JP2003277002A - Hydrogen supplying apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen supplying apparatus which can be operated stably for supplying the hydrogen produced from liquid fuel in a hydrogen separating means to a hydrogen consuming instrument even when a dehydrogenation reaction product produced in the hydrogen separating means is a dehydrogenated compound of a solid state at normal temperature. <P>SOLUTION: This hydrogen supplying apparatus has the hydrogen separating means 2 composed of a dehydrogenating means for dehydrogenating the liquid fuel consisting of hydrogen derivatives obtained by hydrogenating an aromatic compound and separating the dehydrogenated liquid fuel into hydrogen and other components and a hydrogen purifying means for purifying the hydrogen separated from the dehydrogenated liquid fuel by the dehydrogenating means so that the hydrogen purified by the hydrogen purifying means can be supplied to the hydrogen consuming instrument from the means 2. This apparatus is furthermore provided with a solid-liquid separating means 3 for separating the other components into the liquid fuel and a solid of the dehydrogenated compound produced by the dehydrogenation reaction and a returning means 4 for returning the liquid fuel separated by the means 3 to the dehydrogenating means. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen supply device for supplying hydrogen to a hydrogen consuming device such as a fuel cell and a hydrogen engine, and more particularly, a liquid containing a hydrogen derivative obtained by hydrogenating an aromatic compound. The present invention relates to a hydrogen supply device that generates hydrogen from a fuel by a dehydrogenation reaction and supplies the hydrogen to a hydrogen consuming device.

[0002]

2. Description of the Related Art In recent years, a polymer electrolyte fuel cell (PEFC) has attracted attention as a power source for electric vehicles. A polymer electrolyte fuel cell (PEFC) can generate power even at room temperature, and is being put to practical use in various applications.

The polymer electrolyte fuel cell (PEFC) is
The solid polymer electrolyte membrane is sandwiched between the cathode electrode on one side and the anode electrode on the other side. Oxygen in the air supplied to the cathode electrode and hydrogen supplied to the anode electrode. Generates electricity by electrochemical reaction with.

As a method of securing hydrogen as fuel in a fuel cell vehicle equipped with such a fuel cell on the vehicle side, (1) liquid hydrogen or pure hydrogen such as high-pressure hydrogen is used, and a liquid hydrogen tank, A method of supplying hydrogen to a high-pressure tank or a hydrogen storage material such as a hydrogen storage alloy (pure hydrogen type), (2) using a hydrocarbon, for example, a reforming type for generating hydrogen by steam reforming an aqueous methanol solution, Examples thereof include a method of taking out hydrogen from a hydrogenated aromatic compound such as cyclohexane or decalin by a dehydrogenation reaction.

[0005]

However, among these methods for securing hydrogen as fuel for a fuel cell vehicle on the vehicle side, hydrogen is taken out from a hydrogenated aromatic compound-based chemical hydride, for example, a saturated condensed ring compound. The method had the following problems. That is, a compound in which the product after the dehydrogenation reaction exists as a solid at room temperature, for example, naphthalene which is a dehydrogenation compound of decalin, is solidified and fixed in the recovery tank or the pipe even after the operation is stopped. Difficult to do. In addition, the dehydrogenation reaction
Since it is difficult to completely proceed, it is necessary to recover and reuse unreacted fuel that has passed through the dehydrogenation reactor, such as decalin, to improve reaction efficiency.

The present invention has been made to solve the above-mentioned problems, and hydrogen generated by a hydrogen separation means from a liquid fuel which is a hydrogen derivative obtained by hydrogenating an aromatic compound is supplied to a hydrogen consuming device. In the supply device, even if the product of the dehydrogenation reaction in the hydrogen separation means is a dehydrogenation compound that exists as a solid at room temperature, it does not solidify or stick in the recovery tank or the pipe when the operation is stopped, and An object of the present invention is to provide a hydrogen supply device capable of improving the reaction efficiency of the liquid fuel.

[0007]

In order to solve the above-mentioned problems, the hydrogen supply apparatus according to the first aspect of the present invention is configured to dehydrogenate a liquid fuel composed of a hydrogen derivative obtained by hydrogenating an aromatic compound, thereby hydrogenating the liquid fuel. And a hydrogen purifying means for separating hydrogen into other components, and a hydrogen purifying means for purifying the hydrogen separated from the liquid fuel by the dehydrogenating reaction means. In the hydrogen supply device for supplying hydrogen purified by the means from the hydrogen separation means to the hydrogen consuming device, the other components are the unreacted liquid fuel and the solid content of the dehydrogenation compound produced by the dehydrogenation reaction. Equipped with a solid-liquid separation means for separating into
The liquid fuel separated by the solid-liquid separation means,
It is characterized in that a return means for returning to the dehydrogenation reaction means is provided.

