JP6757058B1 - Dehydrogenation system, catalyst holding device - Google Patents

Abstract

Provide a dehydrogenation system that facilitates maintenance of catalysts and heaters. The dehydrogenation system includes a reaction vessel, a resistance wire 21 that generates heat due to power supply, a cylinder portion 27 that covers the side portion of the resistance wire 21, and a catalyst coating portion 33 that covers at least a part of the side portion of the cylinder portion 27. A catalyst holding device 20 having a catalyst 31 provided between the cylinder portion 27 and the catalyst coating portion 33 and activating the dehydrogenation reaction is provided. Organic hydride is supplied from above the catalyst holding device 20. The catalyst coating portion 33 has pores through which hydrogen is passed through the organic hydride and the aromatic compound generated by the dehydrogenation reaction without passing through the catalyst 31. The reaction vessel holds the catalyst holding device 20 in a state where the catalyst coating portion 33 is located inside the reaction vessel and a part of the terminal 23 of the resistance wire 21 is exposed to the outside of the reaction vessel.

Description

The present invention relates to a dehydrogenation system and the like.

Conventionally, as in Patent Document 1, an apparatus including a dehydrogenation system has been proposed.

Japanese Unexamined Patent Publication No. 2002-184436

However, for the maintenance of the heater to warm the catalyst or catalyst which activates the dehydrogenation reaction, it has not been particularly considered.

Therefore, an object of the present invention is to provide a dehydrogenation system or the like that facilitates maintenance of catalysts and heaters.

The dehydrogenation system according to the present invention includes a reaction vessel, a resistance wire that generates heat due to power supply, a cylinder portion that covers the side portion of the resistance wire, a catalyst coating portion that covers at least a part of the side portion of the cylinder portion, and a cylinder. It is provided with a catalyst holding device provided between the portion and the catalyst coating portion and having a catalyst for activating the dehydrogenation reaction. The raw material is supplied from above the catalyst holding device in the reaction vessel. The catalyst coating portion has holes for passing the raw material, hydrogen generated by the dehydrogenation reaction, and a substance desorbed from the raw material without passing the catalyst. The reaction vessel holds the catalyst holding device in a state where the catalyst coating portion is located inside the reaction vessel and a part of the terminal of the resistance wire is exposed to the outside of the reaction vessel.

In the dehydrogenation system, the catalyst holding device can be easily removed from the reaction vessel, and maintenance of the catalyst and the heater (resistance wire, etc.) in the catalyst holding device can be facilitated.
In addition, since the resistance wire and terminal through which the current flows are provided in the region where hydrogen is desorbed from the raw material such as organic hydride or the raw material such as an aromatic compound or in the region where hydrogen does not come into contact, the resistance wire and terminal can be prevented from deteriorating. ..

Preferably, the cylinder portion is provided with fins for heat dissipation. The fins are covered with a catalyst coating.

More preferably, the catalyst coating is attached to the cylinder in a removable state.

When the catalyst coating portion is attached to the cylinder portion in a removable state, the catalyst coating portion can be easily removed from the cylinder portion to replenish or replace the catalyst, or to replace the catalyst coating portion.

More preferably, the dehydrogenation system further comprises a spray section that is housed in a reaction vessel and atomizes the raw material.

By spraying the raw material, it is possible to easily pass through the pores of the catalyst coating portion, and it is possible to easily adjust the amount of the raw material supplied to the inside of the reaction vessel while supplying the raw material over a wide range.

More preferably, the spraying section sprays the raw material upward or diagonally upward.

In the case of spraying the raw material upward or diagonally upward, as compared with the form of spraying the raw material downward, the raw material is gently sprayed over a wide area inside the reaction vessel. Can be sprayed.

More preferably, the dehydrogenation system further comprises a hydrogen extractor for separating the hydrogen generated in the reaction vessel from other substances. The hydrogen extraction unit has a hydrogen separation membrane.

More preferably, the hydrogen extractor has a gas-liquid separator that cools the gas discharged from the reaction vessel and then separates the gas into a liquid. For the gas discharged from the gas-liquid separator, the hydrogen separation membrane is arranged downstream of the gas flow with respect to the gas-liquid separator so as to separate hydrogen from other substances.

