JP2017001914A - Equipment and process for producing hydrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the energy efficiency of entire equipment by effectively utilizing the thermal energy of a combustion exhaust gas generated when a heat medium for heating a dehydrogenation reactor is heated by a heat medium boiler.SOLUTION: The equipment for producing hydrogen is provided in which a dehydrogenation reaction product produced by a dehydrogenation reactor 10 for heating MCH (Methylcyclohexane) to decompose it into hydrogen and dehydrogenated substance is subjected to a separation into a hydrogen V31 and a first hydrogen-containing material G31 by a hydrogen purifier 30. The equipment for producing hydrogen comprises: a heat medium boiler 21 for heating a heat medium L11 that heats the dehydrogenation reactor 10; and a supply line LN40 for supplying the thermal energy of the combustion exhaust gas from a heat medium boiler 21 into a case 45 of a hydrogen purifier 30 to heat-insulate the hydrogen purifier 30.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hydrogen production apparatus and hydrogen production capable of improving the energy efficiency of the entire apparatus by effectively using the thermal energy of combustion exhaust gas generated when a heat medium for heating a dehydrogenation reactor is heated by a heat medium boiler. Regarding the method.

  Conventionally, hydrogen is purified from a dehydrogenation product produced by a dehydrogenation reactor that heats an aromatic hydrocarbon hydride, which is a kind of organic hydride, and decomposes it into hydrogen and a dehydrogenated material. Hydrogen production apparatuses such as hydrogen stations are known. The hydrogen purifier is sometimes called a hydrogen separator.

  Here, Patent Document 1 describes a high-purity hydrogen production method in which hydrogen is separated from a dehydrogenation reaction product after a dehydrogenation reaction by a cooling separation means, and further separated into hydrogen and a non-permeate gas by a membrane separation means. Has been.

JP 2005-213087 A

  By the way, since the dehydrogenation reactor is an endothermic reaction, it is necessary to heat the dehydrogenation reactor. As a heating means of this dehydrogenation reactor, there is one that heats the dehydrogenation reactor via a heat medium. The heat medium boiler heats the heat medium circulating through the dehydrogenation reactor. When such a heating means using a heating medium is employed, the dehydrogenation reactor can be heated more uniformly than, for example, a heating means that directly heats with a burner. It can be performed stably.

  Combustion exhaust gas is derived from this heat medium boiler. This combustion exhaust gas is generally released to the outside air. However, since the temperature of the combustion exhaust gas is close to 400 ° C., an air preheater as a heat exchanger is provided in the combustion exhaust gas path, and the air temperature introduced into the heat medium boiler There is something that preheats.

  However, the temperature of the combustion exhaust gas passing through the air preheater is about 200 ° C., and it is desired to increase the energy efficiency of the entire apparatus using this thermal energy.

  The present invention has been made in view of the above, and effectively uses the thermal energy of combustion exhaust gas generated when a heat medium for heating a dehydrogenation reactor is heated by a heat medium boiler. It is an object of the present invention to provide a hydrogen production apparatus and a hydrogen production method that can improve the efficiency.

  In order to solve the above-mentioned problems and achieve the object, a hydrogen production apparatus according to the present invention uses a dehydrogenation reactor to heat an organic hydride to generate a gas containing hydrogen and dansya hydrogen, and to generate hydrocarbons. A hydrogen production apparatus for obtaining high-purity hydrogen gas from a contained gas by a hydrogen purifier, a heat medium boiler for heating a heat medium for heating a dehydrogenation reactor, and heat energy of combustion exhaust gas of the heat medium boiler for hydrogen And a supply line for supplying heat to the heating device in the manufacturing apparatus and keeping the heating device warm.

  In the hydrogen production apparatus according to the present invention, in the above invention, the heating device is a case of the hydrogen purifier, and the supply line supplies thermal energy of combustion exhaust gas of the heat medium boiler to the hydrogen purifier. In this case, the hydrogen purifier is kept warm.

  The hydrogen production apparatus according to the present invention is characterized in that, in the above-mentioned invention, an air preheater is provided in the path of the combustion exhaust gas, and the heat exchanger is provided upstream or downstream of the air preheater.

  The hydrogen production apparatus according to the present invention is characterized in that, in the above invention, the supply line supplies combustion exhaust gas directly into the case of the hydrogen separator to keep the hydrogen purifier warm.