According to the first aspect of the present invention, the dehydrogenation compound, which is the other main component, can be suitably recovered as a solid content, and the separated unreacted liquid fuel is recovered and dehydrogenated. As a result of being reusable by the reaction means, the reaction efficiency of the liquid fuel can be improved.

The hydrogen supply device according to a second aspect of the present invention is characterized by comprising a recovery means for recovering a solid content of the dehydrogenation compound separated by the solid-liquid separation means. It is the described hydrogen supply device.

According to the second aspect of the present invention, even if the product after the dehydrogenation reaction is a dehydrogenated compound which is solid at room temperature, it is separated and removed from the liquid fuel by the solid-liquid separation means. When the operation of the hydrogen supply device is stopped, the device can be operated stably because it does not solidify or adhere in the recovery tank or the pipe for recovering the liquid fuel.

The hydrogen supply device according to claim 3 is characterized in that the recovery means is configured to recover the solid content of the dehydrogenation compound by pellet molding. It is a supply device.

According to the third aspect of the present invention, pelletization is performed to collect the solid content, so that the solid content after the collection can be easily stored and transported.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of a hydrogen supply device according to the present invention will be described with reference to FIGS. Figure 1
FIG. 2 is a diagram showing the overall configuration of a hydrogen supply device according to an embodiment of the present invention, FIG. 2 is a perspective view of a pellet molding machine main body of the hydrogen supply device according to an embodiment, and FIG. FIG. 4 is a diagram for explaining the recovery device, and FIG. 4 is a diagram showing the solid-liquid separation means of the second embodiment.

The “liquid fuel which is a hydrogen derivative obtained by hydrogenating an aromatic compound” which can be used in the present invention mainly means “a liquid fuel of a saturated condensed ring compound” and has two benzene rings. It is convenient if it is a saturated compound of condensed hydrogen as described above, which can easily separate hydrogen by a dehydrogenation reaction and produces a compound that is a solid at room temperature as a dehydrogenation compound. As the liquid fuel, for example, decalin or methyldecalin which is a derivative of decalin,
Examples thereof include tetradecahydroanthracene and tetradecahydromethylanthracene.

Here, a hydrogen supply device when hydrogen is produced by a decalin / naphthalene system as a reaction system will be described. In addition, decalin, which is a saturated condensed ring compound, contains c
is type (bp: 193 ° C.) and trans type (bp: 18)
Although there is an isomer of 5 ° C.), either decalin has no problem in explaining the embodiment of the invention, and hence is hereinafter representatively referred to as decalin.

As shown in FIG. 1, the hydrogen supply apparatus according to the present invention comprises a liquid fuel supply means 1, a dehydrogenation reaction means and a hydrogen purification means, and the liquid fuel supplied from the liquid fuel supply means 1 From the hydrogen by the dehydrogenation reaction means, the separated hydrogen is purified by the hydrogen purification means and supplied to the hydrogen consumption equipment, and products other than hydrogen produced by the dehydrogenation reaction and unreacted hydrogen. Solid-liquid separating means 3 for cooling the liquid fuel to perform solid-liquid separation, and returning means 4 for returning the separated liquid subjected to solid-liquid separation to the dehydrogenation reaction means.
And a recovery means 5 for transporting / storing and recovering the solid content separated by the solid-liquid separation.

As shown in FIG. 1, the liquid fuel supply means 1 includes a decalin storage container 1a for storing decalin which is a liquid fuel, and a fuel with a heater 2a1 of a dehydrogenation reaction device 2a which is a dehydrogenation reaction means for decalin. It is composed of a decalin supply pump 1b for supplying the atomizer 2a2, and a pipe 1c for connecting the decalin storage container 1a and the heater 2a1 of the fuel atomizer 2a2. In addition, in the middle of the pipe 1c,
There is provided a confluence section for converging the return pipe 4c for decalin returned from the return means 4 described later and the heater 2a1 of the fuel sprayer 2a2.