By a two-step hydrogen extraction process using a gas-liquid separator and a hydrogen separation membrane, it is possible to extract hydrogen with less impurities and higher purity than the form using only one of the gas-liquid separator and the hydrogen separation membrane. It will be possible.

More preferably, the dehydrogenation system further comprises a suction pump that sucks the gas in the reaction vessel and guides it to the hydrogen extractor.

More preferably, the dehydrogenation system further comprises a gas discharge pipe that connects the reaction vessel and the hydrogen extractor. The gas discharge pipe has a slope portion extending in an oblique direction from the gas discharge port of the reaction vessel.

More preferably, the tubular portion has a cylindrical shape. The tubular portion is rotatably attached to the wall constituting the reaction vessel.

It is possible to rotate the catalyst holding device to stir the catalyst filled between the cylinder portion and the catalyst coating portion, and to adjust the portion where the sprayed raw material invades.

More preferably, the dehydrogenation system further comprises a second reaction vessel. From above the catalyst holding device in the second reaction vessel, the raw material discharged from the reaction vessel and the substance in which hydrogen is desorbed from the raw material are supplied.

More preferably, the wall constituting the reaction vessel has an opening for passing the catalyst holding device when the catalyst holding device is attached.

The catalyst holding device according to the present invention includes a resistance wire that generates heat due to power supply, a cylinder portion that covers the side portion of the resistance wire, a catalyst coating portion that covers at least a part of the side portion of the cylinder portion, and a cylinder portion and a catalyst coating. It is provided with a catalyst provided between the parts. The raw material is supplied from above the catalyst holding device in the reaction vessel. The catalyst coating portion has holes for passing the raw material, hydrogen generated by the dehydrogenation reaction, and a substance desorbed from the raw material without passing the catalyst. The catalyst holding device is held in the reaction vessel with a part of the terminals of the resistance wire exposed to the outside of the reaction vessel.

As described above, according to the present invention, it is possible to provide a dehydrogenation system or the like that facilitates maintenance of a catalyst or a heater.

It is a block diagram of the dehydrogenation system in this embodiment. It is sectional drawing of the catalyst holding apparatus. It is sectional drawing of the catalyst holding device at the time of filling a catalyst through an opening. In a modified example of this embodiment, it is a block diagram of a dehydrogenation system including a spraying portion for spraying upward and a gradient portion extending diagonally upward from the reaction vessel. It is a block diagram of the dehydrogenation system further provided with the 2nd reaction vessel.

Hereinafter, the first embodiment will be described with reference to the drawings.
The embodiment is not limited to the following embodiments. In principle, the contents described in one embodiment are similarly applied to other embodiments. In addition, each embodiment and each modification can be combined as appropriate.

The dehydrogenation system 1 in the present embodiment is a device that extracts hydrogen from an organic hydride (saturated condensed ring hydrocarbon) such as methylcyclohexane and supplies the hydrogen to an external power generator (not shown) or the like.
The dehydrogenation system 1 includes a raw material (organic hydride) tank 5, a dehydrogenation reactor 10, a gas discharge pipe 50, a liquid discharge pipe 52, a suction pump 60, a hydrogen extraction unit 70, a hydrogen tank 81, a separation liquid tank 82, and a detection unit. 91 and a control unit 93 are provided (see FIG. 1).

(Raw material tank 5)
The raw material tank 5 is a tank for storing the organic hydride, and the organic hydride stored in the raw material tank 5 is supplied to the spray section 43 of the dehydrogenation reactor 10 via a raw material pump (not shown) to perform a dehydrogenation reaction. By the dehydrogenation reaction in the vessel 10, it is separated into an aromatic compound such as toluene and hydrogen.

(Dehydrogenation reactor 10)
The dehydrogenation reactor 10 includes a catalyst holding device 20, a reaction vessel 41, and a spray unit 43.

(Catalyst holding device 20)
A plurality of catalyst holding devices 20 are provided while being held in the reaction vessel 41.
The catalyst holding device 20 is a device that heats the catalyst 31 by electric heating while holding the catalyst 31, and is held in the reaction vessel 41.
The catalyst holding device 20 includes a resistance wire 21, a caulking 22, a terminal (bobin) 23, an insulating powder 24, an insulating member 25, a nut 26, a tubular portion (heater pipe) 27, fins 29, a resistor fixing member 30, and a catalyst 31. It has a catalyst coating portion 33 and a coating portion fixing member 35 (see FIG. 2).

