JP2005213069A - Hydrogen supply/storage apparatus and hydrogen supply/storage system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To perform the supply and storage of hydrogen inexpensively by utilizing the dehydrogenation reaction and hydrogen addition reaction between a saturated hydrocarbon and an unsaturated hydrocarbon. <P>SOLUTION: The hydrogen supply/storage apparatus is equipped with a raw material tank 1 containing a hydrogen supply body or a hydrogen storage body as a raw material, a reaction tower 2 for causing the dehydrogenation reaction or hydrogen addition reaction of the raw material supplied from the raw material tank 1, and a recovery tank 3 for recovering, from the reaction tower 2, a product formed by the dehydrogenation reaction or hydrogen addition reaction. The reaction tower 2 is equipped with a combustion apparatus 23 for burning a part of the raw material from the raw material tank 1 and a catalyst-filled body 24 filled with a catalyst 27 and for introducing thereinto the raw material from the raw material tank 1. The catalyst-filled body 24 has a reaction tube 25 connected to the raw material tank 23 and to the recovery tank 3 and filled with the catalyst 27 and has a fin 26 attached to the periphery thereof. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a hydrogen supply / storage that supplies or stores hydrogen using a hydrogen supplier capable of supplying hydrogen to the outside by a dehydrogenation reaction or a hydrogen reservoir capable of storing hydrogen from the outside by a hydrogen addition reaction. The present invention relates to an apparatus and a hydrogen supply / storage system.

  At present, thermal power generation and nuclear power generation are mainly methods for supplying electric energy, but such methods have various problems such as influence on the global environment, safety, and residual amount. In addition, automobiles mainly use hydrocarbon-based fuels such as gasoline, light oil, and propane gas, but such fuels have a problem of adversely affecting the global environment.

  In view of the above problems, hydrogen has recently attracted attention as a fuel for power generation. Since hydrogen can be generated by electrolysis of water, it is almost inexhaustible and is also a clean energy source that does not generate carbon dioxide after combustion.

  On the other hand, benzene and cyclohexane are known as cyclic hydrocarbons having the same carbon number. The former benzene is an unsaturated hydrocarbon in which carbon-carbon bonds are partially double bonds, while the latter cyclohexane is a saturated hydrocarbon that has no double bonds in carbon-carbon bonds. is there. For this reason, when hydrogen is added to benzene, cyclohexane is obtained, and when a part of hydrogen is removed from cyclohexane, benzene is obtained. Similarly, decalin is obtained by the hydrogenation reaction of naphthalene, and naphthalene is obtained by the dehydrogenation reaction of decalin. Thus, hydrogen can be stored and supplied by utilizing the hydrogenation reaction and dehydrogenation reaction of these hydrocarbons. Such hydrogen storage or supply technology is expected to be used as power for automobiles in addition to home-use power generation systems for home use (see, for example, Patent Document 1).

JP 2002-187702 A (abstract, etc.)

  However, for practical use of hydrogen supply and storage using dehydrogenation and hydrogenation reactions between saturated and unsaturated hydrocarbons, for example, effective use of raw materials or improvement of thermal efficiency Therefore, it is necessary to further reduce the cost.

  The present invention has been made in view of such a problem, and implements supply and storage of hydrogen using a dehydrogenation reaction and a hydrogenation reaction between a saturated hydrocarbon and an unsaturated hydrocarbon at a low cost. With the goal.

  In view of the above problems, the present invention, as a raw material, a raw material tank containing a hydrogen supply body capable of supplying hydrogen to the outside by a dehydrogenation reaction or a hydrogen storage body capable of storing hydrogen from the outside by a hydrogen addition reaction, A reaction tower for causing a dehydrogenation reaction or a hydrogenation reaction of the raw material from the raw material tank, and a recovery tank for recovering a product produced by the dehydrogenation reaction or the hydrogenation reaction from the reaction tower, A combustion apparatus for combusting a part of the raw material from the raw material tank, and a catalyst filling body that is filled with a catalyst for dehydrogenation reaction or hydrogen addition reaction and introduces the raw material from the raw material tank, the catalyst filling body being a raw material tank And a recovery tank, a hydrogen supply / storage device having a reaction tube filled with a catalyst and fins around the reaction tube. For this reason, since the hot air from the combustion apparatus moves in the direction of the other end of the catalyst packed body while coming into contact with the fins of the catalyst packed body, heat can be efficiently transmitted to the catalyst in the reaction tube. In addition, since the dehydrogenation reaction or hydrogenation reaction is caused by using the heat generated when the raw material in the raw material tank is burned, it is not necessary to use electric energy, and no fuel other than the raw material is used. I'll do it. Therefore, supply of hydrogen to the outside or storage of hydrogen from the outside can be realized at low cost.

  In addition to the above-mentioned invention, another invention of the present invention is a hydrogen supply / storage system having a structure in which a combustion device is connected to a recovery tank, and a part or all of the products in the recovery tank are introduced into the combustion device and burned It is a device. For this reason, the by-product of hydrogen generation can be used effectively as a fuel, and it is not necessary to use a fuel other than the raw material, thereby further reducing the cost.