The hydrogen separating means 2 comprises a fuel atomizer 2a having a heater 2a1 above a catalyst layer 2a3 having a heater 2a4.
Dehydrogenation reactor 2a which is a dehydrogenation reaction means equipped with
And a membrane separation device 2b, which is a hydrogen purification means provided on the upper side of the dehydrogenation reaction device 2a, constitutes the main part.

The fuel atomizer 2a2 is an internal mixing type one-fluid nozzle equipped with a heater 2a1.
It is provided on the upper part of a. The heater 2a1 is provided in order to prevent the crystal of naphthalene, which is a dehydrogenation compound, from depositing in the decalin solution before the decalin is supplied from the fuel atomizer 2a2 into the dehydrogenation reaction device 2a so as to block the fuel atomizer 2a2. Has been. In the present embodiment, the entire decalin solution is heated to, for example, 100 ° C. or higher (boiling point or lower) and then sprayed into the dehydrogenation reaction apparatus 2a and supplied, so that the catalyst layer 2a3 is highly cooled without being cooled by decalin. You can keep efficiency. A catalyst layer 2a3 containing a heater 2a4 is provided in the dehydrogenation reactor 2a at a substantially central portion thereof.
Is provided. The dehydrogenation reaction in the catalyst layer 2a3 is represented by the following reaction formula. _{C 10 H 18 = C 10 H} 8 + 5H 2 -Q f [kcal / mol] -------- (1) heat of reaction _{Q f = 76.46 [kcal / mol} ] (cis
Type), 79.65 [kcal / mol] (trans)
Type). As an active component of the catalyst forming the catalyst layer 2a3, a metal such as Pt or Pd which is generally a white metal or Ni which is often used as a hydrogenation catalyst is used. Further, when the decalin contains a large amount of sulfur, a C _O / M _O type metal can also be used as an active component of the catalyst. In this embodiment, a catalyst in which a precious metal such as platinum is carried on a carrier such as carbon or silica is used. When the above catalyst is used, the reaction temperature of the dehydrogenation reaction needs to be about 200 ° C. or higher. As the heater 2a4, an electric heater is used to secure the reaction temperature of the catalyst layer 2a3 with a margin.

A hydrogen permeation type membrane module using a metal palladium membrane as a hydrogen separation membrane is used as the membrane separation device 2b which is a hydrogen purification means. As a membrane that can be used as the hydrogen separation membrane, a polyamide hollow fiber membrane may be used in addition to the palladium membrane.

The solid-liquid separating means 3 is continuously provided below the dehydrogenation reactor 2a, and its main part is composed of two heat exchangers 3a and 3b and a filter 3c. The first heat exchanger 3a is provided in the outlet pipe below the dehydrogenation reactor 2a, and is a reaction product other than hydrogen produced by the dehydrogenation reaction at 210 ° C. (mainly of naphthalene and unreacted decalin). (Mixed gas) is used as a precooler for cooling to about 100 ° C. and liquefying. The first heat exchanger 3a uses a water-cooled heat exchanger of a spiral tube type.
On the other hand, the second heat exchanger 3b is a cooler for crystallizing naphthalene, which is a main reaction product other than hydrogen, from the liquid liquefied in the first heat exchanger 3a and dropping downward. is there. The second heat exchanger 3b is provided on an inclined surface, and is a water-cooled multi-tube in which the solubility of naphthalene in the decalin liquid is lowered to precipitate crystals by further cooling the liquid using a water-cooled cooling surface. Type heat exchanger. Second
The cooling water used for the heat exchanger 3b is made to flow countercurrent to the flowing direction of the slurry of decalin and naphthalene flowing on the inclined surface. Further, the cooling surface of the second heat exchanger 3b is formed in a corrugated shape in order to increase a heat transfer area involved in cooling (the corrugated shape referred to here is a direction in which a slurry of decalin and naphthalene flows). On the other hand, the surface shape when the cross section of the heat exchanger is taken at a right angle). The temperature of the cooling water is preferably 0 to 15 ° C in order to precipitate naphthalene. The slurry of decalin and naphthalene, which has been cooled to deposit naphthalene, descends along the inclined surface because the second heat exchanger 3b is provided on the inclined surface, and the naphthalene is collected as solid matter to the filtering device 3c. Supplied with.