The resistance wire 21 has a coil shape such as a nichrome wire, and generates heat by supplying electric power.

The terminal 23 is electrically connected to the resistance wire 21 and is provided at both ends of the resistance wire 21.
The terminal 23 has a first end portion 23a, a second end portion 23b, and an intermediate portion 23c, and the first end portion 23a, the intermediate portion 23c, and the second end portion 23b are integrally formed.
The first end portion 23a has a male screw shape for screwing with the nut 26, and a part thereof is exposed from the tubular portion 27.
The second end portion 23b has a substantially cylindrical shape.
A part of the resistance wire 21 is wound around the second end portion 23b and fixed by spot welding or the like.
The intermediate portion 23c is sandwiched between the first end portion 23a and the second end portion 23b.

The portion of the terminal 23 exposed from the tubular portion 27 is exposed to the outside from the wall constituting the reaction vessel 41.
The portion of the terminal 23 exposed from the tubular portion 27 is connected to a power supply line (cable or the like) from a commercial power source.
The resistance wire 21 and the terminal 23 receive electric power from the commercial power source or the like.
However, the power supply source is not limited to the commercial power source, and may be a power generation device or a power storage device.

The tubular portion 27 holds the terminal 23 via the insulating member 25.
Further, the tubular portion 27 covers a part of the terminal 23 and the side surface of the resistance wire 21.
A part of the terminal 23 covered with the tubular portion 27 is a portion not exposed to the outside from the wall constituting the reaction vessel 41.

The cross-sectional configuration views of FIGS. 2 and 3 show a cross section of a portion other than the resistance wire 21, the terminal 23, and the nut 26, and show the side surfaces of the resistance wire 21, the terminal 23, and the nut 26.

Fins 29 for heat dissipation are provided on the side surface of the tubular portion 27.
It is desirable that the fins 29 are attached to the side surface of the tubular portion 27 in a detachable state.
The fin 29 radiates the heat generated by the resistance wire 21 to warm the adjacent catalyst 31 and activate the dehydrogenation reaction.

The inside of the tubular portion 27 is filled with an insulating powder 24 such as magnesia, and is hardened by compression and heat.
The insulating powder 24 is filled so as to cover a part of the first end portion 23a, the entire second end portion 23b, and the entire intermediate portion 23c.
The portion of the insulating powder 24 facing the insulating member 25, that is, the boundary portion between the insulating powder 24 and the insulating member 25 and a part of the male screw-shaped portion of the first end portion 23a are caulked 22 with silicone or the like. ..
A part of the male screw-shaped portion of the first end portion 23a and the insulating powder 24 are fixed via the caulking 22.

The nut 26 is screwed into the first end portion 23a with the insulating member 25 and the tubular portion 27 sandwiched between them.

The portion of the catalyst holding device 20 that does not conduct with the terminal 23 is held by the wall constituting the reaction vessel 41 via the resistor fixing member 30.
The portion of the catalyst holding device 20 that does not conduct with the terminal 23 may be near both ends of the tubular portion 27 that holds the terminal 23 via the insulating member 25.
The resistor fixing member 30 is formed of an insulating member at least in a region in contact with the cylinder portion 27, and holds the cylinder portion 27 so as to sandwich the cylinder.
The resistor fixing member 30 is fixed to the wall so as to close the first opening hole 41a and the second opening hole 41b in the wall constituting the reaction vessel 41 via a screw or the like, and the reaction vessel 41 and the catalyst holding device 30 are fixed to the wall. Seal between 20 and 20.

The tubular portion 27 has a cylindrical shape and holds the catalyst so that the terminal 23 can rotate around the axis on which the resistance wire 21 extends when the terminal 23 is loosened from the reaction vessel 41 by the resistor fixing member 30. It is desirable that the device 20 be held in the reaction vessel 41 in a rotatable state.
In this case, it is possible to rotate the catalyst holding device 20 to stir the catalyst 31 filled between the cylinder portion 27 and the catalyst coating portion 33, or to adjust the portion where the sprayed organic hydride invades. become.

(Catalyst 31, catalyst coating 33, coating fixing member 35)
The catalyst 31 is composed of platinum, a platinum salt, or the like that promotes the dehydrogenation reaction.
The regions marked with x in FIGS. 2 and 3 will be described as the regions filled with the catalyst 31.