  Further, in addition to the above-described invention, another present invention is a heat exchanger disposed between the raw material tank and the reaction tube, and a waste heat supply pipe connecting the exhaust heat port of the reaction tube and the heat exchanger. And a hydrogen supply / storage device. For this reason, before introducing a raw material into a reaction tower, a raw material can be preheated using exhaust heat. Therefore, heat can be used efficiently, and further cost reduction and labor saving can be achieved.

  In addition to the above-mentioned inventions, another invention of the present invention is provided with a pressure regulating valve that opens when the pressure in the reaction tube reaches a predetermined pressure or higher, between the product discharge port of the reaction tube and the recovery tank. Hydrogen supply / storage device. For this reason, the reaction rate in the reaction tube can be further increased. This is particularly effective when a hydrogen storage material is used as a raw material and a hydrogen addition reaction is carried out by hydrogenation with external hydrogen.

  In addition to the above-mentioned inventions, another invention of the present invention is provided with a pressure adjusting valve that opens when the pressure in the reaction tube reaches a predetermined pressure or higher in the fuel supply pipe connecting the recovery tank and the combustion device. Hydrogen supply / storage device. For this reason, the reaction rate in the reaction tube can be further increased. This is particularly effective when a hydrogen storage material is used as a raw material and a hydrogen addition reaction is carried out by hydrogenation with external hydrogen. In addition, when hydrogen addition reaction is performed, only an amount of hydrogen necessary for the reaction is supplied, and it is not necessary to recover surplus hydrogen. For this reason, further cost reduction and labor saving can be achieved.

  In another aspect of the present invention, when the hydrogen supply / storage device is used as a hydrogen storage device, in addition to the above-described invention, the recovery tank and the hydrogen supply port side of the reaction tube are connected, and the hydrogen in the recovery tank is Is a hydrogen supply / storage device that reacts with a hydrogen storage body. For this reason, the hydrogen reacted with the hydrogen storage body can be used effectively. Therefore, further cost reduction can be achieved.

  In addition to the above-described inventions, another invention of the present invention is a hydrogen supply / storage device provided with fins in the inner periphery of the reaction tower. For this reason, the hot air from the combustion apparatus is disturbed between the fins in the tower and the fins around the reaction tube, and the efficiency with which the hot air contacts the fins can be improved. As a result, the thermal efficiency is increased. Therefore, further cost reduction can be achieved.

  In addition to the above-mentioned invention, another invention of the present invention is a hydrogen supply / storage device in which the fins in the tower are ring-shaped or spiral-shaped and are alternately formed in the vertical direction with the fins of the reaction tube. The hot air from the combustor transfers heat to the fins while passing through the route formed by the fins in the tower and the fins around the reaction tube, so that the efficiency of hot air contacting the fins can be improved, and as a result , Increase thermal efficiency. Therefore, further cost reduction can be achieved.

  In addition to the above-described inventions, another invention of the present invention is a hydrogen supply / storage in which a reaction tube is arranged so that the direction in which the raw material moves and the direction in which the hot air from the combustion device moves intersect in the reaction tower. It is a device. For this reason, the probability that the hot air from a combustion apparatus contacts a fin increases, and thermal efficiency increases. Therefore, further cost reduction can be achieved.

  Another embodiment of the present invention is a raw material tank containing a hydrogen supply body capable of supplying hydrogen to the outside by a dehydrogenation reaction or a hydrogen storage body capable of storing hydrogen from the outside by a hydrogen addition reaction, and a raw material tank. A reaction tower for causing a dehydrogenation reaction or a hydrogenation reaction of the raw material from, and a recovery tank for recovering a product generated by the dehydrogenation reaction or the hydrogenation reaction from the reaction tower, wherein the reaction tower is a raw material tank A combustion apparatus for combusting a part of the raw material from and a catalyst filling body charged with a catalyst for dehydrogenation reaction or hydrogen addition reaction and introducing the raw material from the raw material tank, and the catalyst filling body has a moving direction of the raw material A plurality of first openings that are open at both ends, and a plurality of second openings that are open at both ends in a direction crossing the first opening, a direction facing each other, or a parallel direction. The catalyst was loaded into parts, the second opening, and a hydrogen supply and storage device through the hot air from the combustion device. For this reason, the hot air from a combustion apparatus can be efficiently transmitted to a catalyst, and thermal efficiency increases. Therefore, further cost reduction can be achieved.

  In another aspect of the present invention, a plurality of the hydrogen supply / storage devices described above are arranged, a recovery tank of the hydrogen supply / storage device on the upper stream side, and an adjacent hydrogen supply / storage located on the lower stream side thereof. The hydrogen supply / storage system is connected to the raw material supply port of the catalyst packing body of the apparatus, and the raw material in the recovery tank is used for the reaction of the adjacent hydrogen supply / storage device. For this reason, the raw material which exists in a collection | recovery tank can be used again as a raw material in the downstream apparatus. Therefore, the conversion rate between the hydrogen supply body and the hydrogen storage body can be further increased, and hydrogen can be supplied or stored at low cost.