The filtration device 3c is a membrane filtration device, and the naphthalene crystals cooled and deposited by the two heat exchangers 3a and 3b are preferably separated and removed from the decalin solution by a membrane, and the recovery means 5 in the subsequent stage is used. It is a device for supplying to. The membrane may be a solvent resistant polymer membrane or a ceramic membrane as long as naphthalene can be separated. The solid-liquid separation operation described above is all performed in the closed casing 3d.

The returning means 4 includes a sub-tank 4a for storing and supplying decalin, which is the separated liquid separated by the filtering device 3c, and a dehydrogenation reaction device 2 of the hydrogen separating means 2 for decalin.
A main part is composed of a return pump 4b for returning to a and a pipe 4c for connecting the sub-tank 4a to the confluence of the pipe 1c of the hydrogen separation means 2 via the return pump 4b. In the sub tank 4a, one end of the pipe 4c is provided so as to extend to near the bottom of the tank 4a. By providing the pipe 4c in this way, the residual liquid amount in the sub tank 4a can be reduced.

The hydrogen supply device is provided with a solid-liquid separation means 3 for separating other components other than hydrogen thus produced by the dehydrogenation reaction into decalin and naphthalene produced by the dehydrogenation reaction. By providing the returning means 4 for returning the decalin separated by the means 3 to the dehydrogenation reaction apparatus 2a, the separated unreacted decalin can be recovered and reused in the dehydrogenation reaction apparatus 2a. The reaction efficiency of dehydrogenation of decalin can be improved. Furthermore, even if the product after the dehydrogenation reaction is naphthalene that is solid at room temperature, it is separated and removed from the decalin solution by the solid-liquid separation means 3, so that decalin is removed when the hydrogen supply device is stopped. Since the naphthalene is not solidified and fixed in the sub tank 4a or the pipe 4c to be recovered, the hydrogen supply device can be operated stably.

The recovery means 5 includes a screw conveyor 5a for transporting the solid matter separated by the filtration device 3c of the solid-liquid separation means 3 to the pellet molding machine 5b, and the pellet molding machine 5b.
The main part is composed of b and a recovery tank 5c for recovering and storing the formed pellets.

The screw conveyor 5a is a transporting device for transporting the naphthalene separated by the solid-liquid separating means 3 to the recovery tank 5c. Since naphthalene easily sublimes, a closed screw conveyor 5a is used.

As shown in FIG. 2, the pellet molding machine 5b rotates the two rolls 5b1 and 5b2 relatively to drop naphthalene from the discharge port of the screw conveyor 5a located at the upper part of the two rolls. It is a briquetting roll type pellet molding machine for compressing and molding naphthalene supplied to the rectangular groove (mold) g provided on the surface of each roll by the pressure between 5b1 and 5b2. The rotation speed of the roll of the pellet molding machine 5b is variable because a motor (not shown) is equipped with a speed reducer. The pellet molding machine 5
The pellets molded by b are collected in a collection tray 5d provided in a collection tank 5c, as shown in FIG.

The recovery tank 5c is a closed-type container as shown in FIG. 1, and has a discharge port for the screw conveyor 5a in the upper part and compresses naphthalene falling from the discharge port in the central part. A pellet molding machine 5b for molding is disposed, and a tray 5d for receiving the naphthalene pellets falling from the pellet molding machine 5b and transporting the naphthalene pellets to the outside of the system is built in the lower part. The tray 5d is a rectangular box-shaped container, and has an upper opening.

Here, as a naphthalene pellet collecting means 5'instead of the tray 5d of the collecting means 5, a pellet carrying-out method for carrying out and collecting the pellets by a vacuum suction method will be described with reference to FIG. . The same members as those of the recovery means 5 of the hydrogen supply device of the embodiment and the recovery means 5'in FIG. 3 will be described with the same reference numerals. The major difference between the recovery means 5'in FIG. 3 and the recovery means 5 of the hydrogen supply device according to the embodiment is (1) that the tray 5d is not provided in the recovery tank 5c, and (2) the recovery tank. A male portion 5f of the coupler for connecting to a female portion 5g of the coupler provided at one end of the pressure reducing pipe 5h is provided on the bottom side portion of 5c so as to project to the outside. (3) The screw conveyor 5a A valve 5e is provided between the discharge port and the upper portion of the recovery tank 5c.
The valve 5e is opened (recovery tank 5c has normal pressure) when the recovery operation is not performed in the recovery tank 5c, and the naphthalene supplied from the screw conveyor 5a passes through the valve 5e to pass through the pellet molding machine. 5b. On the other hand, when performing the recovery operation in the recovery tank 5c, the valve 5e is closed, and the decompression pipe 5h is connected to reduce the pressure in the recovery tank 5c, so that the pelletized naphthalene is discharged out of the system.

