JP2002274802A - Hydrogen storage and supply means - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen storage and supply system by which a fuel battery system capable of rapidly responding with a load fluctuation in electric power is made possible. SOLUTION: This hydrogen storage and supply system utilizes at least either of hydrogenation reaction of a hydrogen storage body consisting of an aromatic compound and dehydrogenation reaction of the hydrogen supply body consisting of the hydrogenation derivative of the aromatic compound. This system consists of (a) raw material storage means 2 housing the hydrogen storage body and/or the hydrogen supply body, (b) a reaction apparatus 4 housing a metal deposited catalyst for effecting the hydrogenation of the hydrogen storage body and/or dehydrogenation of the hydrogen supply body, (c) raw material supplying means 3 for supplying the hydrogen supply body and/or the hydrogen supply body in the raw material storage means to the reaction apparatus, (d) gas-liquid separating means for condensing the formed gas from the reaction apparatus and separating this gas to the hydrogen storage body and/or the hydrogen supply body and (e) reactant recovering means 10 for recovering the separated hydrogen storage body and/or the hydrogen supply body.

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).

In such a hydrogen storage / supply system, it is desirable that the raw material be continuously injected into the catalyst and the reaction be continued stably from the viewpoint of the stability and continuity of the reaction. In particular, when hydrogen is generated by a dehydrogenation reaction and supplied to a fuel cell for power generation, if the amount of generated hydrogen fluctuates, the amount of generated power fluctuates, so that hydrogen can be supplied more stably. Is required.

However, since the above-mentioned hydrogen storage / supply system uses a single reactor, when the raw material is continuously injected, especially when hydrogen is generated, 200 hours are required.
The catalyst heated to about 350 ° C. is cooled by the low-temperature liquid raw material to lower the catalyst temperature, and the endotherm accompanying the dehydrogenation reaction causes the catalyst temperature to drop sharply, and the reaction may be stopped halfway. Was. In order to keep the catalyst temperature from dropping and continue the dehydrogenation reaction, lower the injection amount of the raw material,
Alternatively, it is necessary to intermittently inject the raw material, but in the former case, the desired amount of hydrogen generation cannot be obtained, and in the latter case, the desired amount is secured as the total amount of hydrogen generation per predetermined time. Although it is possible, the amount of generated hydrogen fluctuates cyclically, so that hydrogen can be supplied stably.
It was difficult to precisely control the amount of hydrogen generated.

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 performed. 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 material storage means, a reaction device, a material supply means, a gas-liquid separation means, It has been found that the above object can be achieved by constructing a system consisting of a reactant recovery means and forming a reactor with at least one tubular body, and the present invention is completed based on such knowledge. Reached.

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.
Or (c) 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 reaction apparatus, which contains a metal-supported catalyst for performing dehydrogenation of the hydrogen supply body; d) gas-liquid separation means for condensing the gas produced from the reactor to separate hydrogen and hydrogen storage and / or hydrogen supply; and (e) reaction for recovering the separated hydrogen storage and / or hydrogen supply. Hydrogen storage comprising a material recovery means, and wherein the reactor is formed of at least one cylindrical body in which a hydrogen supplier or a hydrogen storage forms a coexistence interface between a gas phase and a liquid phase. A supply system is provided;

Further, according to the second aspect of the present invention, the first aspect is provided.
The present invention provides the hydrogen storage / supply system further comprising (f) a control unit for controlling conditions of the hydrogenation reaction and / or the dehydrogenation reaction in the reactor.

According to the third aspect of the present invention, the first aspect is provided.
Alternatively, in the second invention, there is provided a hydrogen storage / supply system, wherein the metal-supported catalyst is applied to a tube wall of the cylindrical body or is filled in the tube.

According to the fourth aspect of the present invention, the first aspect is provided.
In any one of the third to third inventions, the metal-supported catalyst is selected from the group consisting of nickel, palladium, platinum, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, and iron. A hydrogen storage and supply system is provided, wherein the hydrogen storage and supply system is at least one metal selected.

According to the fifth aspect of the present invention, the fourth aspect
In the invention of the present invention, the carrier carrying the supporting metal is activated carbon, carbon nanotubes, molecular sieves, zeolite,
A hydrogen storage and supply system is provided, which is selected from silica gel and alumina.

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

[0020]

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 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;
(D) gas-liquid separation means for condensing the gas produced from the reactor to separate hydrogen and hydrogen storage and / or hydrogen supply, and (e) recovering the separated hydrogen storage and / or hydrogen supply. And (f) preferably a control means for controlling the conditions of the hydrogenation reaction and / or the dehydrogenation reaction in the reaction apparatus. An embodiment of the supply system will be described in detail with reference to the drawings.

