Nishi-ku, Sapporo, Hokkaido (72) Inventor Nobuko Kaiya 2-21-348-201 2-72, Kita 15 Nishi, Kita-ku, Sapporo, Hokkaido Inventor Kazuo Tsuchiyama 32 Wadai, Tsukuba, Ibaraki Prefecture Sekisui Chemical Co., Ltd. (72) Inventor Kazuhiro Fukaya 32nd Wadai, Tsukuba City, Ibaraki Sekisui Chemical Co., Ltd. (72) Inventor Yasushi Goto Tsukuba Ibaraki Prefecture 32 Ichiwadai Sekisui Chemical Co., Ltd. (72) Inventor Yasunori Sugai 1-2-1, Shimonopporo Techno Park, Atsubetsu-ku, Sapporo, Hokkaido ) Inventor Tadashi Utagawa 1-2-1 Shimonopporo Techno Park, Atsubetsu-ku, Sapporo, Hokkaido (72) Inventor Tadashi Sakuramoto 1-1-2 Shimonopporo Techno Park, Atsubetsu-ku, Sapporo, Hokkaido F-term (Dennai) Reference) 3E072 EA10 4G040 AA42 4G066 AB03B CA38 GA03 4H006 AA05 AC11 AC12 BA12 BA14 BA16 BA19 BA20 BA21 BA22 BA23 BA24 BA25 BA26 4H039 CA40 CA41 CB10 CC20

Claims (5)

[Claims] 1. A method for storing and / or storing hydrogen by utilizing at least one of a hydrogenation reaction of a hydrogen storage made of an aromatic compound and a dehydrogenation reaction of a hydrogen supply made of a hydrogenated derivative of the aromatic compound. A hydrogen storage / supply system for supplying, comprising: (a) a hydrogen storage body and / or a raw material storage means for storing the hydrogen supply body; and (b) hydrogenation and / or hydrogen supply of the hydrogen storage body. A reaction device containing a metal-supported catalyst for carrying out a dehydrogenation reaction of the body, (c) a heating unit for heating the metal-supported catalyst, and (d) a hydrogen storage unit and / or a hydrogen supply unit in the raw material storage unit. (E) gas-liquid separation means for condensing the gas produced from the reactor to separate it into hydrogen and a hydrogen storage body and / or a hydrogen supply body, and (f) a separated hydrogen storage body And / or recover hydrogen supply The reaction recovered consists of a unit, and the heating means, hydrogen storage and supply system, which is a high-frequency induction heating by the electromagnetic induction method of the high frequency. 2. The hydrogen storage / supply according to claim 1, wherein the system further comprises: (g) control means for controlling conditions of a hydrogenation reaction and / or a dehydrogenation reaction in the reactor. system. 3. The metal-supported catalyst, wherein the supported metal is nickel,
3. The method according to claim 1, wherein the metal is at least one metal selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, and iron. A hydrogen storage / supply system as described. 4. The hydrogen storage / supply system according to claim 3, wherein the carrier supporting the supported metal includes a conductor or a conductor as a part. 5. The aromatic compound is benzene, toluene,
The hydrogen storage according to any one of claims 1 to 4, wherein the hydrogen storage is at least one compound selected from xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthrene, and an alkyl derivative thereof.・ Supply system.