JP2013076146A

JP2013076146A - Hydrogen generation system

Info

Publication number: JP2013076146A
Application number: JP2011217949A
Authority: JP
Inventors: Kenichi Tokuhiro; 憲一徳弘; Kazuhito Hado; 一仁羽藤; Takahiro Suzuki; 孝浩鈴木; Satoshi Tamura; 聡田村
Original assignee: Panasonic Corp
Current assignee: Panasonic Corp
Priority date: 2011-09-30
Filing date: 2011-09-30
Publication date: 2013-04-25

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen generation system that prevents the efficiency of generating hydrogen from reducing and can also recover heat efficiency.SOLUTION: The hydrogen generation system includes: a hydrogen generation device 100 that includes a fist electrode having a photocatalytic semiconductor, an electrolyte (a first electrolyte and a second electrolyte) containing water, and the like, and in which light is emitted to the photocatalytic semiconductor and thereby the water is decomposed to generate hydrogen; a mechanism that includes a first circulation path 201 leading out the first electrolyte outside the hydrogen generation device 100 and leading the first electrolyte again into the hydrogen generation device 100, and uses the first circulation path 201 to circulate the first electrolyte; a first heat exchanger 204 provided on the first circulation path 201; and a temperature measuring device 203 for measuring a temperature of the first electrolyte. When the temperature of the first electrolyte is equal to or higher than a predetermined temperature, heat exchange is provided between the first electrolyte of the first circulation path 201 and water of a first water flow line 205 in the heat exchanger 204, and the first electrolyte is cooled and water is heated.

Description

本発明は、光の照射により水素を生成するデバイスを備えた水素生成システムに関する。 The present invention relates to a hydrogen generation system including a device that generates hydrogen by light irradiation.

従来、光により電解質を水素へ開裂するための光電気化学システムにおいて、前記電解質から熱を引き出し、熱を家庭用温水等に供給するよう構成された熱交換器を備えたシステムが開示されている（例えば、特許文献１参照）。この光電気化学システムは、太陽熱により熱を得た電解質から、熱交換器を介して熱を回収し、回収された熱を家庭用温水等に供給するものである。 Conventionally, in a photoelectrochemical system for cleaving an electrolyte into hydrogen by light, a system including a heat exchanger configured to draw heat from the electrolyte and supply the heat to domestic hot water or the like has been disclosed. (For example, refer to Patent Document 1). In this photoelectrochemical system, heat is recovered from an electrolyte obtained by solar heat through a heat exchanger, and the recovered heat is supplied to domestic hot water or the like.

特表２００８−５０７４６４号公報Special table 2008-507464

従来、太陽熱を利用して水を加熱する際の課題として、太陽熱から得られる熱エネルギーは大きいものの、水の比熱の大きさ及び太陽エネルギー密度の希薄さにより、高温の水を得るためには時間を要するという課題がある。 Conventionally, as a problem when heating water using solar heat, although the heat energy obtained from solar heat is large, it takes time to obtain hot water due to the specific heat of water and the thinness of solar energy density. There is a problem of requiring.

特許文献１に記載の光電気化学システムにおいては、電解質は、その温度が十分に上がるよりも前に熱交換器で熱を奪われて冷却されてしまうため、電解質の温度が高温に達することはなかった。したがって、このシステムは、高温の熱を得ることができないという課題を有していた。 In the photoelectrochemical system described in Patent Document 1, since the electrolyte is deprived of heat by the heat exchanger before the temperature sufficiently rises, the electrolyte temperature reaches a high temperature. There wasn't. Therefore, this system has a problem that high-temperature heat cannot be obtained.

本発明は、前記従来の課題を解決するもので、水素の生成効率を低下させることなく、併せて効率良く熱の回収も可能とした、水素生成システムを提供することを目的とする。 The present invention solves the above-described conventional problems, and an object of the present invention is to provide a hydrogen generation system capable of efficiently recovering heat without reducing the hydrogen generation efficiency.