  According to the present invention, supply and storage of hydrogen using a dehydrogenation reaction and a hydrogen addition reaction between a saturated hydrocarbon and an unsaturated hydrocarbon can be performed at a low cost.

  Embodiments of a hydrogen supply / storage device and a hydrogen supply / storage system according to the present invention will be described below in detail with reference to the drawings.

  The following two reaction formulas are formulas showing the dehydrogenation reaction of saturated hydrocarbons. As shown in these reaction formulas, unsaturated hydrocarbons are produced by dehydrogenation of saturated hydrocarbons.

C ₁₀ H ₁₈ → C ₁₀ H ₈ + 5H ₂ (Decalin dehydrogenation reaction)
C ₆ H ₁₂ → C ₆ H ₆ + 3H ₂ (cyclohexane dehydrogenation reaction)
C ₇ H ₁₄ → C ₇ H ₈ + 3H ₂ (dehydrogenation of methylcyclohexane)

  On the other hand, the following two reaction formulas are formulas showing the hydrogenation reaction of unsaturated hydrocarbons. As shown in these reaction formulas, saturated hydrocarbons are produced by hydrogen addition to unsaturated hydrocarbons.

C ₁₀ H ₈ + 5H ₂ → C ₁₀ H ₁₈ (Naphthalene hydrogenation reaction)
C ₆ H ₆ + 3H ₂ → C ₆ H ₁₂ (benzene hydrogenation reaction)
C ₇ H ₈ + 3H ₂ → C ₇ H ₁₄ (hydrogen addition reaction of toluene)

  In this manner, hydrogen can be supplied to the outside by utilizing a dehydrogenation reaction of a hydrocarbon-based raw material in which carbons are single-bonded like a saturated hydrocarbon. In addition, hydrogen from the outside can be stored by utilizing a hydrogen addition reaction of a hydrocarbon-based raw material containing a double bond or a triple bond in a bond between carbons such as an unsaturated hydrocarbon. Hereinafter, hydrocarbon-based raw materials that release hydrogen present in itself, such as decalin, cyclohexane, or methylcyclohexane, are referred to as “hydrogen suppliers”, and, from the outside, such as naphthalene, benzene, or toluene. A hydrocarbon-based raw material that stores hydrogen by combining with hydrogen is referred to as a “hydrogen storage body”.

  Hereinafter, the configuration and function of an apparatus capable of supplying hydrogen to the outside using decalin dehydrogenation will be mainly described. However, the hydrogen supply / storage apparatus of the present invention is for saturated hydrocarbons other than decalin. A device for supplying hydrogen to the outside using a dehydrogenation reaction or a device for storing hydrogen from the outside using a hydrogenation reaction of an unsaturated hydrocarbon is included.

(First embodiment)
FIG. 1 is a diagram showing a configuration of a first embodiment of a hydrogen supply / storage device according to the present invention.

  The hydrogen supply / storage device according to the first embodiment is generated by a raw material tank 1 containing decalin, which is an example of a hydrogen supplier, a reaction tower 2 for causing decalin dehydrogenation, and decalin dehydrogenation. A recovery tank 3 for recovering naphthalene out of the resulting products (naphthalene, hydrogen, etc., which is an example of a hydrogen storage body) is provided.

  A raw material discharge port 4 a of the raw material tank 1 and a raw material supply port 4 b of the reaction tower 2 are connected by a raw material supply pipe 4, and a liquid feed pump 5 is disposed in the middle of the raw material supply pipe 4. Yes. For this reason, decalin in the raw material tank 1 can be supplied into the reaction tower 2 by the liquid feed pump 5. The product discharge port 6a of the reaction tower 2 and the product supply port 6b of the recovery tank 3 are connected by a product discharge pipe 6, and a cooling device is provided in the middle of the product discharge pipe 6. 7 is arranged. Of the products discharged from the reaction tower 2, naphthalene, unreacted decalin, intermediates before becoming naphthalene, and the like are recovered in the recovery tank 3 while being cooled by the cooling device 7 and liquefied. On the other hand, the hydrogen produced by the dehydrogenation reaction of decalin is not liquefied even when cooled by the cooling device 7, is separated from naphthalene or unreacted decalin by gas-liquid separation, enters the recovery tank 3, and is discharged outside the device. Is done.

  The fuel discharge port 8 a of the recovery tank 3 and the fuel supply port 8 b of the reaction tower 2 are connected by a fuel supply pipe 8. A liquid feed pump 9 is disposed in the middle of the fuel supply pipe 8. Yes. In this embodiment, products such as naphthalene and unreacted decalin in the recovery tank 3 are used as fuel for heating the catalyst required for decalin dehydrogenation. The contents in the collection tank 3 are sent by a liquid feed pump 9 to a combustion device 23 (described later) attached to the reaction tower 2. The fuel may be either naphthalene alone, a mixture of naphthalene and decalin, or a mixture of naphthalene, decalin, and other intermediate products as long as it is the contents in the recovery tank 3.