The method of carrying out pellets from the recovery tank 5c constructed as described above by the reduced pressure suction method is as follows: (1) Reduced pressure piping 5h depressurized by a vacuum pump (not shown)
The female portion 5g of the coupler provided at one end of the is connected to the male portion 5f of the coupler provided at the bottom side portion of the recovery tank 5c. The pressure in the decompression pipe 5h at this time is, for example, 0.06 MPaG at maximum. (2) The inside of the recovery tank 5c is depressurized by closing the valve 5e. (3) The naphthalene pellets stored in the recovery tank 5c are sucked into the decompression pipe 5h, which is decompressed by the vacuum pump, and carried out of the recovery tank 5c to the outside of the system.

As described above, the solid naphthalene is recovered from the decalin solution at room temperature and stored / conveyed in a closed system for processing, so that the carrying-out operation can be easily performed.

Next, the operation of the hydrogen supply device of one embodiment configured as described above will be described with reference to FIGS. 1 to 3. The decalin storage container 1 of the liquid fuel supply means 1
It is assumed that a is already filled with decalin. (1) Decalin, which is a liquid fuel, is a liquid fuel supply means 1
It is supplied to the dehydrogenation reaction device 2a of the hydrogen separation means 2 by the decalin supply pump 1b. Dehydrogenation reactor 2a
The decalin supplied to the fuel sprayer 2a2 is heated to 100 ° C. by the heater 2a1 installed in front of the fuel sprayer 2a2, and then heated by the heater 2a4 from the fuel sprayer 2a2 to 210 ° C.
The catalyst layer 2a3 heated to 0 ° C. is sprayed.

(2) Catalyst layer 2a3 of dehydrogenation reactor 2a
The decalin sprayed on the mixture produces a mixed gas of hydrogen, naphthalene, and unreacted decalin by the dehydrogenation reaction. (3) The hydrogen generated in the dehydrogenation reaction device 2a is highly purified (for example, 99.9) by the membrane separation device 2b provided with the hydrogen separation membrane (Pd membrane, silica membrane, etc.) which is the hydrogen purification means of the hydrogen separation means 2. % Or more is desirable) and is supplied to the fuel cell 6, which is a hydrogen consuming device. (4) The hydrogen supplied to the anode electrode of the fuel cell 6 reacts with oxygen in the air supplied to the cathode electrode of the fuel cell 6 to generate electricity in the fuel cell 6.

(5) On the other hand, the mixed gas of naphthalene which is another component and unreacted decalin generated in the dehydrogenation reactor 2a is introduced into the solid-liquid separation means 3. In addition, in the other components after the dehydrogenation reaction, it is difficult to completely progress the dehydrogenation reaction, and unreacted decalin is present together with naphthalene. Therefore, it is necessary to separate the unreacted decalin and cause it to react again to improve the fuel efficiency. (6) The mixed gas introduced into the solid-liquid separation means 3 is cooled to a temperature (preferably 100 ° C.) at which it is liquefied by the first heat exchanger 3a in the lower outlet pipe of the dehydrogenation reactor 2a, and droplets are formed. The resulting liquid drops into the second heat exchanger 3b in the subsequent stage.

(7) Decalin and naphthalene in the liquid dropped in the second heat exchanger 3b are decalin liquid at room temperature,
It is separated by utilizing the fact that naphthalene is a solid (melting point 80.3 ° C). That is, by cooling the liquid dropped in the second heat exchanger 3b to a temperature lower than the melting point of naphthalene of 80.3 ° C (preferably 0 to 15 ° C), the naphthalene is deposited as crystals. Since the second heat exchanger 3b is provided on the inclined surface, the slurry in which the solid naphthalene and the liquid decalin are mixed flows naturally in the direction of the filtering device 3c and the screw conveyor 5a (downstream). Go.

