JP6198677B2 - Hydrogen supply system - Google Patents

Description

  The present invention relates to a hydrogen supply system that supplies hydrogen.

  As a conventional hydrogen supply system, for example, one disclosed in Patent Document 1 is known. The hydrogen supply system of Patent Document 1 includes a tank that stores a raw material aromatic hydrocarbon hydride, and a dehydrogenation reactor (dehydrogenation) that obtains a hydrogen-containing gas by dehydrogenating the raw material supplied from the tank. Reaction section), a gas-liquid separator (gas-liquid separation section) for gas-liquid separation of the hydrogen-containing gas obtained in the dehydrogenation reactor, and a hydrogen purifier (hydrogen purification section) for purifying the gas-liquid separated hydrogen-containing gas And).

JP 2006-232607 A

  By the way, in the hydrogen supply system as described above, a hydrogen purification unit is used that removes a dehydrogenated product from a hydrogen-containing gas by a membrane separation method or a temperature swing adsorption method (TSA method) to obtain a purified gas. There is. In this case, it is necessary to heat the hydrogen purification unit in order to remove the dehydrogenation product of the hydrogen-containing gas. For example, it is possible to efficiently supply heat to the hydrogen purification unit and improve the thermal efficiency. desired.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the hydrogen supply system which can improve thermal efficiency.

  A hydrogen supply system according to the present invention is a hydrogen supply system that supplies hydrogen, and includes a dehydrogenation reaction unit that obtains a hydrogen-containing gas by dehydrogenating a raw material, and a dehydrogenation reaction unit that generates combustion gas. A heat supply part for supplying heat to the gas, a gas-liquid separation part for gas-liquid separation of the hydrogen-containing gas obtained in the dehydrogenation reaction part, and a dehydrogenation product from the hydrogen-containing gas separated in the gas-liquid separation part A hydrogen purification unit that is removed by a membrane separation method or a temperature swing adsorption method to obtain a purified gas, a pressure-up unit that pressurizes the purified gas obtained in the hydrogen purification unit, a combustion gas generated in the heat supply unit, and dehydrogenation A heating unit that heats the hydrogen purification unit by circulating at least one of the hydrogen-containing gas obtained in the reaction unit and the purified gas that has been pressurized in the pressure unit as a heating gas.

  A hydrogen supply system according to the present invention is a hydrogen supply system that supplies hydrogen, and includes a dehydrogenation reaction unit that obtains a hydrogen-containing gas by dehydrogenating a raw material, and a dehydrogenation reaction unit that generates combustion gas. A heat supply part for supplying heat to the gas, a gas-liquid separation part for gas-liquid separation of the hydrogen-containing gas obtained in the dehydrogenation reaction part, and a dehydrogenation product from the hydrogen-containing gas separated in the gas-liquid separation part A hydrogen purification unit that is removed by a membrane separation method or a temperature swing adsorption method to obtain a purified gas, a pressure-up unit that pressurizes the purified gas obtained in the hydrogen purification unit, and a combustion gas and a pressure-up unit generated in the heat supply unit And a heating unit that heats the hydrogen-containing gas supplied to the hydrogen purification unit by circulating at least one of the purified gas boosted in step 1 as a heating gas.

  In these hydrogen supply systems, a heating gas (at least one of a combustion gas generated in the heat supply unit, a hydrogen-containing gas obtained in the dehydrogenation reaction unit, and a purified gas boosted in the pressurization unit) is generated by the heating unit. The hydrogen-containing gas is supplied to the hydrogen purification section or the hydrogen purification section. Therefore, when removing the dehydrogenation product in the hydrogen purification section, it is possible to efficiently supply the necessary heat and improve the thermal efficiency.

  In the hydrogen supply system according to the present invention, the heating section may be provided so as to cover the hydrogen purification section, and may have a jacket section or a helical tube section that circulates a heating gas and heats the hydrogen purification section. In this case, the hydrogen purification unit is directly heated by the jacket unit or the helical tube unit.

  The hydrogen supply system according to the present invention further includes a heat exchange unit that moves heat of the purified gas to at least one of a raw material supplied to the dehydrogenation reaction unit and an off-gas supplied from the hydrogen purification unit to the dehydrogenation reaction unit. You may have. In this case, the thermal efficiency can be further improved.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the hydrogen supply system which can improve thermal efficiency.

It is a block diagram which shows the hydrogen supply system which concerns on 1st Embodiment. It is a schematic perspective view which shows the hydrogen purifier which concerns on 1st Embodiment. It is a cross-sectional view of the hydrogen purifier of FIG. It is a block diagram which shows the modification of the hydrogen supply system which concerns on 1st Embodiment. (A) is a block diagram which shows the hydrogen supply system which concerns on 2nd Embodiment, (b) is a block diagram which shows the modification of the hydrogen supply system which concerns on 2nd Embodiment. (A) is a block diagram which shows the hydrogen supply system which concerns on 3rd Embodiment, (b) is a block diagram which shows the modification of the hydrogen supply system which concerns on 3rd Embodiment. It is a cross-sectional view showing a hydrogen purifier of a hydrogen supply system according to a fourth embodiment.

  DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

[First Embodiment]
FIG. 1 is a block diagram showing a configuration according to the hydrogen supply system of the first embodiment. The hydrogen supply system 100 according to the present embodiment uses an organic compound (liquid at normal temperature) as a raw material. In the process of hydrogen purification, the dehydrogenated product (organic compound (liquid at room temperature)) obtained by dehydrogenating the organic compound (liquid at room temperature) as a raw material is removed. Examples of the raw material organic compound include organic hydride. An organic hydride is preferably a hydride obtained by reacting a large amount of hydrogen produced in a refinery with an aromatic hydrocarbon. In addition, the organic hydride is not limited to an aromatic hydrogenated compound, and there is a system of 2-propanol (hydrogen and acetone are generated). The organic hydride can be transported to the hydrogen supply system 100 as a liquid fuel by a tank lorry as in the case of gasoline. In this embodiment, methylcyclohexane (hereinafter referred to as MCH) is used as the organic hydride. In addition, hydrides of aromatic hydrocarbons such as cyclohexane, dimethylcyclohexane, ethylcyclohexane, decalin, methyldecalin, dimethyldecalin, and ethyldecalin can be used as organic hydrides. This is a preferred example). The hydrogen supply system 100 can supply hydrogen to a fuel cell vehicle (FCV) or a hydrogen engine vehicle. The present invention can also be applied to the production of hydrogen from liquid hydrocarbon raw materials such as natural gas mainly composed of methane, LPG mainly composed of propane, or gasoline, naphtha, kerosene, and light oil.

  In the present embodiment, the hydrogen supply system 100 will be described using a hydrogen station that supplies high-purity hydrogen to the FCV 10 as an example. As shown in FIG. 1, the hydrogen supply system 100 according to this embodiment includes an MCH tank 1, a vaporizer 2, a dehydrogenation reactor (dehydrogenation reaction unit) 3, a gas-liquid separator (gas-liquid separation unit) 4, A toluene tank 5, a hydrogen purifier (hydrogen purifying unit) 6, a compressor (pressurizing unit) 7, a pressure accumulator 8, a dispenser 9, a heat source (heat supply unit) 11 and cold heat sources 12 and 13 are provided. Further, the hydrogen supply system 100 includes lines L1 to L9. In the present embodiment, an example will be described in which MCH is employed as a raw material, and the dehydrogenation product removed in the process of hydrogen purification is toluene. In practice, not only toluene but also unreacted MCH and a small amount of by-products and impurities are present, but in this embodiment, the same behavior as toluene is exhibited when mixed with toluene. Therefore, in the following description, what is referred to as “toluene” includes unreacted MCH and by-products.

  Lines L1 to L9 are flow paths through which MCH, toluene, hydrogen-containing gas, off-gas, or high-purity hydrogen passes. Line L1 connects MCH tank 1 and vaporizer 2 via heat exchanger (heat exchange part) 15A mentioned below. Line L2 connects vaporizer 2 and dehydrogenation reactor 3. The line L3 connects the dehydrogenation reactor 3 and the gas-liquid separator 4. The line L3 passes through a jacket part (heating part) 21 described later, and the heat of the hydrogen-containing gas flowing through the line L3 is transmitted to the hydrogen purifier 6 through the jacket part 21. The line L4 connects the gas-liquid separator 4 and the hydrogen purifier 6. The line L5 connects the gas / liquid separator 4 and the toluene tank 5.

  The line L6 connects the hydrogen purifier 6 and the compressor 7. The line L6 passes through a heat exchanger 15A described later, and the heat of high purity hydrogen (purified gas) flowing through the line L6 is transmitted to the MCH through the heat exchanger 15A. The line L7 connects the hydrogen purifier 6 and the vaporizer 2. The line L7 functions as a recycle line for refluxing off-gas discharged from the hydrogen purifier 6 to the upstream side of the dehydrogenation reactor 3. In the following description, the line L7 will be referred to as “recycle line L7”. The line L8 connects the compressor 7 and the pressure accumulator 8. Line L9 connects pressure accumulator 8 and dispenser 9.

  The MCH tank 1 is a tank that stores MCH as a raw material. MCH transported from outside by a tank lorry or the like is stored in the MCH tank 1. MCH stored in the MCH tank 1 is supplied to the vaporizer 2 via a line L1 by a compressor (not shown).