The catalyst coating portion 33 is arranged around the cylinder portion 27 between both ends held by the reaction vessel 41 of the cylinder portion 27 so that the catalyst coating portion 33 is located inside the reaction vessel.
The catalyst coating portion 33 covers a part of the tubular portion 27, the fins 29 attached to the tubular portion 27, and the catalyst 31.
The catalyst 31 is held between the outer wall of the tubular portion 27 and the inner wall of the catalyst coating portion 33.
The catalyst coating portion 33 has pores that allow the organic hydride, the aromatic compound, and hydrogen to pass through without passing through the catalyst 31 (grains).
The catalyst coating portion 33 is composed of, for example, a sheet-like porous membrane.

It is desirable that the catalyst coating portion 33 is attached to the tubular portion 27 in a removable state by the coating portion fixing member 35.
The catalyst coating portion 33 may be attached to the cylinder portion 27 by the coating portion fixing member 35 by fastening with a binding band or brazing.

Therefore, by releasing the attachment of the catalyst coating portion 33 to the tubular portion 27 by the coating portion fixing member 35, the portion of the catalyst holding device 20 excluding the catalyst 31, the catalyst coating portion 33, and the coating portion fixing member 35 remains as it is. Therefore, at least one of the catalyst 31, the catalyst coating portion 33, and the coating portion fixing member 35 can be replaced with new ones.

The catalyst holding device 20 has a configuration in which a catalyst 31 and a catalyst coating portion 33 are attached to a resistor including a resistance wire 21 via a coating portion fixing member 35.

(Catalyst 31 filling procedure)
Filling of the catalyst 31 between the catalyst coating portion 33 and the cylinder portion 27 proceeds according to the following procedure or the like.
One end of the catalyst coating 33 is attached to one end of the cylinder 27 (one between the fins 29 and the insulating member 25) using the coating fixing member 35 (see FIG. 3).
At this time, the other end of the tubular portion 27 (the other between the fin 29 and the wall of the insulating member 25) is not attached using the covering portion fixing member 35, and the catalyst coating portion 33 and the tubular portion 27 In the meantime, the opening OP for catalyst injection is created.
While holding the catalyst coating portion 33 and the cylinder portion 27 so that the catalyst charging opening OP faces substantially upward, the catalyst coating portion 33 and the cylinder portion 27 are separated from each other through the catalyst charging opening OP. , The catalyst 31 is charged.
It is desirable to vibrate or rotate the cylinder portion 27 and the catalyst coating portion 33 so that the catalyst 31 is uniformly arranged between the cylinder portion 27 and the catalyst coating portion 33.
After the charging of the catalyst 31 is completed, the other end of the covering portion fixing member 35 is attached to the other end of the tubular portion 27 (the other between the fin 29 and the insulating member 25).
As a result, the catalyst 31 is held between the tubular portion 27 and the catalyst coating portion 33 in a state where it can come into contact with the fins 29.

(Reaction vessel 41)
The reaction vessel 41 is a vessel that promotes a dehydrogenation reaction that separates the raw material (organic hydride) sprayed from the spray unit 43 into hydrogen and an aromatic compound via the catalyst holding device 20 (see FIG. 1).
The wall constituting the reaction vessel 41 holds a plurality of catalyst holding devices 20.
The wall constituting the reaction vessel 41 has a first opening hole 41a and a second opening hole 41b.
When the catalyst holding device 20 is attached to the wall, the first opening hole 41a has a hole shape larger than the maximum diameter portion of the catalyst holding device 20 in order to pass the catalyst holding device 20. In the present embodiment, the first opening hole 41a has a hole shape through which the catalyst coating portion 33 corresponding to the maximum diameter portion passes.
The second opening hole 41b has substantially the same shape as the outer shape of the tubular portion 27 in order to hold the tubular portion 27.

Further, the spray unit 43 is held inside the reaction vessel 41.
Further, on the side of the wall constituting the reaction vessel 41, an opening (gas discharge port 45) for discharging the gas obtained by the dehydrogenation reaction is provided.
Further, below the wall constituting the reaction vessel, an opening (liquid discharge port 47) for discharging the liquid is provided.
The gas discharge port 45 may be provided on the upper surface of the wall constituting the reaction vessel 41.