  Further, the hydrogen production method according to the present invention is such that a hydrogen purifier separates hydrogen and off-gas from a dehydrogenation reaction product generated by a dehydrogenation reactor that heats an organic hydride to decompose it into hydrogen and a dehydrogenated substance. A method for producing hydrogen comprising: supplying heat energy of combustion exhaust gas of a heat medium boiler for heating a heat medium for heating a dehydrogenation reactor into a heating device, for example, a case of a hydrogen purifier, and It is characterized by keeping warm.

  According to the present invention, the heat energy of the combustion exhaust gas of the heat medium boiler that heats the heat medium that heats the dehydrogenation reactor is supplied into the heating device, for example, the case of the hydrogen purifier to keep the hydrogen purifier warm. Therefore, the energy efficiency of the entire apparatus can be improved by effectively using the thermal energy of the combustion exhaust gas generated when heated by the heat medium boiler.

FIG. 1 is a circuit diagram showing a configuration of a hydrogen production apparatus according to Embodiment 1 of the present invention. FIG. 2 is a schematic diagram showing the relationship between the introduction / derivation component flow rates of the hydrogen purifier. FIG. 3 is a circuit diagram showing a configuration of a hydrogen production apparatus according to Embodiment 2 of the present invention. FIG. 4 is a circuit diagram showing a configuration of a hydrogen production apparatus according to Embodiment 3 of the present invention. FIG. 5 is a circuit diagram showing a configuration of a hydrogen production apparatus according to Embodiment 4 of the present invention.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the accompanying drawings.

(Embodiment 1)
[overall structure]
FIG. 1 is a circuit diagram showing a configuration of a hydrogen production apparatus 1 according to Embodiment 1 of the present invention. The hydrogen production apparatus 1 is an apparatus for producing hydrogen from an organic hydride by a dehydrogenation reaction, and is employed in a hydrogen station that supplies hydrogen to, for example, a fuel cell vehicle or a hydrogen engine vehicle. As shown in FIG. 1, the hydrogen production apparatus 1 includes a dehydrogenation reaction system 1A and a hydrogen separation system 1B. The dehydrogenation reaction system 1A decomposes the organic hydride into hydrogen and a dehydrogenated substance by the dehydrogenation reactor 10, and removes the dehydrogenated reactant containing the hydrogen and the undecomposed reactant that was not decomposed. To derive. The hydrogen separation system 1B separates hydrogen from the dehydrogenation reaction product derived from the dehydrogenation reaction system 1A by the hydrogen separator 30 and derives it to the outside.

  An organic hydride is a hydride of an organic compound having an unsaturated bond, and can be decomposed into a dehydrogenation reactant containing hydrogen and a dehydrogenated substance (an organic compound having an unsaturated bond) using a dehydrogenation catalyst. it can. The organic hydride is preferably in a liquid state at normal temperature and normal pressure, and when such an organic hydride is employed, it can be transported as a liquid fuel to the hydrogen production apparatus 1 such as a hydrogen station as a liquid fuel in the same manner as gasoline. In the first embodiment, description will be made using methylcyclohexane (hereinafter referred to as MCH) as the organic hydride, but the present invention is not limited to this. The organic compound having an unsaturated bond is an organic compound that has one or more double bonds or triple bonds in the molecule and is liquid at normal temperature and pressure. As the double bond, carbon-carbon double bond (C = C), carbon-nitrogen double bond (C = N), carbon-oxygen double bond (C = O), nitrogen-oxygen double bond (N = O). Examples of the triple bond include a carbon-carbon triple bond and a carbon-nitrogen triple bond. The organic compound having an unsaturated bond is preferably a liquid organic compound under normal temperature and pressure from the viewpoints of storage properties and transportability.