  The vaporizer 2 is a device that vaporizes MCH supplied from the MCH tank 1 via an injector or the like. The vaporized MCH is supplied to the dehydrogenation reactor 3 through the line L2 together with the off gas supplied from the hydrogen purifier 6 through the recycle line L7.

  The dehydrogenation reactor 3 is a device that obtains hydrogen by dehydrogenating MCH. That is, the dehydrogenation reactor 3 is a device that extracts hydrogen from MCH by a dehydrogenation reaction using a dehydrogenation catalyst. The organic hydride reaction is a reversible reaction, and the direction of the reaction changes depending on the reaction conditions (temperature, pressure) (restricted by chemical equilibrium). On the other hand, the dehydrogenation reaction is a reaction in which the number of molecules is always increased by an endothermic reaction. Therefore, high temperature and low pressure conditions are advantageous. Since the dehydrogenation reaction is an endothermic reaction, the dehydrogenation reactor 3 is supplied with heat from the heat source 11 via the combustion gas (heat medium). The dehydrogenation reactor 3 has a mechanism capable of exchanging heat between the MCH flowing in the dehydrogenation catalyst and the combustion gas from the heat source 11. Any heat source 11 may be employed as long as it can generate combustion gas and supply heat to the dehydrogenation reactor 3. For example, the heat source 11 may directly heat the dehydrogenation reactor 3. For example, the MCH supplied to the dehydrogenation reactor 3 is heated by heating the vaporizer 2 or the lines L1 and L2. Also good. Further, the heat source 11 may heat both the dehydrogenation reactor 3 and the MCH supplied to the dehydrogenation reactor 3. For example, a burner or an engine can be adopted as the heat source 11. The hydrogen-containing gas taken out by the dehydrogenation reactor 3 is supplied to the gas-liquid separator 4 via the line L3. The hydrogen-containing gas in the line L3 is supplied to the gas-liquid separator 4 in a state where the liquid toluene is contained as a mixture.

  The gas-liquid separator 4 is a tank that separates toluene from the hydrogen-containing gas. The gas-liquid separator 4 gas-liquid separates hydrogen as a gas and toluene as a liquid by storing a hydrogen-containing gas containing toluene as a mixture. The gas-liquid separator 4 is cooled by a cooling medium from the cold heat source 12. The gas-liquid separator 4 has a mechanism capable of exchanging heat between the hydrogen-containing gas in the gas-liquid separator 4 and the cooling medium from the cold heat source 12. As long as the cold-heat source 12 can cool the gas-liquid separator 4, what kind of thing may be employ | adopted. For example, a cooler such as a chiller can be employed as the cold heat source 12. The toluene separated by the gas-liquid separator 4 is supplied to the toluene tank 5 via the line L5. The hydrogen-containing gas separated by the gas-liquid separator 4 is supplied to the hydrogen purifier 6 via the line L4. When the hydrogen-containing gas is cooled, a part of the gas (toluene) is liquefied and can be separated from the gas (hydrogen) that is not liquefied by the gas-liquid separator 4. The efficiency of the separation is improved when the gas is at a low temperature, and the liquefaction of toluene further proceeds when the pressure is increased.

  The toluene tank 5 is a tank that stores liquid toluene separated by the gas-liquid separator 4. The toluene stored in the toluene tank 5 can be recovered and used.

  The hydrogen purifier 6 is obtained from the hydrogen-containing gas obtained in the dehydrogenation reactor 3 and gas-liquid separated in the gas-liquid separator 4 by a membrane separation method or a temperature swing adsorption method (TSA method). In an embodiment, toluene) is removed. The hydrogen purifier 6 of this embodiment removes toluene by a membrane separation method. Thereby, the hydrogen purifier 6 purifies the hydrogen-containing gas to obtain high purity hydrogen. The obtained high-purity hydrogen is supplied to the line L6, and the off gas containing hydrogen and a dehydrogenation product is discharged to the recycle line L7. The off gas supplied to the recycle line L7 is supplied to the vaporizer 2 via a compressor (not shown), and is supplied to the dehydrogenation reactor 3 via the line L2.

  The compressor 7 pressurizes the high-purity hydrogen obtained by the hydrogen purifier 6 to a high pressure state. The compressor 7 makes high-purity hydrogen into a high-pressure state at a pressure of 20 to 90 MPa, for example. The compressor 7 is in a high pressure state so that high purity hydrogen can be supplied to the FCV 10, and then supplied to the pressure accumulator 8 via the line L8. In addition, according to the target pressure, it is good also as a structure which provides multiple compression units which compress, and performs compression in steps.