  The fuel discharge port 10 a of the raw material tank 1 and the fuel supply port 10 b of the reaction tower 2 are connected by a fuel supply pipe 10, and a liquid feed pump 11 is arranged in the middle of the fuel supply pipe 10. Has been. In this embodiment, decalin in the raw material tank 1 is used as a fuel for heating a catalyst required for decalin dehydrogenation. Decalin in the raw material tank 1 is sent to the combustion device 23 attached to the reaction tower 2 by the liquid feed pump 11.

  Furthermore, the hydrogen supply / storage device of the first embodiment includes an air supply fan 12. The air from the air supply fan 12 is supplied to the reaction tower 2 through the air supply pipe 13 that connects the air discharge port 13 a of the air supply fan 12 and the air supply port 13 b of the reaction tower 2. It is used to send the generated heat into the reaction tower 2. A flow rate regulator 14 is disposed in the middle of the air supply pipe 13, and the flow rate of the air supplied to the reaction tower 2 through the air supply pipe 13 is controlled by the flow rate regulator 14.

  The air from the air supply fan 12 is also supplied to the air supply port 15 b of the combustion device 23 through the air supply piping 15 extending from the branch point 15 a in the middle of the air supply piping 13, and the fuel in the combustion device 23 Used for combustion. A flow rate regulator 16 is disposed in the middle of the air supply pipe 15, and the flow rate regulator 16 controls the flow rate of air supplied to the combustion device 23 through the air supply pipe 15.

  The reaction tower 2 includes a reaction chamber 21 and a hot air generation chamber 22. The reaction chamber 23 is connected to the raw material tank 1 on the decalin supply side, and is connected to the recovery tank 3 on the side of discharging products such as naphthalene and hydrogen. On the other hand, the hot air generation chamber 22 is connected to the air supply pipe 13 and supplied with air from the air supply fan 12.

  A combustion device 23 is attached to the opposite side of the reaction chamber 21 across the hot air generation chamber 22. In the combustion device 23, the contents in the recovery tank 3 and the decalin in the raw material tank 1 are burned. The heat generated thereby is carried into the reaction chamber 21 by the air supplied to the hot air generation chamber 22 through the air supply pipe 13.

  Inside the reaction chamber 21, a fin tube 24, which is a catalyst filler, is attached. The fin tube 24 has a large number of fins 26 around one reaction tube 25. The reaction tube 25 is filled with a pellet-shaped catalyst 27. Decalin from the raw material tank 1 flows from one side of the reaction tube 25 to the other side through the gap of the catalyst 27 filled in the reaction tube 25. In the middle, decalin causes a dehydrogenation reaction on the surface of the catalyst 27 heated by the hot air from the hot air generating chamber 22 and decomposes into naphthalene and hydrogen.

  Since the hot air from the hot air generating chamber 22 moves in the direction of the other end of the fin tube 24 while making contact with many fins 26, heat can be efficiently transferred to the catalyst 27 in the reaction tube 25. Further, since decalin in the raw material tank 1 is used as a fuel and the dehydrogenation reaction or hydrogenation reaction is caused by using the heat generated when it is burned, it is not necessary to use electrical energy. In addition to decalin, no special fuel is required. Therefore, supply of hydrogen to the outside can be realized at low cost.

  In this embodiment, the hot air flow direction is opposite to the decalin movement direction, but the hot air flow direction may be the same as the decalin movement direction. However, it is possible to increase the reaction efficiency by increasing the downstream side of decalin to a high temperature and gradually decalin moving to the high temperature side while being preheated to dehydrogenate.Therefore, the direction of hot air flow and the direction of decalin flow can be determined. The reverse direction is more desirable.

  In this embodiment, the pellet-shaped catalyst 27 is used, but the shape of the catalyst is not limited to such a shape, and may be any shape such as powder, granule, or plate. In addition to the oil burner using decalin and naphthalene as fuel, a combustion catalyst type heating device using a noble metal catalyst may be used as the combustion device 23.

  Further, the fuel supplied to the combustion device 23 uses a part of decalin in the raw material tank 1 as fuel when a product such as naphthalene is not stored in the recovery tank 3, and as the dehydrogenation reaction proceeds, A product such as naphthalene stored in the recovery tank 3 may be used as a fuel, and thereafter, the use of decalin in the raw material tank 1 as a fuel may be stopped. Alternatively, naphthalene may be put in the recovery tank 3 from the beginning, and only the contents in the recovery tank 3 may be supplied to the combustion device 23 as fuel. Alternatively, only decalin in the raw material tank 1 may be supplied to the combustion device 23 as fuel.

  In addition, when the raw material in the raw material tank 1 is a liquid, the liquid feeding pumps 5 and 11 are pumps which send the raw material in the liquid state. However, when the raw material in the raw material tank 1 is a gas, a pump for discharging gas may be adopted instead of the liquid feed pumps 5 and 11. Furthermore, the liquid feed pumps 5 and 11 are not essential components in the present invention. When liquid raw material is put into the raw material tank 1 and the raw material tank 1 is arranged at a position higher than the reaction tower 2, the raw material is put into the reaction tower 2 and the combustion device 23 without using the liquid feed pumps 5 and 11. It can be supplied. Further, the raw material can be supplied into the reaction tower 2 and the combustion device 23 by putting a compressed gaseous raw material into the raw material tank 1 and disposing a pressure regulator at the position of the liquid feed pumps 5 and 11.