  Examples of the organic compound having an unsaturated bond include olefins, dienes, acetylenes, benzene, carbon chain-substituted aromatics, hetero-substituted aromatics, polycyclic aromatics, Schiff bases, and heteroaromatics. , Hetero 5-membered ring compounds, quinones, and ketones. Examples of olefins include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and the like. Examples of dienes include allene, butadiene, pentadiene, hexadiene, hebutadiene, octadiene, piperylene, isoprene and the like. Examples of acetylenes include acetylene, propyne, and vinyl acetylene. Examples of the carbon chain-substituted aromatics include alkyl-substituted aromatics. Examples of the alkyl-substituted aromatics include toluene, xylene, trimethylbenzene, ethylbenzene, cumene, benzoic acid and the like. Examples of hetero-substituted aromatics include anisole, dimethoxybenzene, phenol, aniline, N, N-dimethylaniline and the like. Examples of polycyclic aromatics include naphthalene, methylnaphthalene, anthracene, tetracene, phenanthrene, tetralin, and azulene. Examples of Schiff bases include 2-aza-hept-1-en-1-yl-cyclohexane. Heteroaromatics include pyridine, pyrimidine, quinoline, isoquinoline and the like. Examples of the hetero 5-membered ring compounds include furan, thiophene, pyrrole, and imidazole. Examples of quinones include benzoquinone and naphthoquinone. Examples of ketones include acetone and methyl ethyl ketone. Needless to say, carbon dioxide and carbon monoxide have an unsaturated bond, but are generally not regarded as organic compounds, and thus are excluded from the organic compounds having an unsaturated bond in the present embodiment. .

  Among the above unsaturated compounds, benzene, toluene, xylene, ethylbenzene, naphthalene, methylnaphthalene, tetralin and the like (hereinafter referred to as “benzene etc.”) are water-insoluble before and after hydrogenation, Since phase separation is possible, it is preferable to water-soluble organic compounds such as acetone in that it is very easy to recover as a product. As these benzenes and the like, pure compounds may be used, or a mixture of a plurality of compounds may be used.

[Dehydrogenation reaction system]
As shown in FIG. 1, the MCH transported by a lorry or the like is stored in a tank T1. The stored MCH is sucked up by the pump P1. The discharge flow rate from the pump P1 is controlled by the flow controller 100. The MCH (L1) discharged from the pump P1 is heated by the preheater 11, for example, from 20 ° C. near room temperature to 110 ° C. to 120 ° C. The heated liquid MCH (L2) is evaporated by the evaporator 12 to become vaporized MCH (V1) of, for example, 170 ° C. to 190 ° C., preferably about 180 ° C. MCH (V1) is further heated to, for example, 290 ° C. to 310 ° C., preferably about 300 ° C. by the heater 13, and introduced into the dehydrogenation reactor 10 as MCH (V2).

  In the dehydrogenation reactor 10, a pipe through which a heat medium such as heat medium oil passes is meandered. A dehydrogenation catalyst is attached in the dehydrogenation reactor 10. Since the dehydrogenation reaction of MCH (V2) is an endothermic reaction, MCH (V2) passing through the dehydrogenation reactor 10 using, for example, a heat medium of 340 ° C. to 360 ° C., preferably about 350 ° C. The inside of the dehydrogenation reactor 10 is heated so that it can be maintained at 290 ° C. to 310 ° C., preferably about 300 ° C., where the dehydrogenation catalyst is moderately deteriorated by heat. MCH (V2) introduced into the dehydrogenation reactor 10 is decomposed into hydrogen and toluene, and is, for example, 320 ° C. to 340 ° C., preferably 330 as a dehydrogenation reaction product V3 containing hydrogen, toluene, and undecomposed MCH. It is derived from the dehydrogenation reactor 10 at about ° C.

  In the heater 13, the dehydrogenation reactant V3 exchanges heat with MCH (V1) introduced into the heater 13. The heat-exchanged dehydrogenation reaction product V3 becomes, for example, a dehydrogenation reaction product V4 that has been cooled to about 200 ° C. to 220 ° C., preferably about 215 ° C. The dehydrogenation reactant V4 exchanges heat with MCH (L1) introduced into the preheater 11 in the preheater 11. In this preheater 11, heat exchange between the dehydrogenation reactant V4 and MCH (L1) can be reduced in the subsequent evaporator 12. That is, by setting it as such a structure, since the energy consumption for heating a heat medium can be suppressed so that it may mention later, the energy efficiency of the whole apparatus can be improved. The MCH (V5) heat-exchanged in the preheater 11 is cooled to 139 ° C., and then led out to the hydrogen separation system 1B.