  The pressure accumulator 8 stores high purity hydrogen in a high pressure state. The high purity hydrogen stored in the pressure accumulator 8 is supplied to the FCV 10 by the dispenser 9 via the line L9. Since the pressure accumulator 8 can store a certain amount of high-purity hydrogen in the hydrogen supply system 100, hydrogen can be stably supplied to the FCV 10. However, since the pressure accumulator 8 is not essential for supplying hydrogen, it may be omitted. The high purity hydrogen passing through the line L9 is cooled by the cooling medium from the cold heat source 13. The line L9 has a mechanism capable of exchanging heat between the high purity hydrogen flowing through the line L9 and the cooling medium from the cold heat source 13. Any cooling source 13 may be used as long as it can cool the high purity hydrogen flowing through the line L9. For example, a cooler such as a chiller can be employed as the cold heat source 13.

  2 is a schematic perspective view showing a hydrogen purifier in the hydrogen supply system of FIG. 1, and FIG. 3 is a cross-sectional view of the hydrogen purifier of FIG. As shown in FIG. 2, the hydrogen purifier 6 is a hydrogen separation device that uses a membrane separation method as a hydrogen purification method, and includes a hydrogen separation membrane. This hydrogen purifier 6 allows a hydrogen-containing gas pressurized to a predetermined pressure by a compressor (not shown) to pass through a hydrogen separation membrane (separation membrane) heated to a predetermined temperature, thereby removing a dehydrogenated product. Removal to obtain high purity hydrogen. The non-permeate gas that has not permeated the hydrogen separation membrane corresponds to the off-gas of the hydrogen purifier 6.

  Specifically, as shown in FIG. 3, the hydrogen purifier 6 separates hydrogen contained in the hydrogen-containing gas by a hydrogen separation membrane 61 that selectively permeates hydrogen. The hydrogen purifier 6 is configured by arranging a cylindrical hydrogen separation membrane 61 inside a cylindrical body 65. The space on the outer peripheral side (the space between the hydrogen separation membrane 61 and the cylinder 65) constitutes a recovery chamber RC that recovers hydrogen that has permeated the hydrogen separation membrane 61. A space inside the hydrogen separation membrane 61 constitutes a supply chamber SP to which a hydrogen-containing gas is supplied.

  One end surface in the axial direction of the cylindrical body 65 communicates with a line L4 for supplying a hydrogen-containing gas to the supply chamber SP and a line L7 for discharging off-gas from the supply chamber SP. The end surface on the other side in the axial direction of the cylindrical body 65 communicates with a line L6 of hydrogen-containing gas that has been transmitted to the recovery chamber RC. The permeation of the hydrogen-containing gas occurs due to the pressure difference between the supply pressure in the supply chamber SP and the pressure in the recovery chamber RC, and the chemical adsorption ability of the hydrogen separation membrane 61. Note that the configuration of the hydrogen purifier 6 is not limited to that shown in FIG. 2, and any configuration may be adopted. For example, a plurality of cylindrical hydrogen separation membranes may be provided in the cylinder 65, or a planar hydrogen separation membrane may be used instead of a cylindrical shape.

  The hydrogen separation membrane 61 is not particularly limited as long as it can selectively permeate hydrogen, and any kind of hydrogen separation membrane can be applied. For example, the hydrogen separation membrane 61 may be a porous membrane (separated by molecular flow, separated by surface diffusion flow, separated by capillary condensation, separated by molecular sieving, etc.), non-porous membrane Can be applied. As the hydrogen separation membrane 61, for example, a metal membrane (PbAg, PdCu, Nb, etc.), a zeolite membrane, an inorganic membrane (silica membrane, carbon membrane, etc.), and a polymer membrane (polyimide membrane, etc.) can be adopted. The use temperature of the hydrogen separation membrane 61 is preferably 100 ° C. to 140 ° C., for example, in order for the gas separation membrane to exhibit sufficient permeation performance and durability. The hydrogen recovery rate of the hydrogen purifier 6 by membrane separation is 70 to 90%. The separation factor of “hydrogen / toluene” of the membrane used in the hydrogen purifier 6 is preferably 1000 or more, and more preferably 10,000 or more.

  Here, the hydrogen supply system 100 of the present embodiment includes a jacket portion 21 that heats (heats) the hydrogen purifier 6. The jacket portion 21 circulates a high-temperature hydrogen-containing gas supplied from the dehydrogenation reactor 3 to the gas-liquid separator 4 and heats the hydrogen purifier 6 using the heat of the hydrogen-containing gas as a heat source. The jacket portion 21 is provided so as to cover the hydrogen purifier 6 and has a cylindrical shape coaxial with the hydrogen purifier 6. In other words, the jacket portion 21 is provided on the radially outer side of the cylinder 65 of the hydrogen purifier 6 so as to closely surround the cylinder 65. Inside the jacket portion 21, the hydrogen-containing gas flowing through the line L <b> 3 flows so as to be in thermal contact with the hydrogen purifier 6.