(Second Embodiment)
FIG. 2 is a diagram showing the configuration of the second embodiment of the hydrogen supply / storage device according to the present invention.

  Since the hydrogen supply / storage device of the second embodiment has a configuration similar to that of the first embodiment described above, the same reference numerals are given to the components common to both embodiments. The description is omitted.

  The hydrogen supply / storage device of the second embodiment is different from the hydrogen supply / storage device of the first embodiment in that a heat exchanger 28 is arranged in the middle of the raw material supply pipe 4. Yes. The exhaust heat outlet 29 a on the hot air exhaust side in the reaction chamber 21 and the exhaust heat supply port 29 b of the heat exchanger 28 are connected by an exhaust heat supply pipe 29. The hot air that has passed through the reaction chamber 21 from the combustion chamber 22 is sent to the heat exchanger 28 through the exhaust heat supply pipe 29. In the heat exchanger 28, decalin is preheated by hot air. For this reason, since decalin can be preheated using exhaust heat before introducing decalin into the reaction tower 2, the dehydrogenation reaction of decalin can be further promoted. The heat exchanger 28 may be disposed on the upstream side of the raw material instead of the downstream side of the raw material with respect to the liquid feed pump 5.

(Third embodiment)
FIG. 3 is a diagram showing a configuration of a third embodiment of the hydrogen supply / storage device according to the present invention.

  The hydrogen supply / storage device of the third embodiment is generated by a raw material tank 1 containing naphthalene, which is an example of a hydrogen storage body, a reaction tower 2 for causing a hydrogenation reaction of naphthalene, and a hydrogenation reaction of naphthalene. A recovery tank 3 for recovering the product (decalin, which is an example of a hydrogen supplier) and a hydrogen supply unit 31 for supplying hydrogen necessary for the hydrogen addition reaction to the reaction tower 2. Although the hydrogen supply part 31 will not be specifically limited if hydrogen can be supplied, In this embodiment, the hydrogen cylinder is employ | adopted. In addition, for example, a container containing a hydrogen storage alloy, organic hydride, or the like may be employed as the hydrogen supply unit.

  Note that the hydrogen supply / storage device of the third embodiment has a configuration similar to that of the first embodiment described above, and the same components are common to both the embodiments. Reference numerals are assigned and description thereof is omitted.

  The hydrogen port 32 a of the hydrogen supply unit 31 and the hydrogen supply port 32 b of the reaction tower 2 are connected by a hydrogen supply pipe 32. A check valve 33 and a flow rate regulator 34 are attached to the hydrogen supply pipe 32 in order from the hydrogen supply unit 31 side. Further, the hydrogen supply port 35 b connected to the hydrogen supply port 35 b and the hydrogen supply port 35 b connected to the hydrogen supply piping 32 are connected to each other at the upper part of the recovery tank 3. A check valve 36 is attached in the middle of the hydrogen recovery pipe 35.

  For this reason, in addition to hydrogen from the hydrogen supply unit 31, surplus hydrogen that has flowed from the reaction tower 2 to the recovery tank 3 is also supplied to the reaction tower 2. Therefore, since the hydrogen that has been carried to the recovery tank 3 without reacting with naphthalene can be used effectively, the cost of storing hydrogen can be further reduced.

  Further, a pressure regulating valve 37 is attached to the product discharge port 6 a side from the cooling device 7 in the product discharge pipe 6. The pressure regulating valve 37 is a valve that is closed until the pressure in the upstream reaction tube 25 is less than a predetermined pressure, but is opened when the pressure exceeds the predetermined pressure. The predetermined pressure can be set to a pressure that can improve the reaction rate of the hydrogenation reaction as long as the tensile strength of the reaction tube 25 and the product discharge pipe 6 is not exceeded. The predetermined pressure varies depending on the reaction conditions such as the raw material such as the hydrogen storage body and the temperature of the catalyst 27. The hydrogen addition reaction proceeds with a higher pressure than the dehydrogenation reaction. For this reason, in a hydrogen supply / storage device used for adding hydrogen to naphthalene and storing hydrogen from the outside, a pressure regulating valve 37 is attached to the outlet side of the reaction tube 25, It is preferable to cause the reaction to occur under conditions where the pressure is increased. However, a pressure regulating valve may be attached to a hydrogen supply / storage device used to supply hydrogen generated by decalin dehydrogenation to the outside.

(Fourth embodiment)
FIG. 4 is a diagram showing a configuration of a fourth embodiment of the hydrogen supply / storage device according to the present invention.