(Spraying unit 43)
The spray unit 43 is provided inside the reaction vessel 41 and sprays the raw material (organic hydride) supplied from the raw material tank 5 in the form of mist.
The spraying unit 43 may be in the form of spraying the raw material downward, but may be in the form of spraying the raw material upward or diagonally upward as shown in FIG.
In the case of spraying the raw material upward or diagonally upward, as compared with the form of spraying the raw material downward, the amount of the raw material sprayed upward is slower and the inside of the reaction vessel 41 is wider. It becomes possible to spray the raw material.
A plurality of catalyst holding devices 20 are arranged below the spraying unit 43.

By spraying the organic hydride, it is possible to easily pass through the pores of the catalyst coating portion 33, and it is possible to easily adjust the amount of the organic hydride to be supplied to the inside of the reaction vessel 41 while supplying the organic hydride to a wide range.
However, the supply of the organic hydride from above the catalyst holding device 20 is not limited to the spraying using the spraying unit 43, and the organic hydride may be poured from above the catalyst holding device 20.

(Gas discharge pipe 50)
One end of the gas discharge pipe 50 communicates with the gas discharge port 45.
The other end of the gas discharge pipe 50 communicates with the hydrogen extraction unit 70.
The gas discharge pipe 50 is provided with a suction pump 60 for sucking gas from the reaction vessel 41 and guiding it to the hydrogen extraction unit 70.
It is desirable that one end of the gas discharge pipe 50 is provided with a gradient portion 50a in an oblique direction so that a gas such as hydrogen sucked by the suction pump 60 can easily flow.
FIG. 1 shows an example of a gas discharge pipe 50 provided with a slope portion 50a diagonally downward from the gas discharge port 45.
FIG. 4 shows an example of a gas discharge pipe 50 provided with a slope portion 50a in an obliquely upward direction from the gas discharge port 45.
The gas generated in the reaction vessel 41 is supplied to the hydrogen extraction unit 70 through the gas discharge pipe 50 by suction of the suction pump 60.
The gas generated in the reaction vessel 41 contains hydrogen, vaporized organic hydride, vaporized aromatic compound and the like.

As shown in FIGS. 1 and 4, the suction pump 60 may be provided between the reaction vessel 41 and the first separation unit 71, or between the first separation unit 71 and the second separation unit 72. Alternatively, it may be provided between the second separation portion 72 and the hydrogen tank 81. Further, suction pumps 60 are provided at two or more locations between the reaction vessel 41 and the first separation unit 71, between the first separation unit 71 and the second separation unit 72, and between the second separation unit 72 and the hydrogen tank 81. It may be in the form of

(Liquid discharge pipe 52)
One end of the liquid discharge pipe 52 communicates with the liquid discharge port 47.
The other end of the liquid discharge pipe 52 communicates with the separation liquid tank 82.
In the reaction vessel 41, the liquid flowing below the catalyst holding device 20 is supplied to the separation liquid tank 82 through the liquid discharge pipe 52.

(Hydrogen extraction unit 70)
The hydrogen extraction unit 70 has a first separation unit 71 and a second separation unit 72.

The first separation unit 71 includes a cooling device and a gas-liquid separator.
The cooling device of the first separation unit 71 is composed of a chiller or the like and cools the gas from the reaction vessel 41.
The gas-liquid separator of the first separation unit 71 separates the substance cooled by the cooling device of the first separation unit 71 into a liquid and a gas.
The liquid (liquefied organic hydride and liquefied aromatic compound) separated by the first separation unit 71 is supplied to the separation liquid tank 82.
The gas separated by the first separation unit 71 (hydrogen, unliquefied organic hydride, unliquefied aromatic compound, and impurities) is supplied to the second separation unit 72.

The second separation unit 72 has a hydrogen separation membrane for separating hydrogen and other substances other than hydrogen.
The hydrogen separation membrane of the second separation unit 72 is attached to the gas-liquid separator of the first separation unit 71 so that hydrogen is separated from other substances in the gas discharged from the gas-liquid separator of the first separation unit 71. On the other hand, it is located downstream of the gas flow.
The hydrogen separated by the second separation section 72, that is, the hydrogen that has passed through the hydrogen separation membrane is supplied to the hydrogen tank 81.
A substance other than hydrogen separated by the second separation section 72, that is, a substance that has not passed through the hydrogen separation membrane is supplied to the separation liquid tank 82 or another tank (not shown).