  On one side (the upper side in the figure) of the jacket part 21 in the axial direction, an inflow part 21 b for allowing the hydrogen-containing gas to flow into the jacket part 21 is provided. Further, an outflow portion 21 c for allowing the hydrogen-containing gas to flow out from the jacket portion 21 is provided on the other side (lower side in the drawing) of the jacket portion 21 in the axial direction. The inflow part 21b and the outflow part 21c constitute the above-described line L3, that is, the jacket part 21 is disposed on the line L3 between the dehydrogenation reactor 3 and the gas-liquid separator 4. In order to suppress heat dissipation from the jacket portion 21, it is preferable to provide a heat insulating material or the like around the jacket portion 21.

  Returning to FIG. 1, as described above, the hydrogen supply system 100 includes the heat exchanger 15 </ b> A for transferring the heat of high-purity hydrogen to the MCH supplied to the dehydrogenation reactor 3. The heat exchanger 15A is disposed on the lines L1 and L6. The heat exchanger 15A circulates MCH from the MCH tank 1 and circulates high-purity hydrogen from the hydrogen purifier 6, thereby transferring heat from the high-purity hydrogen to the MCH to heat the MCH.

  In the hydrogen supply system 100 of this embodiment, the heat of the hydrogen-containing gas is transferred to the hydrogen purifier 6 by circulating the hydrogen-containing gas obtained in the dehydrogenation reactor 3 in the jacket portion 21 (dehydration). The heat of the hydrogen-containing gas immediately after the elementary reactor 3 is recovered), and for example, the hydrogen purifier 6 can be heated until the hydrogen separation membrane 61 reaches the operating temperature (about 100 ° C. to 140 ° C.). Therefore, when toluene is removed by membrane separation in the hydrogen purifier 6, it is possible to efficiently supply necessary heat and to improve the thermal efficiency. In particular, in the hydrogen supply system 100, since the hydrogen purifier 6 is heated by the jacket portion 21, the hydrogen separation membrane 61 can be directly and effectively heated.

  Further, the hydrogen supply system 100 of the present embodiment includes a heat exchanger 15A, and heat of the high-purity hydrogen can be transferred to the MCH by the heat exchanger 15A and heated (giving residual heat to the MCH). . Thereby, the thermal efficiency of the hydrogen supply system 100 can be further improved.

  FIG. 4 is a block diagram showing a modification of the hydrogen supply system of FIG. As shown in FIG. 4, the hydrogen supply system 200 according to the modification is configured in the same manner as the hydrogen supply system 100 except that a heat exchanger 15B is provided instead of the heat exchanger 15A. The heat exchanger 15B moves the heat of high-purity hydrogen to off-gas supplied from the hydrogen purifier 6 to the dehydrogenation reactor 3 via the vaporizer 2. The heat exchanger 15B is disposed on the lines L6 and L7.

  The heat exchanger 15A circulates the off-gas from the hydrogen purifier 6 and also circulates the high-purity hydrogen from the hydrogen purifier 6, and transfers the heat from the high-purity hydrogen to the off-gas to heat the off-gas (off-gas). Can give residual heat). Thereby, also in the hydrogen supply system 200, the thermal efficiency can be further improved. In the above description, the hydrogen-containing gas flowing through the jacket portion 21 of the hydrogen supply systems 100 and 200 constitutes a “heating gas”.

[Second Embodiment]
Next, a second embodiment will be described. In the description of the second embodiment, the description overlapping with the first embodiment is omitted, and different points will be mainly described.

  FIG. 5A is a block diagram showing a configuration according to the hydrogen supply system of the second embodiment. In FIG. 5A, only the main part of the hydrogen supply system 300 of the present embodiment is shown. As shown in FIG. 5A, the hydrogen supply system 300 of this embodiment is different from the first embodiment in that a jacket portion 22 is provided instead of the jacket portion 21 (see FIG. 1).

  The jacket portion 22 distributes the high-temperature combustion gas H1 generated by the heat source 11, and heats the hydrogen purifier 6 using the heat of the combustion gas H1 as a heat source. The jacket portion 22 is configured in the same manner as the jacket portion 21 except that the combustion gas H1 flows in place of the hydrogen-containing gas. Inside the jacket portion 22, the combustion gas H1 is thermally connected to the hydrogen purifier 6. Circulate in contact with In order to suppress heat dissipation from the jacket portion 22, it is preferable to provide a heat insulating material or the like around the jacket portion 22.

  According to such a hydrogen supply system 300, the combustion gas H1 from the heat source 11 is circulated in the jacket portion 22, thereby moving the heat of the combustion gas H1 to the hydrogen purifier 6 (recovering the heat of the combustion gas H1). ), The hydrogen purifier 6 can be heated. Therefore, the above-described operational effect, that is, the effect of efficiently supplying the heat necessary for the hydrogen purifier 6 and improving the thermal efficiency is achieved.