  The heat medium L11 introduced into the dehydrogenation reactor 10 is heated in the heat medium boiler 21. The heat medium L12 that has absorbed heat in the dehydrogenation reactor 10 exchanges heat with MCH (L1) in the evaporator 12 to evaporate MCH (L1), and rises to, for example, 170 ° C. to 190 ° C., preferably 180 ° C. Warm up. Thereafter, the cooled heat medium L13 is again introduced into the heat medium boiler 21 by the pump P2 and heated. In the first embodiment, the heat medium employs heat medium oil from the viewpoint of heat transfer efficiency, but is not limited thereto. The heat medium is stored in the tank T2, and when the heat medium is insufficient in the heat medium circulation system, the heat medium is replenished to the pipes constituting the circulation system, and when the heat medium is large, the circulation is performed. It is pulled out from the pipelines that make up the system.

  The heat medium boiler 21 receives the LP gas G1 flowing through the line LN11 and the air G2 flowing through the line LN12, and burns the LP gas G1 to heat the heat medium L13. The air G <b> 2 is sucked by the blower 22, preheated by the air preheater 23, and then introduced into the heat medium boiler 21. The combustion exhaust gas G3 combusted by the heat medium boiler 21 is exchanged with the air G2 by the air preheater 23, and then discharged to the atmosphere as combustion exhaust gas. Energy efficiency can be increased by air preheating using the air preheater 23. In the heating medium heating control by the heat medium boiler 21, the temperature controller 200 detects the temperature in the dehydrogenation reactor 10, and the flow rate of the heat medium to the heat medium boiler 21 by the pump P2 is determined based on the detected temperature. LP which adjusts and detects the temperature of the heat medium L11 flowing into the dehydrogenation reactor 10 detected by the temperature controller 201 and burns in the heat medium boiler 21 via the flow controller 103 based on the detected temperature. This is done by adjusting the flow rate of the gas G1. The flow controller 103 performs opening / closing control of the valve VL103.

  In the first embodiment, the heat medium is heated using the heat medium boiler 21, and the dehydrogenation reactor 10 is heated by the heated heat medium. When such a heating mechanism using a heating medium is employed, the temperature of the dehydrogenation reactor 10 can be controlled more stably because, for example, heating can be performed more uniformly than a heating mechanism that directly heats with a burner. be able to. The heating mechanism using the heat medium is not limited to the one using a liquid heat medium. For example, the combustion gas obtained by burning LP gas with a burner or the like flows into the pipe in the dehydrogenation reactor 10 and flows into MCH ( A gaseous heat medium that heats V2) may be used. Further, the heating mechanism is not limited to one using a heat medium, and other mechanisms may be adopted as long as the same effect is obtained.

  In the dehydrogenation reaction system 1A according to the first embodiment, MCH (V1) flowing into the dehydrogenation reactor 10 by the heater 13 using the thermal energy of the dehydrogenation reactant V3 derived from the dehydrogenation reactor 10 is used. While being heated, the preheater 11 arranged in front of the evaporator 12 preheats the liquid MCH (L1) before evaporation using the thermal energy of the dehydrogenation reactant V4 after the heat exchange by the heater 13. I am doing so. As a result, the heat energy of the heat medium L12 consumed for the evaporation of MCH (L1) in the evaporator 12 can be reduced. This reduction in heat energy lost from the heat medium L12 results in a decrease in energy consumed in the heat medium boiler 21, and as a result, the energy efficiency of the entire apparatus can be improved.

[Hydrogen purification system]
On the other hand, the dehydrogenation reaction product V5 via the preheater 11 flows into the hydrogen purification system 1B. The dehydrogenation reaction product V <b> 5 is cooled from, for example, 135 ° C. to 140 ° C. to about 40 ° C. by the cooler 31, and is gas-liquid separated by the gas / liquid separator 35. The dehydrogenation reactant V6 having a high hydrogen content that is not separated as a liquid substance by the gas-liquid separator 35 is further cooled from 40 ° C. to about 15 ° C. by the cooler 32, and is separated by the gas-liquid separator 36. . The dehydrogenation reactant V7 that is not separated as a liquid substance by the gas-liquid separator 36 and has a further increased hydrogen content is introduced into the hydrogen purifier 30 as the dehydrogenation reactant V30 pressurized by the compressor P3. Since the dehydrogenation reactant V30 pressurized by the compressor P3 rises in temperature due to the pressurization, it is cooled to, for example, 80 to 100 ° C., preferably 90 ° C. by the cooler 33 before being introduced into the hydrogen purifier 30. Is done.