FIG. 1 is an explanatory diagram schematically showing a configuration of a hydrogen storage / supply system capable of storing and / or supplying hydrogen. Although the configuration in FIG. 1 illustrates a system capable of both storing and supplying hydrogen, an unnecessary unit may be omitted and the configuration may be such that only one of them is possible. 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 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 causing a hydrogenation reaction or a dehydrogenation reaction by bringing benzene or cyclohexane into contact with a catalyst. In the present invention, at least one cylindrical body is used. Forming a reactor. Further, as shown in FIG.
It is formed of a cylindrical body of an insulator having high heat resistance, such as alumina or ceramic. A porous catalyst 41 is housed inside a cylindrical body 42. One end 42a of the tubular body 42 is connected to the raw material supply means 3 by piping, and the raw material from the raw material supply device 3 is supplied to the catalyst 41 by, for example, a dispersion plate.
Dispersed uniformly on top. The reactor 4 is preferably formed of a plurality of small tubes from the viewpoint of uniform dispersion of the raw materials, heating efficiency of the catalyst, and the like.

Here, the cylindrical body 42 may have any shape as long as it can fill the metal-carrying catalyst while maintaining the flow path. Alternatively, the cylindrical body 42 may have an inner diameter changed like a mortar or bellows. The shape and dimensions can be appropriately selected according to the use condition. When the catalyst is heated by a heater such as a nichrome wire, the tubular body 42 is preferably formed of a material having good thermal conductivity such as aluminum.

In the present embodiment, as the catalyst 41, a porous catalyst in which platinum is supported on an activated carbon material and which is permeable to raw materials and reaction products is used, and the weight of the catalyst in each reactor is 25 g. However, its weight and size are factors to be adjusted as necessary, and are not particularly limited.

The means for heating the catalyst is not particularly limited, and resistance heating using a nichrome wire heater, high-frequency induction heating, or the like can be used. In the present embodiment, the tubular body 42 of the reactor 4 is Surrounding the catalyst 41
A coil-shaped electromagnetic induction coil 11 that heats the catalyst 4 is provided. 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.
1 is adjusted.

In the high-frequency induction heating, a conductor is induction-heated 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 Joule heat is generated. The conductor 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 employed 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, when a high-frequency current is continuously supplied to the electromagnetic induction coil, the conductor is continuously 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.

In order to perform heating more efficiently and with good response, the metal-supported catalyst is formed by using a conductor such as carbon as a carrier of the metal-supported catalyst and forming the metal-supported catalyst in a shape that generates an eddy current. Direct heating is preferred. 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. Furthermore, in order to heat only the metal-carrying catalyst efficiently and instantaneously, the cylindrical body is formed of an insulator having high heat resistance such as alumina or ceramic. When there are a plurality of cylindrical body bodies, each cylindrical body body may be surrounded by an electromagnetic induction coil and each may be heated, or a plurality of cylindrical body bodies may be collectively surrounded by one electromagnetic induction coil and heated. May be. Note that a plurality of electromagnetic induction coils may be arranged in the longitudinal direction of the cylindrical body, and for example, heating may be performed so that the catalyst temperature increases in order from the raw material supply side.

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. The other end 42b of the tubular body 42 of the reactor 4 is connected to the gas separating means 5 via a valve 6 formed of an electromagnetic valve, and the pipe between the reactor 4 and the raw material supply means 3 is branched. 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 hydrogenation reaction occurs between hydrogen and benzene, and benzene and hydrogen are generated when a dehydrogenation reaction of cyclohexane occurs. These products are gases. Therefore, 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. But higher purity (99.9%
Above), when activated hydrogen is required,
Since it is necessary to use a conventional technique such as a silica separation membrane or a palladium / silver separation membrane as the hydrogen separator membrane to purify hydrogen, the present embodiment is additionally provided. still,
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 to reduce the entrainment amount of droplets to the hydrogen extraction unit 52. It 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. 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 unit 52 of the gas-liquid separation unit 5 is usually unnecessary, the steam condensing unit 51 of the gas-liquid separation unit 5 and the outlet of the hydrogen extraction unit 52 are directly connected to the pipe, and the hydrogen extraction unit 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, the 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.

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 the power control circuit 106.