  FIG. 5B is a block diagram showing a modification of the hydrogen supply system of the second embodiment. In FIG.5 (b), only the principal part is shown among the hydrogen supply systems 400 which concern on a modification. As shown in FIG. 5B, the hydrogen supply system 400 according to the modification is configured in the same manner as the hydrogen supply system 300 except that the heat exchanger 31 is provided instead of the jacket portion 22. The heat exchanger 31 moves the heat of the combustion gas H1 of the heat source 11 to the hydrogen-containing gas supplied to the hydrogen purifier 6. The heat exchanger 31 is disposed on the line L4 and on the flow path through which the combustion gas H1 flows.

  In such a hydrogen supply system 400, the hydrogen-containing gas directed to the hydrogen purifier 6 is circulated through the heat exchanger 31, and the combustion gas H1 from the heat source 11 is circulated through the heat exchanger 31, and the heat of the combustion gas H1 is generated. The hydrogen-containing gas can be heated by moving to the hydrogen-containing gas. Therefore, the above-described operational effect, that is, the effect of efficiently supplying the heat necessary for the hydrogen purifier 6 and improving the thermal efficiency is achieved. In the above, the combustion gas H1 flowing through the jacket portion 21 of the hydrogen supply system 300 and the combustion gas H1 flowing through the heat exchanger 31 of the hydrogen supply system 400 constitute the “heating gas”.

[Third Embodiment]
Next, a third embodiment will be described. In the description of the third embodiment, the description overlapping with the first embodiment is omitted, and different points will be mainly described.

  FIG. 6A is a block diagram showing a configuration according to the hydrogen supply system of the third embodiment. In FIG. 6A, only the main part of the hydrogen supply system 500 of the present embodiment is shown. As shown in FIG. 6A, the hydrogen supply system 500 according to this embodiment is different from the first embodiment in that a jacket portion 23 is provided instead of the jacket portion 21 (see FIG. 1).

  The jacket portion 23 circulates high-temperature high-purity hydrogen boosted by the compressor 7 and heats the hydrogen purifier 6 using the heat of the high-purity hydrogen as a heat source. The jacket portion 23 is configured in the same manner as the jacket portion 21 except that high-purity hydrogen flows in place of the hydrogen-containing gas. Inside the jacket portion 23, the high-purity hydrogen is thermally connected to the hydrogen purifier 6. Circulate in contact with In order to suppress heat dissipation from the jacket portion 23, it is preferable to provide a heat insulating material or the like around the jacket portion 23.

  In such a hydrogen supply system 500, the high purity hydrogen from the compressor 7 is circulated in the jacket portion 23, and the heat of the high purity hydrogen is transferred to the hydrogen purifier 6 (the heat of the high purity hydrogen immediately after the compressor 7 is transferred). The hydrogen purifier 6 can be heated. Therefore, the above-described operational effect, that is, the effect of efficiently supplying the heat necessary for the hydrogen purifier 6 and improving the thermal efficiency is achieved.

  FIG.6 (b) is a block diagram which shows the modification of the hydrogen supply system of 3rd Embodiment. In FIG.6 (b), only the principal part is shown among the hydrogen supply systems 600 which concern on a modification. As shown in FIG. 6B, the hydrogen supply system 600 according to the modification is configured in the same manner as the hydrogen supply system 500 except that the heat exchanger 32 is provided instead of the jacket portion 23. The heat exchanger 32 moves the heat of the high-purity hydrogen boosted by the compressor 7 to the hydrogen-containing gas supplied to the hydrogen purifier 6. The heat exchanger 32 is disposed on the lines L4 and L8.

  In such a hydrogen supply system 600, the hydrogen-containing gas directed to the hydrogen purifier 6 is circulated through the heat exchanger 32, and the high-purity hydrogen from the compressor 7 is circulated through the heat exchanger 32, so that the heat of the high-purity hydrogen is increased. Can be moved to the hydrogen-containing gas to heat the hydrogen-containing gas. Therefore, the above-described operational effect, that is, the effect of efficiently supplying the heat necessary for the hydrogen purifier 6 and improving the thermal efficiency is achieved. In the above description, the high-purity hydrogen flowing through the jacket portion 23 of the hydrogen supply system 500 and the high-purity hydrogen flowing through the heat exchanger 32 of the hydrogen supply system 600 constitute the “heating gas”.

[Fourth Embodiment]
Next, a fourth embodiment will be described. In the description of the fourth embodiment, the description overlapping with the first embodiment is omitted, and different points will be mainly described.