  The hydrogen supply / storage device according to the fourth embodiment is generated by a raw material tank 1 containing naphthalene as an example of a hydrogen storage body, a reaction tower 2 for causing a hydrogenation reaction of naphthalene, and a hydrogenation reaction of naphthalene. A recovery tank 3 for recovering the product (decalin, which is an example of a hydrogen supplier), and a hydrogen supply unit 31 for supplying hydrogen necessary for the hydrogen addition reaction to the reaction tower 2. Although the hydrogen supply part 31 will not be specifically limited if hydrogen can be supplied, In this embodiment, the hydrogen cylinder is employ | adopted. In addition, for example, a container containing a hydrogen storage alloy, organic hydride, or the like may be employed as the hydrogen supply unit.

  Note that the hydrogen supply / storage device of the fourth embodiment has a configuration similar to that of the third embodiment described above, and the same components are common to both embodiments. Reference numerals are assigned and description thereof is omitted.

  The hydrogen port 32 a of the hydrogen supply unit 31 and the hydrogen supply port 32 b of the reaction tower 2 are connected by a hydrogen supply pipe 32. A check valve 33 is attached to the hydrogen supply pipe 32 in order from the hydrogen supply unit 31 side. The fuel discharge port 8a at the lower portion of the recovery tank 3 and the fuel supply port 8b of the reaction tower 2 are connected by a fuel supply pipe 8, and a liquid feed pump is provided in the middle of the fuel supply pipe 8. 9 is arranged. Further, a pressure adjustment valve 38 is attached between the fuel discharge port 8 a and the liquid feed pump 9. The pressure regulating valve 38 is a closed state until the pressure in the recovery tank 3 is less than a predetermined pressure, but is opened when the pressure exceeds the predetermined pressure. The predetermined pressure can be set to a pressure capable of improving the reaction rate of the hydrogen addition reaction within a range not exceeding the tensile strength of the reaction tube 25, the product discharge pipe 6 and the recovery tank 3. For this reason, surplus hydrogen is not generated by the hydrogen addition reaction at a predetermined pressure, so that further cost reduction and labor saving of hydrogen storage can be achieved.

  When the pressure regulating valve 38 is in a closed state, the reaction tube 25 is also placed under a predetermined pressure. For this reason, the reaction efficiency of the hydrogenation reaction can be increased. Excess hydrogen discharged from the reaction tube 25 is sent to the combustion device 23 via the recovery tank 3.

  Next, the reaction tower 2 having a form other than the form of the reaction tower 2 shown in FIGS. 1 to 4 will be described with reference to FIGS.

  FIG. 5 transparently shows the reaction tower 2 provided with the fins 40 inside the outer tower of the reaction tower 2.

  The tower fins 40 are provided inside the outer tower in a form in which the gap between the reaction tube 25 and the fins 26 is narrowed. For this reason, the hot air from the hot air generating chamber 22 is disturbed by the fins 26 and the fins 40 in the tower, and rises in the reaction tower 2 in a turbulent state. For this reason, the contact efficiency with which the hot air contacts the reaction tube 25 is increased, and the thermal efficiency of the catalyst 27 is improved. Therefore, the reaction rate of the dehydrogenation reaction or hydrogenation reaction is also improved.

  FIG. 6 transparently shows the reaction tower 2 provided with the fins 40 in the tower so as to alternate with the fins 26 inside the outer tower of the reaction tower 2.

  The tower fins 40 are formed inside the outer tower in a ring shape with a hole in the center. Further, the fins 26 are provided in the shape of a bowl around the reaction tube 25. For this reason, the hot air from the hot air generating chamber 22 rises inside the reaction tower 2 so as to sew the gap between the fin 26 and the tower fin 40. For this reason, the contact efficiency with which the hot air contacts the reaction tube 25 is increased, and the thermal efficiency of the catalyst 27 is improved. Therefore, the reaction rate of the dehydrogenation reaction or hydrogenation reaction is also improved. Note that the fins 40 in the tower may be formed in a spiral shape alternately with the fins 26 in the vertical direction. In this case, the hot air ascends inside the reaction tower 2 while traveling around the reaction tube 25 along the spiral fin 40 in the tower. Also in this case, the contact efficiency with which the hot air contacts the reaction tube 25 is increased, and the thermal efficiency of the catalyst 27 is improved. Therefore, the reaction rate of the dehydrogenation reaction or hydrogenation reaction is also improved.

  FIG. 7 transparently shows the reaction tower 2 in which the reaction tube 25 is arranged so that the hot air passage direction in the reaction tower 2 and the hydrogen supply body or hydrogen storage body passage direction are substantially perpendicular to each other.

  The hot air rises inside the reaction tower 2 so as to sew the gaps between the fins 26. For this reason, the contact efficiency with which the hot air contacts the reaction tube 25 is increased, and the thermal efficiency of the catalyst 27 is improved. Therefore, the reaction rate of the dehydrogenation reaction or hydrogenation reaction is also improved. The passing direction of the hot air and the passing direction of the hydrogen supply body or the hydrogen storage body do not necessarily need to be at right angles, and may intersect at any angle as long as they are not parallel.

  FIG. 8 has a structure other than the configuration of the reaction tower 2 shown in FIG. 7, in which the hot air passage direction in the reaction tower 2 and the hydrogen supply body or hydrogen storage body passage direction are substantially perpendicular to each other. The reaction tower 2 is shown transparently.