Compared with the form using only one of the gas-liquid separator and the hydrogen separation membrane by the two-step hydrogen extraction treatment by the gas-liquid separator of the first separation part 71 and the hydrogen separation membrane of the second separation part 72. It is possible to extract hydrogen with few impurities and high purity.

(Hydrogen tank 81)
The hydrogen tank 81 stores the hydrogen generated in the reaction vessel 41 and extracted by the hydrogen extraction unit 70.
The hydrogen tank 81 may communicate with a power generator (not shown) in a state where hydrogen can be supplied.
The electric power generator generates electric power based on the electric power supplied from the hydrogen tank 81, and supplies electric power to a power storage device (not shown) and an electric device (not shown).
Further, the hydrogen extracted by the hydrogen extraction unit 70 may be directly supplied to the electric power generator without providing the hydrogen tank 81.

(Separation liquid tank 82)
The separation liquid tank 82 stores substances other than hydrogen (organic hydride, aromatic compound, etc.) discharged from the reaction vessel 41.

(Detection unit 91, control unit 93)
The detection unit 91 is provided with a temperature sensor or the like inside the reaction vessel 41 and in the vicinity of the catalyst holding device 20, and acquires information on the temperature in the vicinity of the catalyst holding device 20.
The control unit 93 controls the electrical equipment constituting the dehydrogenation system 1, such as the catalyst holding device 20, the spray unit 43, and the suction pump 60.
In particular, the control unit 93 adjusts the power supply to the catalyst holding device 20 based on the information regarding the temperature in the vicinity of the catalyst holding device 20 obtained by the detection unit 91.
The amount of heat generated from the resistance wire 21 is adjusted by adjusting the power supply to the catalyst holding device 20.
This makes it possible to adjust the amount and timing of spraying the raw material (organic hydride) from the spray unit 43 and the amount and timing of sucking the gas by the suction pump 60 in a state where the dehydrogenation reaction is activated.

(Hydrogen extraction procedure)
Next, the procedure for extracting hydrogen using the dehydrogenation system 1 in the present embodiment will be described.
A catalyst holding device 20 and a spraying portion 43 are attached to the reaction vessel 41 in advance.
The raw material tank 5 is communicated with the spray unit 43.
A gas discharge pipe 50 is attached to the gas discharge port 45 of the reaction vessel 41, and a liquid discharge pipe 52 is attached to the liquid discharge port 47 of the reaction vessel 41.
A suction pump 60, a hydrogen extraction unit 70, and a hydrogen tank 81 are attached to the gas discharge pipe 50.
A separation liquid tank 82 is attached to the liquid discharge pipe 52.

The control unit 93 causes the catalyst holding device 20 to supply electric power to a commercial power source or the like.
As a result, the resistance wire 21 generates heat, and the heat of the resistance wire 21 is transferred to the fins 29 via the insulating powder 24 and the tubular portion 27.
The catalyst 31 is heated by heat from the cylinder portion 27 and the fins 29.
When the catalyst 31 reaches a predetermined temperature (for example, 350 ° C.), the dehydrogenation reaction becomes active.
When the control unit 93 determines that the catalyst 31 has reached the predetermined temperature based on the information from the detection unit 91 or the elapsed time after the power supply to the catalyst holding device 20 is started, the control unit 93 Starts spraying of organic hydride by the spraying unit 43.
After a predetermined time has elapsed after the spraying of the organic hydride by the spraying unit 43 is started, the control unit 93 starts the operation of the suction pump 60.
A part of the organic hydride sprayed from the spray portion 43 passes through the hole of the catalyst coating portion 33 of the catalyst holding device 20 and comes into contact with the catalyst 31.
At this time, the organic hydride is separated into hydrogen and an aromatic compound by a dehydrogenation reaction.
Organic hydrides, aromatic compounds, and hydrogen are discharged from between the tubular portion 27 and the catalyst coating portion 33 in the catalyst holding device 20 through the holes of the catalyst coating portion 33.
Of the substances discharged from the catalyst coating unit 33, the gas in the reaction vessel 41 is sent to the hydrogen extraction unit 70 via the gas discharge pipe 50 by suction by the suction pump 60.
Among the substances discharged from the catalyst coating portion 33, the liquid in the reaction vessel is sent to the separation liquid tank 82 via the liquid discharge pipe 52.