  FIG. 7 is a longitudinal sectional view showing a hydrogen purifier of the hydrogen supply system according to the fourth embodiment. As shown in FIG. 7, the hydrogen supply system 700 of the present embodiment is different from the first embodiment in that a spiral tube portion 24 is provided instead of the jacket portion 21 (see FIG. 3).

  The spiral tube portion 24 circulates the hydrogen-containing gas supplied from the dehydrogenation reactor 3 to the gas-liquid separator 4 and heats the hydrogen purifier 6 using the heat of the hydrogen-containing gas as a heat source. The spiral tube portion 24 has a tubular shape extending spirally so as to cover the hydrogen purifier 6. In other words, the spiral tube portion 24 is disposed on the radially outer side of the cylinder 65 of the hydrogen purifier 6 from one end side to the other end side in the axial direction of the hydrogen purifier 6 while being wound in contact with the cylinder 65. It extends towards. In the spiral tube portion 24, the hydrogen-containing gas flowing through the line L <b> 3 flows so as to be in thermal contact with the hydrogen purifier 6. In order to suppress heat radiation from the spiral tube portion 24, it is preferable to provide a heat insulating material or the like around the spiral tube portion 24.

  In such a hydrogen supply system 700, the hydrogen-containing gas from the dehydrogenation reactor 3 is circulated in the spiral tube section 24, and the heat of the hydrogen-containing gas is transferred to the hydrogen purifier 6 (the heat of the hydrogen-containing gas is reduced). The hydrogen purifier 6 can be heated. Therefore, the above-described operational effect, that is, the effect of efficiently supplying the heat necessary for the hydrogen purifier 6 and improving the thermal efficiency is achieved.

  In the above, the hydrogen-containing gas flowing through the spiral tube portion 24 constitutes “heating gas”. In each of the hydrogen supply systems 300 and 500, instead of the jacket portions 22 and 23, the same as the spiral tube portion 24 of the present embodiment (a tube shape extending spirally so as to cover the hydrogen purifier 6). ) A spiral tube portion may be provided.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, It changed within the range which does not change the summary described in each claim, or was applied to another thing. May be.

  For example, in the above-described embodiment, the hydrogen separation apparatus employing the membrane separation method is used as the hydrogen purifier 6. However, as will be described below, the hydrogen separation apparatus removes the dehydrogenated product from the hydrogen-containing gas by the TSA method. May be used as the hydrogen purifier 6.

  The adsorbent used in the TSA method has the property of adsorbing toluene contained in the hydrogen-containing gas at room temperature and desorbing the adsorbed toluene at high temperature. The TSA method utilizes such properties of the adsorbent. That is, by setting the inside of the adsorption tower to room temperature, toluene contained in the hydrogen-containing gas is adsorbed and removed by the adsorbent to obtain high-purity hydrogen gas (high-purity hydrogen). If the adsorption function of the adsorbent in the adsorption tower is reduced due to adsorption, the toluene adsorbed on the adsorbent is desorbed by raising the temperature in the adsorption tower, and a part of the high-purity hydrogen that has been removed is backflowed. By removing the desorbed toluene from the adsorption tower, the adsorption function of the adsorbent is regenerated (at this time, at least hydrogen and hydrogen containing toluene discharged by removing toluene from the adsorption tower) The contained gas corresponds to the off-gas from the hydrogen purifier 6).

  The method for adjusting the temperature in the adsorption tower is not particularly limited. For example, the temperature can be adjusted for each adsorption tower by an operation such as switching ON / OFF of a heater provided for each adsorption tower. Therefore, for the adsorption tower in which the adsorption function of the adsorbent is lowered, the adsorbent is regenerated and the off-gas is discharged by raising the temperature. On the other hand, with respect to the remaining adsorption towers, toluene contained in the hydrogen-containing gas is removed by adsorbing the adsorbent by maintaining the temperature at room temperature. When the adsorbent regeneration for the adsorption tower being regenerated is completed, the removal of toluene is started and high purity hydrogen is obtained for the adsorption tower by keeping the inside of the adsorption tower at room temperature. On the other hand, for all or part of the adsorption tower from which toluene has been removed, regeneration of the adsorbent is started and the off-gas is discharged by raising the temperature in the adsorption tower. Thus, by repeatedly switching the adsorption tower for regeneration and the adsorption tower for removing toluene, the hydrogen supply system 100 as a whole can obtain high-purity hydrogen and off-gas continuously. The hydrogen recovery rate when the hydrogen purifier 6 employs the TSA method is about 60 to 90%, depending on the number of adsorption towers.