3. Operation method of hydrogen storage / supply system The hydrogen storage / supply system of the present invention has the above-described configuration, and includes at least one hydrogen supply or hydrogen storage that forms a coexistence interface between a gas phase and a liquid phase. The present invention is characterized in that a reaction device is formed by a tubular body. 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 feedback-controlled by the thermocouple 45.
While adjusting the temperature of Step 1 to around 100 ° C., the valve 7 is opened, hydrogen is supplied to the reactor 4 from a hydrogen supply means (not shown), the valve 32 is opened, and the compressor (pump) 31 is operated. Then, a predetermined amount of benzene in the raw material storage means 2 is continuously supplied to the reactor 4 so that the catalyst 41 is brought into contact with benzene and hydrogen.

At this time, gaseous cyclohexane is generated along with the hydrogenation reaction, and the generated cyclohexane is supplied continuously from the raw material supply side 42a of the cylindrical body 42 of the reactor 4 because the raw material is continuously supplied. The gas is discharged to the gas-liquid separation unit 5, cooled by the vapor condensing unit 51 of the gas-liquid separation unit 5, turned into a liquid state, moved to the reaction product recovery unit 8, and stored in the reaction product recovery unit 8. On the other hand, unreacted hydrogen once enters the reactant recovery means 8, and is supplied to the hydrogen extraction section 52 of the gas-liquid separation means 5.
Although it is moved to the outside via, it may be configured to be connected to hydrogen supply means for recovery and circulating use.

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, cyclohexane in the raw material storage means 2 is continuously supplied to the reactor 4 in a predetermined amount, and the catalyst 41 is brought into contact with cyclohexane.

At this time, gaseous benzene and hydrogen are produced along with the dehydrogenation reaction, and the produced benzene is supplied as a raw material continuously from the raw material supply side 42a of the cylindrical body 42 of the reactor 4. Therefore, it is discharged to the gas-liquid separation means 5,
The liquid is cooled by the vapor condensing unit 51 of the gas-liquid separation unit 5, becomes a liquid, moves to the reactant collecting unit 8, and is stored in the reactant collecting unit 8. On the other hand, the generated hydrogen once enters the reactant recovery unit 8 and moves to the outside from the hydrogen extraction unit 52 of the gas-liquid separation unit 5 via the pipe 91 and the sensor 93.

The hydrogen storage / supply system of the present invention has been described on the premise of application to a fuel cell. Naturally, 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. In addition, M1
And M2 are the metals shown below. 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 as 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-carrying catalyst can be directly heated by using a conductor 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 shape of the metal-supported catalyst is not particularly limited.
Granular, sheet, woven, honeycomb, etc., which are appropriately selected according to the use form, a flow path through which the raw material or the product by the reaction can be formed, and the contact area between the raw material and the catalyst It is preferable to use a porous material having a large particle size. When a thin tube is used as the tubular body, the inner surface of the thin tube may be coated with a metal-supported catalyst.

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.

[0052]

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 cylindrical granular material in which 0.5% by weight of platinum was supported on porous activated carbon was used. The amount of the catalyst was 25 g. Using this metal-supported catalyst, cyclohexane dehydrogenation and benzene hydrogenation were carried out in the following manner. [Hydrogen supply] The metal-supported catalyst was converted to a reactor having a length of 16c.
m, a cylindrical body having an inner diameter of 2 cm, a high-frequency current is passed through an electromagnetic induction coil, and the catalyst is directly heated by electromagnetic induction heating. Continuously. 3
After 0 minute, the rate of hydrogen generation was 22 l / min. The conversion of cyclohexane to benzene was 95%, 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 the hydrogen supply, the metal-supported catalyst was replaced with a reactor having a length of 16c.
m, housed in a cylindrical body having an inner diameter of 2 cm, and set the catalyst temperature to 70 to
At 120 ° C., benzene was continuously fed to the reactor at 36 ml / min. After 30 minutes, the conversion of benzene to cyclohexane was 60%, and the product was only cyclohexane.

(Example 2) In particular, an experiment of hydrogen supply was carried out according to Example 1 using a naphthalene / decalin system instead of the benzene / cyclohexane system. [Hydrogen supply] A hydrogen supply reaction was performed in the same manner as in Example 1 except that the temperature of the catalyst reaction section was set to 300 ° C. The hydrogen generation rate after 30 minutes was 26 l / min. The conversion of decalin to naphthalene was 95%, and naphthalene was recovered by the reaction product recovery means.