  The hydrogen purifier 30 has a function of selectively purifying hydrogen from the dehydrogenation reactant V30, and includes a first hydrogen-containing material whose hydrogen concentration is lower than the standard concentration of product hydrogen, and a hydrogen concentration that is a standard of product hydrogen. A second hydrogen-containing material having a concentration or higher is derived to the outside. In the first embodiment, the hydrogen purifier 30 uses a membrane separation mechanism. Examples of the hydrogen separation membrane employed in the membrane separation mechanism include carbon membranes, palladium membranes, zeolite membranes, etc., as membranes that can withstand the pressure introduced from the compressor P3 (for example, having a pressure resistance of 900 kPa or higher). Carbon membranes and zeolite membranes are relatively preferred in terms of pressure resistance and practical application with a small differential pressure, and carbon membranes are particularly preferred in terms of mechanical strength against vibration. The carbon film has a function of allowing hydrogen having a small molecular weight to permeate and not allowing relatively high molecular weight materials such as toluene and undecomposed substances to permeate. The compressor P3 outputs the dehydrogenation reactant V7 having a pressure of 200 kPa to the hydrogen purifier 30 as a dehydrogenation reactant V30 having a pressure increased to 900 kPa. Since the differential pressure during hydrogen purification in the hydrogen purifier 30 is 200 kPa, the purified hydrogen V31 becomes 700 kPa at 90 ° C. The hydrogen V31 is cooled to 40 ° C. by the cooler 34, adjusted by the flow controller 101, and led out to the outside as hydrogen V32 of 700 kPa. That is, it is supplied to the outside as product hydrogen having the required external pressure and temperature.

  Here, the pressure controller 400 controls the pressure derived from the compressor P3 to be a predetermined pressure. In consideration of pressure loss, this predetermined pressure is higher than the pressure 900 kPa, which is the sum of the differential pressure 200 kPa generated by the hydrogen separation in the hydrogen separator 30 and the pressure 700 kPa led out of the hydrogen V31 separated by the hydrogen separator 30. Use high pressure. By setting the pressure derived by the compressor P3 to such a predetermined pressure, it is necessary to provide a dedicated compressor for deriving product hydrogen, which has been conventionally provided at the subsequent stage of the hydrogen purifier 30, to increase the pressure required for product hydrogen. Disappears. As a result, the entire apparatus can be made compact. Further, the pressure efficiency can be increased by concentrating the compressors in a large compressor without distributing the compressors. As a result, the energy required for the hydrogen purification process by the hydrogen purifier 30 and the product hydrogen supply process are required. Total energy can be reduced.

  The liquefied impurities L21 and L22 containing a large amount of toluene and containing hydrogen separated as liquid substances in the gas-liquid separators 35 and 36 are collected in the tank T3 and used as recovered toluene. The recovered toluene can be repeatedly used as a hydride (MCH) by reacting with hydrogen again.

  The first hydrogen-containing material G31 that has not permeated the hydrogen separation membrane of the membrane separation mechanism in the hydrogen purifier 30 is introduced to the introduction side of the dehydrogenation reactor 10 via the supply line LN1. Even when other than the hydrogen separation membrane is used, a gas containing hydrocarbons other than high-purity hydrogen is used as the first hydrogen-containing material. In the first embodiment, the first hydrogen-containing material G31 is introduced into a pipe between the evaporator 12 and the heater 13 in order to effectively heat the first hydrogen-containing material G31. The first hydrogen-containing material G31 contains hydrogen that could not pass through the hydrogen separation membrane. When hydrogen in the first hydrogen-containing material G31 is introduced into the dehydrogenation reactor 10, deterioration of the dehydrogenation catalyst in the dehydrogenation reactor 10 can be suppressed. In particular, as shown in the first embodiment, by introducing the first hydrogen-containing material G31 from the introduction side (upstream side) of the dehydrogenation reactor 10, the amount of hydrogen present on the introduction side is relatively small. The occurrence of the coking phenomenon can be more effectively suppressed.

  FIG. 2 is a schematic diagram showing the relationship between the introduction / derivation component flow rates of the hydrogen purifier 30. As shown in FIG. 2, the dehydrogenation reactant V30 introduced into the hydrogen purifier 30 has a flow rate distribution of hydrogen: 16.5 kmol / h, others: 0.2 kmol / h, and has a high hydrogen content. Hydrogen V31 purified by the hydrogen purifier 30 is hydrogen: 13.4 kmol / h, and the first hydrogen-containing material G31 not purified by the hydrogen purifier 30 is hydrogen: 3.1 kmol / h, and others: 0 The flow distribution is 2 kmol / h. That is, the first hydrogen-containing material G31 contains hydrogen that could not permeate the hydrogen separation membrane. By introducing this hydrogen into the introduction side of the dehydrogenation reactor 10, the inside of the dehydrogenation reactor 10 Deterioration of the dehydrogenation catalyst can be suppressed.