In the first separation unit 71 of the hydrogen extraction unit 70, after the gas is cooled, it is separated into a gas (mainly hydrogen) and a liquid (mainly an organic hydride and an aromatic compound).
The gas separated by the first separation unit 71 is sent to the second separation unit 72.
The liquid separated by the first separation unit 71 is sent to the separation liquid tank 82.

The second separation section 72 of the hydrogen extraction section 70 separates hydrogen that has passed through the hydrogen separation membrane into other substances that have not passed through the hydrogen separation membrane.
The hydrogen separated by the second separation unit 72 is sent to the hydrogen tank 81.
The substance other than hydrogen separated by the second separation unit 72 is sent to the separation liquid tank 82 (or another tank).

The hydrogen generated in the reaction vessel 41 is stored in the hydrogen tank 81.
Organic hydrides and aromatic compounds are stored in the separation liquid tank 82.

(effect)
The catalyst holding device 20 is held in the reaction vessel 41 in a state where the catalyst 31 is held between the tubular portion 27 and the catalyst coating portion 33 and a part of the terminal 23 (a part of the first end portion 23a) is exposed from the reaction vessel 41. Is held in.
Therefore, in the dehydrogenation system 1, the catalyst holding device 20 can be easily removed from the reaction vessel 41, and maintenance of the catalyst and the heater (resistance wire 21 and the like) in the catalyst holding device 20 can be easily performed.
Further, since the resistance wire 21 and the terminal 23 through which the current flows are provided in the region where they do not come into contact with the organic hydride, the aromatic compound or hydrogen, the resistance wire 21 and the terminal 23 can be prevented from deteriorating.
Further, when the fins 29 are provided, the catalyst 31 is arranged between the cylinder portion 27, the fins 29, and the catalyst coating portion 33, and the cylinder portion 27 and the catalyst coating portion 33 are compared with the form in which the fins 29 are not provided. It is possible to easily arrange the catalyst 31 evenly in the region between them, and to easily transfer heat to the catalyst 31 evenly.
When the catalyst coating portion 33 is attached to the cylinder portion 27 in a removable state, the catalyst coating portion 33 is removed from the cylinder portion 27, and the catalyst 31 is replenished or replaced, or the catalyst coating portion 33 is replaced. You can do that easily.

In this embodiment, the embodiment in which only one reaction vessel 41 is provided has been described, but the embodiment in which two or more reaction vessels 41 are provided may be provided (see FIG. 5).
Specifically, a reaction vessel (second reaction vessel) 41 or the like is provided after the separation liquid tank 82, and a dehydrogenation reaction is carried out using substances (organic hydride and aromatic compound) stored in the separation liquid tank 82 as raw materials. Is done. That is, from above the catalyst holding device 20 in the second reaction vessel, the raw material discharged from the reaction vessel 41 in the previous stage and the substance in which hydrogen is desorbed from the raw material are supplied. In FIG. 5, the hydrogen tank 81 and the separation liquid tank 82 provided after the second reaction vessel 41 are not shown.
Further, a reaction vessel (third reaction vessel) 41 that causes the substances (organic hydride and aromatic compound) stored in the separation liquid tank 82 after the second dehydrogenation reaction to be subjected to the third dehydrogenation reaction. May be provided.
By performing the dehydrogenation reaction in a plurality of times, the amount of hydrogen generated inside each reaction vessel 41 can be suppressed, and the gas containing hydrogen can be easily discharged from the gas discharge pipe 50.

Further, in the present embodiment, it has been described that the raw material of the dehydrogenation system 1 is a ring hydrocarbon and the substance from which hydrogen is desorbed is an aromatic compound, but another substance that dehydrogenates hydrogen using the catalyst 31 ( A compound containing hydrogen) may be used as a raw material.
For example, ethanol , methanol , chain hydrocarbons and the like may be used as a raw material for the dehydrogenation system 1, and ammonia may be used as a raw material for the dehydrogenation system 1.

Although some embodiments of the present invention have been described, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention as well as the invention described in the claims and the equivalent scope thereof.