  The catalyst packed body 24 of the reaction tower 2 has a first opening 50 that opens at both ends in the moving direction of the raw material that is a hydrogen supply body or a hydrogen storage body, and both ends that intersect the first opening 50. A plurality of second openings 51 are provided, the first opening 50 is filled with the catalyst 27, and the hot air from the combustion device 23 is passed through the second opening 51. Since the region filled with the raw material is subdivided and the hot air passage region is subdivided, heat is easily transferred to the catalyst 27. Therefore, the reaction rate of the dehydrogenation reaction or hydrogenation reaction is also improved. In addition, the passage direction of the hot air and the passage direction of the raw material are not necessarily perpendicular to each other, and may be a direction facing each other or a direction parallel to each other.

  Next, an embodiment of a hydrogen supply / storage system in which a plurality of hydrogen supply / storage devices are arranged will be described.

  FIG. 9 is a diagram showing a configuration of an embodiment of a hydrogen supply / storage system according to the present invention.

  It is conceivable that the conversion rate between the hydrogen supply body and the hydrogen storage body is not sufficient only with the above-described hydrogen supply / storage apparatus. The hydrogen supply / storage system shown in FIG. 9 connects the above-described hydrogen supply / storage devices in multiple stages so as to improve the conversion rate. This hydrogen supply / storage system is a system in which the first embodiment of the hydrogen supply / storage device is connected in multiple stages, and decalin, which is an example of a hydrogen supplier, is used as a raw material. However, a hydrogen supplier other than decalin may be used as the raw material.

  The right side of the hydrogen supply / storage system shown in FIG. 9 has substantially the same structure as that of the first embodiment (FIG. 1) of the hydrogen supply / storage device. The hydrogen supply / storage system in this embodiment includes a raw material tank 1 containing decalin and a reaction tower 2 on the left side, and a recovery tank 3 that also serves as the right raw material tank. The connection between the raw material tank 1 and the reaction tower 2 on the left half side of FIG. 9 and the connection between the reaction tower 2 and the recovery tank 3 are the same as those in the first embodiment of the hydrogen supply / storage device. is there.

  Further, the fuel discharge port 10a of the raw material tank 1 on the left half side of FIG. 9 and the fuel supply port 10b of the combustion device 23 on the right half side of FIG. Yes. A liquid feed pump 11 is connected in the middle of the fuel supply pipe 10. Therefore, in the combustion device 23 on the right half side in FIG. 9, the raw material in the raw material tank 1 on the left half side in FIG. 9 and the product in the recovery tank 3 on the right half side in FIG. And are used as fuel.

  Furthermore, the exhaust heat supply port 60a of the reaction tower 2 on the right half side of FIG. 9 and the exhaust heat supply port 60b of the reaction tower 2 on the left half side of FIG. Has been. For this reason, the heat | fever discharged | emitted from the reaction tower 2 in the right half side of FIG. 9 is utilized for the heat source in the reaction tower 2 in the left half side of the same figure.

  In addition, unreacted decalin is collected in the collection tank 3 on the left half side in FIG. 9 in addition to naphthalene produced by decalin dehydrogenation. By sending these to the reaction tower 2 on the right half side of the figure, it is possible to cause dehydrogenation of unreacted decalin and finally improve the conversion rate of decalin to naphthalene. The hydrogen supply / storage system shown in FIG. 9 has a structure in which the hydrogen supply / storage devices are connected in two stages, but may have a structure in which the same apparatus is connected in three or more stages.

  As mentioned above, although each embodiment of the hydrogen supply / storage device and the embodiment of the hydrogen supply / storage system of the present invention has been described, the present invention is not limited to the above-described embodiment, Changes can be made as appropriate without departing from the scope of the invention.

  For example, each reaction tower 2 of the above-described hydrogen supply / storage system may be any of the reaction towers 2 shown in FIGS. In addition, the hydrogen supply / storage system described above may be a system having a structure in which the second embodiment, the third embodiment, or the fourth embodiment of the hydrogen supply / storage device is connected. good.

  The hydrogen supply / storage device or the hydrogen supply / storage system of the present invention is connected to a fuel cell and used to use hydrogen generated through a dehydrogenation reaction as a raw material for a fuel cell, or an oil refinery factory. It can be used to store hydrogen discharged during petroleum refining in the state of organic compounds.