  In FIG. 1, the temperature controllers 202 to 204 detect the gas temperature derived from the coolers 31 to 33 and perform temperature control by adjusting the flow rate of the cooling water flowing into the coolers 31 to 33. ing. Here, since the required cooling capacity is small, the coolers 31, 33, and 34 use cooling water that is naturally cooled via the cooling tower, and the cooler 32 is forced via the chiller because the required cooling capacity is large. Cooling water that is electrically cooled is used. In addition, since the power consumption by forced cooling can be suppressed by effectively using the cooling tower and performing multi-stage cooling by the coolers 31 and 32, the energy efficiency of the entire apparatus can be improved.

  Further, the discharge of the liquefied toluene in the gas-liquid separators 35 and 36 is controlled by the level controllers 301 and 302, respectively. That is, the level controllers 301 and 302 open the valve and discharge toluene to the tank T3 when the liquid level to be detected exceeds a predetermined height. The flow controller 101 controls the valve so that the flow rate of hydrogen V32 is a predetermined flow rate. Furthermore, the flow controller 102 controls the valve so that the flow rate of the first hydrogen-containing material G31 becomes a predetermined flow rate.

[Use of combustion exhaust gas]
The temperature of the combustion exhaust gas G3 from the heat medium boiler 21 is about 400 ° C., and the temperature downstream of the air preheater 23 is about 200 ° C. Therefore, a heat exchanger 40 is provided on the path of the combustion exhaust gas G3 of the heat medium boiler 21 and upstream of the air preheater 23. The supply line LN40 connects between the heat exchanger 40 and the case 45 of the hydrogen purifier 30, and supplies the heat energy of the heat-exchanged medium into the case 45. When the membrane-separated hydrogen purifier 30 is kept at about 90 ° C., the purification efficiency is increased.

  In the first embodiment, the heat energy of the combustion exhaust gas G3 is used for heat retention of the hydrogen purifier 30, and the heat purification efficiency by the hydrogen purifier 30 is increased by this heat retention.

(Embodiment 2)
Next, a second embodiment will be described. In the first embodiment described above, the heat exchanger 40 is disposed upstream of the air preheater 23. However, in the present second embodiment, as shown in FIG. 3, the heat exchanger 50 is disposed downstream of the air preheater 23. The thermal energy of the combustion exhaust gas G3 at about 200 ° C. is supplied into the case 45 of the hydrogen purifier 30 via the supply line LN50.

  In the second embodiment, the temperature of the combustion exhaust gas G3 is about 200 ° C. and the heat energy is low, but the heat energy is sufficient to keep the hydrogen purifier 30 at about 90 ° C.

(Embodiment 3)
Next, Embodiment 3 will be described. In Embodiments 1 and 2 described above, heat energy is supplied to the hydrogen purifier 30 side using the heat exchangers 40 and 50. In Embodiment 3, however, heat exchange is performed as shown in FIG. The combustion exhaust gas G3 is directly supplied to the hydrogen purifier 30 side via the supply line LN60 without using the vessels 40 and 50 and the medium. The combustion exhaust gas G3 is a gas, but even if the temperature of the combustion exhaust gas G3 decreases, sufficient heat energy can be supplied to keep the hydrogen purifier 30 warm. In this case, it is preferable to use the combustion exhaust gas G3 having a high temperature immediately after being discharged from the heat medium boiler 21. Moreover, it is preferable that the position where the combustion exhaust gas G3 is drawn out is a position where it is not necessary to control the heat retention of the hydrogen purifier 30.

(Embodiment 4)
Next, a fourth embodiment will be described. In Embodiments 1 to 3 described above, the heat energy of the combustion exhaust gas G3 is supplied to the hydrogen purifier 30 and used to heat the hydrogen purifier 30, but other heating devices in the hydrogen production apparatus 1 are also used. Can be supplied. As shown in FIG. 5, the periphery of the heater 13 is covered with a case 55, and the heat energy of the combustion exhaust gas G <b> 3 can be supplied to the case 55 through the heat medium supply line LN <b> 70. The preheater 11 and the evaporator 12 can also be provided with the same structure as the case 55 to supply the thermal energy of the combustion exhaust gas G3. Further, as in the third embodiment, the combustion exhaust gas G3 may be directly used for heating the preheater 11, the evaporator 12, and the heater 13 through the supply line.