In the filtering device 3c, the slurry in which solid naphthalene and liquid decalin are mixed is subjected to membrane filtration to separate naphthalene as a solid component and decalin as a separation liquid. Since the content of naphthalene in this separated liquid is much smaller than that in the liquid before membrane filtration (solution before separation of naphthalene in decalin liquid by solid-liquid separation means 3), the separated liquid is It is sucked up from the sub-tank 4a through the pipe 4c by the pump 4b of the returning means 4 and returned (re-supplied) to the dehydrogenation reaction device 2a of the hydrogen separating means 2. By reacting the separated decalin again in the dehydrogenation reactor 2a, the amount of hydrogen generated (the number of moles) per mol of decalin is improved. That is, the reaction efficiency is improved.

On the other hand, the solid naphthalene separated by the filtering device 3c is conveyed to the pellet molding machine 5b by the screw conveyor 5a of the recovery means 5, and is block-shaped (or tablet-shaped) by the drum-shaped rotary compression molding machine. And is collected in the recovery tank 5c. The naphthalene pellet-formed in the recovery tank 5c is collected in a removable tray 5d installed in advance in the recovery tank 5c, and is recovered together with the tray 5d. Since the naphthalene is formed into pellets in this manner, the handling is simple, and the problems that the naphthalene adheres to the wall surface in the recovery tank 5c and solidifies in the pipe are solved. In addition, pelletizing facilitates storage and transportation after collection. For example, by discharging naphthalene with a vacuum car or the like, storage and transportation are facilitated. It is more preferable to apply the pellet collecting apparatus by vacuum suction as shown in FIG. 3 because the sealing property around the collecting tank 5c is improved and the naphthalene pellets can be easily stored and transported.

Next, the solid-liquid separation means of the second embodiment, which is another embodiment of the solid-liquid separation means used in the hydrogen supply apparatus of the embodiment, will be described with reference to FIG. In addition, the same components as those of the hydrogen supply device according to the embodiment will be described with the same reference numerals.

The solid-liquid separating means 3'of the second embodiment is shown in FIG.
As shown in, the first heat exchanger 3a provided in the lower outlet pipe of the dehydrogenation reactor 2a of the hydrogen separation means 2 and the liquid liquefied in the first heat exchanger 3a are further cooled to produce naphthalene. A second heat exchanger 10 for crystallizing and precipitating
A main part is composed of a screw press 11 for pressing a slurry of decalin and naphthalene to separate decalin as a separation liquid and naphthalene as a solid content. In this embodiment, a water-cooled heat exchanger of a spiral tube type is used as the first heat exchanger 3a, and a scraped surface heat exchanger is used as the second heat exchanger 10. Further, the screw press 11 is a pressurizing / pressurizing device for solid-liquid separation of a slurry of decalin and naphthalene.
It is a press.

The operation of the solid-liquid separating means of the second embodiment having such a configuration will be described with reference to FIG. (1) A mixed gas of unreacted decalin and naphthalene discharged from the dehydrogenation reactor 2a of the hydrogen separating means 2 in the preceding stage,
For example, the mixed gas of 210 ° C. is cooled and liquefied by the first heat exchanger 3a. (2) The liquefied liquid is introduced into the second heat exchanger 10. The liquid introduced into the second heat exchanger 10 further has a temperature of 10 ° C.
Cooled to ~ 15 ° C to precipitate the naphthalene as crystals. By using the scraping surface heat exchanger as the second heat exchanger 10, the heat transfer surface involved in cooling is scraped off by the blade (scraping blade) and constantly updated, so that the liquid is cooled. As a result, the deposited naphthalene can be prevented from sticking to the heat transfer surface. Further, by providing the horizontal scraping surface heat exchanger, it is possible to reduce the vehicle height when mounted on a vehicle. (3) The liquid in which the crystals of naphthalene are deposited in the second heat exchanger 10 from the liquid liquefied in the first heat exchanger 3a is introduced into the screw press 11 in the subsequent stage as a slurry of decalin and naphthalene. (4) The slurry introduced into the screw press 11 is
Decalin, which has been pressed and squeezed in the screw press 11 and has passed through the filtration hole provided in the side wall of the cylinder as the separated liquid, is discharged from the gap between the screw conveyor and the presser of the screw press 11 as the solid content. Naphthalene is recovered. Since naphthalene discharged from the screw press 11 has a liquid content of 5% by weight or less, it can be easily stored and transported. (5) The decalin recovered as the separated liquid is returned by the return means 4
The naphthalene returned (re-supplied) to the dehydrogenation reactor 2a by the above and recovered as a solid content is recovered by the recovery means 5. (6) In FIG. 4, the second heat exchanger 10 and the screw press 11 are arranged with a step, but the rotation shafts of the second heat exchanger 10 and the screw press 11 are connected so as to be detachable from each other via a clutch. It is also possible to arrange them on a straight line. With this arrangement, the vehicle height can be further reduced when mounted on a vehicle.