It is a figure which shows the structure of 1st Embodiment of the hydrogen supply / storage apparatus which concerns on this invention. It is a figure which shows the structure of 2nd Embodiment of the hydrogen supply / storage apparatus which concerns on this invention. It is a figure which shows the structure of 3rd Embodiment of the hydrogen supply / storage apparatus which concerns on this invention. It is a figure which shows the structure of 4th Embodiment of the hydrogen supply / storage apparatus which concerns on this invention. 1 is a perspective view of a reaction column provided with fins inside the outer column used in the hydrogen supply / storage device shown in any of FIGS. 1 is a perspective view showing a reaction tower provided with fins in the tower so as to alternate with the fins inside the outer tower, which is used in the hydrogen supply / storage apparatus shown in any of FIGS. Reaction used in the hydrogen supply / storage device shown in any of FIGS. 1 to 4 in which the reaction tubes are arranged so that the passing direction of hot air and the passing direction of the hydrogen supply body or hydrogen storage body are substantially perpendicular to each other. The tower is shown transparently. It is used in the hydrogen supply / storage apparatus shown in any of FIGS. 1 to 4 and is not in the form of the reaction tower shown in FIG. 7, and the hot air passage direction and the hydrogen supply body or hydrogen storage body passage direction are A reaction tower having a structure that is substantially perpendicular is shown transparently. It is a figure which shows the structure of embodiment of the hydrogen supply / storage system which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Raw material tank 2 Reaction tower 3 Recovery tank 4b Raw material supply port 6a Product discharge port 8 Fuel supply piping 23 Combustion device 24 Catalyst filling body 25 Reaction tube 26 Fin 27 Catalyst 28 Heat exchanger 29 Exhaust heat supply piping 29a Exhaust heat Mouth 37 Pressure regulating valve 38 Pressure regulating valve 40 Tower fin 50 First opening 51 Second opening

Claims (11)

As a raw material, a raw material tank containing a hydrogen supply body capable of supplying hydrogen to the outside by a dehydrogenation reaction or a hydrogen storage body capable of storing hydrogen from the outside by a hydrogen addition reaction;
A reaction tower for causing dehydrogenation reaction or hydrogenation reaction of the raw material from the raw material tank;
A recovery tank for recovering the product produced by the dehydrogenation reaction or hydrogenation reaction from the reaction tower;
With
The reaction tower is
A combustion apparatus for burning a part of the raw material from the raw material tank;
A catalyst filling body that is filled with a catalyst for the dehydrogenation reaction or the hydrogenation reaction, and that introduces a raw material from the raw material tank;
With
The catalyst packing is
A reaction tube connected to the raw material tank and the recovery tank and filled with the catalyst;
A hydrogen supply / storage device having fins around the reaction tube.   The hydrogen supply / storage device according to claim 1, wherein the combustion device is connected to the recovery tank and introduces or burns a part or all of the product. A heat exchanger disposed between the raw material tank and the reaction tube;
Exhaust heat supply piping connecting the exhaust heat port of the reaction tube and the heat exchanger;
The hydrogen supply / storage device according to claim 1, further comprising:   The pressure regulating valve which opens when the pressure in the reaction tube reaches a predetermined pressure or more is provided between the product discharge port of the reaction tube and the recovery tank. The hydrogen supply / storage device according to claim 1.   5. The fuel supply piping connecting the recovery tank and the combustion device is provided with a pressure regulating valve that opens when the pressure in the reaction tube reaches a predetermined pressure or higher. The hydrogen supply / storage device according to claim 1. In using the hydrogen supply / storage device as a hydrogen storage device,
6. The hydrogen according to claim 1, wherein the recovery tank is connected to a raw material supply port side of the reaction tube, and hydrogen in the recovery tank is reacted with the hydrogen storage body. Supply and storage equipment.   The hydrogen supply / storage device according to any one of claims 1 to 6, wherein a fin in the tower is provided on an inner periphery of the reaction tower.   8. The hydrogen supply / storage device according to claim 7, wherein the fins in the tower are formed in a ring shape or a spiral shape and are alternately formed in the vertical direction with the fins of the reaction tube. In the reaction tower,
9. The hydrogen according to claim 1, wherein the reaction tube is arranged so that a direction in which the raw material moves and a direction in which hot air from the combustion apparatus moves. Supply and storage equipment. As a raw material, a raw material tank containing a hydrogen supply body capable of supplying hydrogen to the outside by a dehydrogenation reaction or a hydrogen storage body capable of storing hydrogen from the outside by a hydrogen addition reaction;
A reaction tower for causing a dehydrogenation reaction or a hydrogenation reaction of the raw material from the raw material tank;
A recovery tank for recovering the product produced by the dehydrogenation reaction or hydrogenation reaction from the reaction tower;
With
The reaction tower is
A combustion apparatus for burning a part of the raw material from the raw material tank;
A catalyst-filled body charged with the catalyst for the dehydrogenation reaction or the hydrogenation reaction, and introducing the raw material from the raw material tank;
With
The catalyst packing is
There are a plurality of first openings that are open at both ends in the moving direction of the raw material, and a plurality of second openings that are open at both ends in a direction crossing the first opening, a direction facing each other, or a parallel direction. ,
Filling the first opening with the catalyst;
A hydrogen supply / storage device, wherein hot air from the combustion device is passed through the second opening. A plurality of hydrogen supply / storage devices according to claim 1 are arranged,
Connecting the recovery tank of the hydrogen supply / storage device on the upper stream side to the raw material supply port of the catalyst filling body of the adjacent hydrogen supply / storage device located on the lower stream side,
2. A hydrogen supply / storage system, wherein the raw material in the recovery tank is used for the reaction of the adjacent hydrogen supply / storage device.

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