(Embodiment 5)
Next, a fifth embodiment will be described. For example, a heat exchanger is provided in the line of the heat medium L12, and the heat energy of the combustion exhaust gas G3 is used for heating the heat medium L12 via the heat medium supply line connecting the heat exchanger and the combustion exhaust gas G3. Heat can be supplied to the evaporator 12. Further, a heat exchanger may be provided in the line of the heat medium L13 so that the heat energy of the combustion exhaust gas G3 is supplied to the heat medium L13 and used for preheating the heat medium L11 supplied to the dehydrogenation reactor 10.

  Further, in the case of a system that does not require the air preheater 23, the combustion exhaust gas G3 can also be used for heating the dehydrogenation reactor 10 via the supply line as long as the heat balance in the present system can be obtained. It is.

  In addition, you may select suitably and combine the component of Embodiment 1-5 mentioned above. Moreover, the structure which deleted the air preheater 23 may be sufficient.

DESCRIPTION OF SYMBOLS 1 Hydrogen production apparatus 1A Dehydrogenation reaction system 1B Hydrogen purification system 10 Dehydrogenation reactor 11 Preheater 12 Evaporator 13 Heater 21 Heat-medium boiler 22 Blower 23 Air preheater 30 Hydrogen refiner 31,32,33,34 Cooler 35, 36 Gas-liquid separator 40, 50 Heat exchanger 45, 55 Case 100, 101, 102, 103 Flow controller 200, 201, 202, 203, 204 Temperature controller 301, 302 Level controller 400 Pressure controller S1 Concentration sensor G1 LP Gas G2 Air G3 Combustion exhaust gas G31 First hydrogen-containing material L11, L12, L13 Heat medium L21, L22 Liquefied impurities P1, P2 Pump P3 Compressor T1, T2, T3 Tank V3, V4, V5, V6, V7, V30 Dehydrogenation reaction Things V31, V32, V33 Water Element VL103 Valve LN1, LN40, LN50, LN60, LN70 Supply line LN11, LN12 line

Claims (7)

A hydrogen production apparatus that heats an organic hydride by a dehydrogenation reactor, generates a gas containing hydrogen and hydrocarbons, and obtains high-purity hydrogen gas from the gas containing hydrocarbons by a hydrogen purifier,
A heating medium boiler for heating a heating medium for heating the dehydrogenation reactor;
A supply line for supplying heat energy of combustion exhaust gas of the heat medium boiler to a heating device in a hydrogen production apparatus to keep the heating device warm;
A hydrogen production apparatus comprising: The heating device is a case of the hydrogen purifier,
2. The hydrogen production apparatus according to claim 1, wherein the supply line supplies heat energy of combustion exhaust gas of the heating medium boiler into a case of the hydrogen purifier to keep the hydrogen purifier warm.   The hydrogen production apparatus according to claim 1, wherein a heat exchanger that collects heat of the combustion exhaust gas is provided in a path of the combustion exhaust gas.   The hydrogen production apparatus according to any one of claims 1 to 3, wherein an air preheater is provided in a path of the combustion exhaust gas, and the heat exchanger is provided upstream or downstream of the air preheater.   The hydrogen supply apparatus according to claim 2, wherein the supply line supplies combustion exhaust gas directly into the case of the hydrogen purifier to keep the hydrogen purifier warm. A hydrogen production method in which an organic hydride is heated by a dehydrogenation reactor, a gas containing hydrogen and hydrocarbons is produced, and a high purity hydrogen gas is produced from the gas containing hydrocarbons by a hydrogen purifier.
A method for producing hydrogen, characterized in that heat energy of combustion exhaust gas from a heat medium boiler that heats a heat medium that heats the dehydrogenation reactor is supplied to a heating device in a hydrogen production device to keep the heating device warm.   The said heating device is a case of the said hydrogen production apparatus, The thermal energy of the combustion exhaust gas of the said heat-medium boiler is supplied in the case of the said hydrogen purifier, and the said hydrogen purifier is heat-retained. 6. The method for producing hydrogen according to 6.

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