The present invention is not limited to the above-described embodiments, but can be implemented with appropriate modifications without departing from the technical scope of the present invention. For example, if the liquid fuel supply means 1 and the return means 4 are configured by a common device, the entire hydrogen supply device can be simplified and downsized.
That is, the decalin storage container 1a of the liquid fuel supply means 1
And the sub-tank 4a of the return means 4 is configured as one storage container, and the decalin supply pump 1b of the liquid fuel supply means 1 is configured.
The return pump 4b of the return means 4 is configured as one supply pump. Then, the decalin stored in the storage container is supplied to the dehydrogenation reaction device 2a of the hydrogen separation means 2 by the supply pump, unreacted decalin is recovered by the solid-liquid separation means 3, and then returned to the storage container again. Thus, decalin can be circulated and supplied. in this case,
When the amount of decalin in the sub tank 4a becomes equal to or less than a predetermined amount, the naphthalene recovery work is performed and the decalin is replenished. Further, the filtering device 3c may be a basket type centrifuge or a drum flaker, and may be combined with the collecting means 5.

[0042]

According to the present invention having the above-mentioned structure and operation, the following effects can be obtained. 1. According to the invention described in claim 1, the dehydrogenation compound which is the other main component can be suitably recovered as a solid content, and the separated unreacted liquid fuel is recovered so that the dehydrogenation reaction means can be obtained. As a result, the reaction efficiency of the liquid fuel can be improved. 2. According to the invention of claim 2, even if the product after the dehydrogenation reaction is a dehydrogenation compound which exists as a solid at room temperature,
It is separated and removed from the liquid fuel by the solid-liquid separation means, so when the operation of the hydrogen supply device is stopped, it does not solidify or stick in the recovery tank or the piping that collects the liquid fuel, so the device operates stably. can do. 3. According to the third aspect of the present invention, pelletization is performed to collect the solid content, which facilitates storage / transportation of the recovered solid content.

[Brief description of drawings]

FIG. 1 is a diagram showing the overall configuration of a hydrogen supply device according to an embodiment of the present invention.

FIG. 2 is a perspective view of a pellet molding machine main body of the hydrogen supply device according to the embodiment.

FIG. 3 is a diagram for explaining a pellet collecting device using a vacuum suction method.

FIG. 4 is a diagram for explaining solid-liquid separation means of a second embodiment.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Liquid fuel supply means 1a Decalin storage container 1b Decalin supply pump 1c Pipe 2 Hydrogen separation means 2a Dehydrogenation reaction device (dehydrogenation reaction means) 2a1, 2a4 Heater 2a2 Fuel atomizer 2a3 Catalyst layer 2b Membrane separation device (hydrogen purification means) 3 Solid-liquid separating means 3a First heat exchanger 3b Second heat exchanger 3c Filtration device 4 Returning means 4a Sub-tank 4b Return pump 4c Pipe 5 Collecting means 5a Screw conveyor 5b Pellet former 5c Recovery tank 5d Tray 6 Fuel cell ( Hydrogen consumption equipment)

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Claims (3)

[Claims] 1. A dehydrogenation reaction means for dehydrogenating a liquid fuel composed of a hydrogen derivative obtained by hydrogenating an aromatic compound to separate hydrogen and other components, and a dehydrogenation reaction means for separating the liquid fuel from the liquid fuel. In a hydrogen supply device that has a hydrogen separation means configured with a hydrogen purification means for purifying the hydrogen that has been purified, and supplies hydrogen purified by the hydrogen purification means from the hydrogen separation means to a hydrogen consuming device, the other The component of the solid fuel liquid separation means for separating the unreacted liquid fuel and the solid content of the dehydrogenation compound produced by the dehydrogenation reaction, the liquid fuel separated by the solid liquid separation means,
A hydrogen supply device comprising return means for returning to the dehydrogenation reaction means. 2. The hydrogen supply device according to claim 1, further comprising a recovery unit for recovering a solid content of the dehydrogenation compound separated by the solid-liquid separation unit. 3. The hydrogen supply apparatus according to claim 2, wherein the recovery means is configured to recover the solid content of the dehydrogenation compound by pellet molding.