Comparative Example 1 The same metal-supported catalyst as in Example 1 was formed in a sheet shape and housed in the bottom of a container-shaped reactor. The raw material was injected into the catalyst from the upper part of the reactor by an injection nozzle, and the piping was connected so that the product of the reaction was discharged from the vicinity of the upper part of the reactor. Further, the catalyst was subjected to high-frequency induction heating using an electromagnetic induction coil disposed outside the bottom surface of the reactor, and the reaction was carried out under the following conditions particularly for hydrogen supply. [Hydrogen supply] In the same manner as in Example 1 except that the reaction apparatus and the heating means were configured as described above, cyclohexane was supplied in 36 m.
It was continuously supplied to the reactor at 1 / min to carry out a hydrogen supply reaction. After 30 minutes, the rate of hydrogen generation was 16 l / min, and the conversion of cyclohexane to benzene was 70%. Unreacted cyclohexane was recovered in the reactant recovery means in addition to benzene.

[0056]

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 a sectional perspective view of a reactor 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.

[Description of Signs] 1 Hydrogen storage / supply system 2 Raw material storage means 3 Raw material supply means 31 Compressor (pump) 32 Valve 4 Reaction device 41 Catalyst 42 Tubular body 45 Thermocouple 5 Gas-liquid separation means 51 Vapor condensing unit 52 Hydrogen Extraction unit 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 13/50 C07C 13/50 15/04 15/04 15/24 15/24 F17C 11/00 F17C 11 / 00 C // C07B 61/00 300 C07B 61/00 300 (72) Inventor Masaru Ichikawa 4-4-2-22, Hachigen 3-Jo Nishi, Nishi-ku, Sapporo, Hokkaido (72) Inventor Nobuko Tempaya, Kita-ku, Sapporo, Hokkaido Article 21 Nishi 2-chome 21-348-201 (72) Inventor Kazuo Tsuchiyama 32, Wadai, Tsukuba, Ibaraki Prefecture Inside Sekisui Chemical Co., Ltd. (72) Inventor Kazuhiro Fukaya 32, Wadai, Tsukuba, Ibaraki Sekisui Chemical Co., Ltd. Inside the company (72) Inventor Yasushi Goto 32nd Wadai, Tsukuba, Ibaraki Sekisui Chemical Co., Ltd. Inside (72) Inventor Yasunori Sugai 1-2-1, Shimotoro Techno Park, Atsubetsu-ku, Sapporo, Hokkaido (72) Inventor Tadashi Utagawa 1-2-1 Shimonopporo Techno Park, Atsetsu-ku, Sapporo, Hokkaido In-house Corporation (72) Inventor Tadashi Sakuramoto 1-2-1, Shimotoro Techno Park, Atsubetsu-ku, Sapporo, Hokkaido Shares F term (reference) within the company power system

Claims (6)

[Claims] 1. A method for storing and / or storing hydrogen by utilizing at least one of a hydrogenation reaction of a hydrogen storage material composed of an aromatic compound and a dehydrogenation reaction of a hydrogen supply material composed 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 reactor containing a metal-supported catalyst for dehydrogenation of the body, (c) a raw material supply means for supplying the hydrogen storage body and / or hydrogen supply body in the raw material storage means to the reaction apparatus, and (d) a reaction. Gas-liquid separation means for condensing the gas produced from the apparatus to separate hydrogen and hydrogen storage and / or hydrogen supply, and (e) reactant recovery means for recovering the separated hydrogen storage and / or hydrogen supply And a reactor Hydrogen donor or hydrogen reservoir to form a coexistence interface of the gas phase and the liquid phase, hydrogen storage and supply systems, and forming at least one tubular member. 2. The hydrogen storage / supply according to claim 1, wherein the system further comprises: (f) control means for controlling conditions of a hydrogenation reaction and / or a dehydrogenation reaction in the reactor. system. 3. The hydrogen storage / supply system according to claim 1, wherein the metal-supported catalyst is applied to a tube wall of the cylindrical body or is filled in the tube. 4. The metal-supported catalyst, wherein the supported metal is nickel,
The palladium, platinum, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, and at least one metal selected from the group consisting of iron, characterized by the above-mentioned. A hydrogen storage / supply system according to any one of the preceding claims. 5. The carrier supporting the supported metal may be activated carbon, carbon nanotube, molecular sieve, zeolite,
The hydrogen storage / supply system according to claim 4, wherein the hydrogen storage / supply system is any one selected from silica gel and alumina. 6. The aromatic compound is benzene, toluene,
The xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthrene, and at least one compound selected from the group consisting of alkyl derivatives thereof, the compound according to any one of claims 1 to 5, Hydrogen storage and supply system.