1 Dehydrogenation system 5 Raw material (organic hydride) tank 10 Dehydrogenation reactor 20 Catalyst holding device 21 Resistance wire 22 Caulking 23 Terminal (bobbin)
23a 1st end 23b 2nd end 23c Intermediate 24 Insulation powder 25 Insulation member 26 Nut 27 Cylinder 29 Fin 30 Resistor fixing member 31 Catalyst 33 Catalyst coating 35 Coating fixing member 41 Reaction vessel 41a 1st opening hole 41b 2nd opening hole 43 Spraying part 45 Gas discharge port 47 Liquid discharge port 50 Gas discharge pipe 50a Gradient part 52 Liquid discharge pipe 60 Suction pump 70 Hydrogen extraction part 71 1st separation part 72 2nd separation part 81 Hydrogen tank 82 Separation liquid Tank 91 Detection unit 93 Control unit OP Opening for charging catalyst

Claims (13)

Reaction vessel and
Provided between the cylinder portion and the catalyst coating portion, a resistance wire that generates heat due to power supply, a cylinder portion that covers the side portion of the resistance wire, a catalyst coating portion that covers at least a part of the side portion of the cylinder portion, and the catalyst coating portion. It is a dehydrogenation system equipped with a catalyst holding device having a catalyst for activating the dehydrogenation reaction.
The raw material is supplied from above the catalyst holding device in the reaction vessel.
The catalyst coating portion has holes for passing the raw material, hydrogen generated by the dehydrogenation reaction, and a substance desorbed from the raw material without passing the catalyst.
A dehydrogenation system in which the reaction vessel holds the catalyst holding device in a state where the catalyst coating portion is located inside the reaction vessel and a part of the terminal of the resistance wire is exposed to the outside of the reaction vessel. .. The cylinder portion is provided with fins for heat dissipation.
The dehydrogenation system according to claim 1, wherein the fins are covered with the catalyst coating portion. The dehydrogenation system according to claim 1 or 2, wherein the catalyst coating portion is attached to the cylinder portion in a removable state. The dehydrogenation system according to any one of claims 1 to 3, further comprising a spray unit housed in the reaction vessel and spraying the raw material in a mist form. The dehydrogenation system according to claim 4, wherein the spraying unit sprays the raw material in an upward direction or an obliquely upward direction. Further provided with a hydrogen extraction unit for separating hydrogen generated in the reaction vessel from other substances,
The dehydrogenation system according to any one of claims 1 to 5, wherein the hydrogen extraction unit has a hydrogen separation membrane. The hydrogen extractor has a gas-liquid separator that cools the gas discharged from the reaction vessel and then separates the gas into a liquid.
6. The hydrogen separation membrane is arranged downstream of the gas flow with respect to the gas-liquid separator so as to separate hydrogen from other substances in the gas discharged from the gas-liquid separator. Dehydrogenation system described in. The dehydrogenation system according to claim 6 or 7, further comprising a suction pump that sucks the gas in the reaction vessel and guides it to the hydrogen extraction unit. Further provided with a gas discharge pipe for communicating the reaction vessel and the hydrogen extraction unit,
The dehydrogenation system according to claim 8, wherein the gas discharge pipe has a slope portion extending in an oblique direction from the gas discharge port of the reaction vessel. The tubular portion has a cylindrical shape and has a cylindrical shape.
The dehydrogenation system according to any one of claims 1 to 9, wherein the tubular portion is attached to a wall constituting the reaction vessel in a rotatable state. Further equipped with a second reaction vessel
The invention according to any one of claims 1 to 10, wherein the raw material discharged from the reaction vessel and a substance dehydrogenated from the raw material are supplied from above the catalyst holding device in the second reaction vessel. Dehydrogenation system. The dehydrogenation system according to any one of claims 1 to 11, wherein the wall constituting the reaction vessel has an opening for passing the catalyst holding device when the catalyst holding device is attached. A resistance wire that generates heat due to power supply,
A tubular portion that covers the side portion of the resistance wire and
A catalyst coating portion that covers at least a part of the side portion of the cylinder portion,
A catalyst holding device including a catalyst provided between the cylinder portion and the catalyst coating portion .
Raw material is supplied from above the catalyst retainer device at the anti-reaction container unit,
The catalyst coating portion has holes for passing the raw material, hydrogen generated by the dehydrogenation reaction, and a substance desorbed from the raw material without passing the catalyst.
The catalyst holding device is held in the reaction vessel in a state where a part of the terminal of the resistance wire is exposed to the outside of the reaction vessel.

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