  Each structure of embodiment mentioned above is not limited to the said structure, You may comprise so that the hydrogen supply system 100,200,300,400,500,600,700 may mutually be combined. For example, in the hydrogen supply systems 100 and 200, at least one of the combustion gas H1 of the heat source 11 and the high-purity gas immediately after the compressor 7 is further circulated through the jacket portion 21, and the combustion gas H1 and the high-purity gas immediately after the compressor 7 are circulated. The heat of at least one of the above may be transferred to the hydrogen purifier 6. Further, for example, in the hydrogen supply system 400, the high-purity gas immediately after the compressor 7 is further circulated through the heat exchanger 31, and the heat of the high-purity gas is transferred to the hydrogen-containing gas supplied to the hydrogen purifier 6. Good.

  In the embodiment described above, the direction of gas flow in the hydrogen purifier 6 is not particularly limited. For example, in the hydrogen purifier 6, the hydrogen-containing gas from the line L4 flows in from the radially inner side, and the high-purity hydrogen flows out to the line L6 through the radially outer side, which is the direction of the gas flow. In other words, the hydrogen-containing gas from the line L4 may flow from the radially outer side, and the high-purity hydrogen may flow to the line L6 through the radially inner side. Further, the structure in the jacket portions 21, 22, 23 and the spiral tube portion 24 and the direction of the flow of the heating gas are not particularly limited, and the hydrogen gas is provided so as to cover the hydrogen purifier 6 and the heating gas is circulated. Any device that heats the purifier 6 may be used.

  In the above-described embodiment, the hydrogen supply device (including the compressor 7, the accumulator 8, the dispenser 9, and the like) is connected to the downstream side of the hydrogen purifier 6. A hydrogen consuming device (including a power generation device or the like) may be connected to the side and used as a hydrogen station that supplies hydrogen directly to the hydrogen consuming device. In addition, the above-described embodiment may be used for any application, and for example, may be used as a hydrogen supply system for a distributed power source (for example, a household power source or an emergency power source).

  DESCRIPTION OF SYMBOLS 3 ... Dehydrogenation reactor (dehydrogenation reaction part), 4 ... Gas-liquid separator (gas-liquid separation part), 6 ... Hydrogen refiner (hydrogen purification part), 7 ... Compressor (pressurization part), 11 ... Heat source ( Heat supply part), 15A, 15B ... Heat exchanger (heat exchange part) 21, 22, 23 ... Jacket part (heating part), 24 ... Spiral tube part (heating part), 31, 32 ... Heat exchanger (heating) Part), 100, 200, 300, 400, 500, 600, 700 ... hydrogen supply system.

Claims (4)

A hydrogen supply system for supplying hydrogen,
A dehydrogenation reaction section for obtaining a hydrogen-containing gas by dehydrogenating the raw material;
A heat supply unit that generates combustion gas and supplies heat to the dehydrogenation reaction unit;
A gas-liquid separation unit for gas-liquid separation of the hydrogen-containing gas obtained in the dehydrogenation reaction unit;
A hydrogen purification unit that removes a dehydrogenated product from the hydrogen-containing gas that has been gas-liquid separated in the gas-liquid separation unit by a membrane separation method or a temperature swing adsorption method to obtain a purified gas;
A pressurizing unit that pressurizes the purified gas obtained in the hydrogen purifying unit;
By circulating at least one of the combustion gas generated in the heat supply unit, the hydrogen-containing gas obtained in the dehydrogenation reaction unit, and the purified gas boosted in the boosting unit as a heating gas, A hydrogen supply system comprising: a heating unit that heats the hydrogen purification unit.   2. The hydrogen supply system according to claim 1, wherein the heating unit is provided so as to cover the hydrogen purification unit, and includes a jacket unit or a spiral tube unit that circulates the heating gas and heats the hydrogen purification unit. A hydrogen supply system for supplying hydrogen,
A dehydrogenation reaction section for obtaining a hydrogen-containing gas by dehydrogenating the raw material;
A heat supply unit that generates combustion gas and supplies heat to the dehydrogenation reaction unit;
A gas-liquid separation unit for gas-liquid separation of the hydrogen-containing gas obtained in the dehydrogenation reaction unit;
A hydrogen purification unit that removes a dehydrogenated product from the hydrogen-containing gas that has been gas-liquid separated in the gas-liquid separation unit by a membrane separation method or a temperature swing adsorption method to obtain a purified gas;
A pressurizing unit that pressurizes the purified gas obtained in the hydrogen purifying unit;
The hydrogen-containing gas supplied to the hydrogen purification unit is heated by circulating at least one of the combustion gas generated in the heat supply unit and the purified gas boosted by the boosting unit as a heating gas. A hydrogen supply system comprising: a heating unit.   The heat exchange part which moves the heat of the refining gas to at least one of the raw material supplied to the dehydrogenation reaction part, and at least one of off gas supplied from the hydrogen refining part to the dehydrogenation reaction part. The hydrogen supply system according to any one of 1 to 3.

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