本発明の水素生成システムは、
光触媒性半導体を含む第１電極と、前記第１電極と電気的に接続された第２電極と、前記第１電極の表面及び前記第２電極の表面と接する、水を含む電解液と、前記第１電極と前記第２電極との間に配置され、前記電解液を前記第１電極の表面と接する第１電解液と前記第２電極の表面と接する第２電解液とに分割するセパレータと、前記第１電極、前記第２電極、前記電解液及び前記セパレータを収容する筐体と、を備え、前記第１電極の前記光触媒性半導体に光が照射されることによって前記水が分解されて水素が発生する、水素生成デバイスと、
前記第１電解液を前記水素生成デバイス外に導出し、且つ前記水素生成デバイス内に再び導入する第１循環経路を含み、前記第１循環経路を用いて前記第１電解液を循環させる機構と、
前記第１循環経路上に設けられた第１熱交換器と、
前記第１電解液の温度を計測する手段と、
を備え、
計測された前記第１電解液の温度が所定の温度以上である場合に、前記第１熱交換器において、前記第１循環経路の前記第１電解液と第１液体経路の第１液体との熱交換が行われて、前記第１電解液が冷却され且つ前記第１液体が加熱される。 The hydrogen generation system of the present invention comprises:
A first electrode containing a photocatalytic semiconductor; a second electrode electrically connected to the first electrode; an electrolyte containing water in contact with a surface of the first electrode and a surface of the second electrode; A separator disposed between the first electrode and the second electrode and dividing the electrolytic solution into a first electrolytic solution in contact with the surface of the first electrode and a second electrolytic solution in contact with the surface of the second electrode; A housing for housing the first electrode, the second electrode, the electrolytic solution, and the separator, and the water is decomposed by irradiating the photocatalytic semiconductor of the first electrode with light. A hydrogen generation device for generating hydrogen;
A mechanism for leading the first electrolytic solution out of the hydrogen generating device and reintroducing the first electrolytic solution into the hydrogen generating device, and circulating the first electrolytic solution using the first circulating route; ,
A first heat exchanger provided on the first circulation path;
Means for measuring the temperature of the first electrolyte solution;
With
When the measured temperature of the first electrolytic solution is equal to or higher than a predetermined temperature, in the first heat exchanger, the first electrolytic solution in the first circulation path and the first liquid in the first liquid path Heat exchange is performed to cool the first electrolyte and heat the first liquid.

本発明の水素生成システムを構成する水素生成デバイスでは、第１電極に含まれる光触媒性半導体に光（一般的には太陽光）が照射されることによって水素が発生する。したがって、このような水素生成デバイスは、第１電極が光照射側となる向きで設置されることが一般的であり、光照射によって第１電極と接する第１電解液の温度が上昇する。本発明の水素生成システムによれば、第１電解液の熱を別の液体（第１液体）を介して取り出し、種々の用途に利用できる。ただし、本発明の水素生成システムでは、第１電解液の温度が所定の温度以上となった場合に、第１熱交換器において、第１電解液と第１液体との間で熱交換が行われる。したがって、本発明の水素生成デバイスによれば、第１電解液に十分な量の熱を蓄積させて第１電解液の温度を十分に上昇させてから、第１電解液から熱を効率良く回収できる。また、本発明の水素生成システムでは、第１電解液は第１循環経路を流動し続けることができるので、電解液中のイオンの拡散が妨げられない。その結果、本発明の水素生成システムによれば、水素生成効率を低下させることなく、併せて効率良く熱を回収できる。 In the hydrogen generation device constituting the hydrogen generation system of the present invention, hydrogen is generated by irradiating light (generally sunlight) to the photocatalytic semiconductor included in the first electrode. Therefore, such a hydrogen generation device is generally installed in a direction in which the first electrode is on the light irradiation side, and the temperature of the first electrolytic solution in contact with the first electrode is increased by light irradiation. According to the hydrogen generation system of the present invention, the heat of the first electrolytic solution can be taken out via another liquid (first liquid) and used for various applications. However, in the hydrogen generation system of the present invention, when the temperature of the first electrolytic solution becomes a predetermined temperature or higher, heat exchange is performed between the first electrolytic solution and the first liquid in the first heat exchanger. Is called. Therefore, according to the hydrogen generation device of the present invention, after a sufficient amount of heat is accumulated in the first electrolytic solution to sufficiently raise the temperature of the first electrolytic solution, heat is efficiently recovered from the first electrolytic solution. it can. In the hydrogen generation system of the present invention, since the first electrolyte can continue to flow through the first circulation path, the diffusion of ions in the electrolyte is not hindered. As a result, according to the hydrogen generation system of the present invention, heat can be efficiently recovered without reducing the hydrogen generation efficiency.

本発明の実施の形態１における水素生成システムを構成する水素生成デバイスの一構成例を示す概略図Schematic which shows the example of 1 structure of the hydrogen production | generation device which comprises the hydrogen production system in Embodiment 1 of this invention. 本発明の実施の形態１における水素生成システムの例を示す構成図The block diagram which shows the example of the hydrogen generation system in Embodiment 1 of this invention 実施の形態１の水素生成システムにおいて、熱が回収される際の制御部による処理の流れを示すフローチャートThe flowchart which shows the flow of a process by the control part when heat is collect | recovered in the hydrogen production system of Embodiment 1. FIG. 本発明の実施の形態２における水素生成システムの例を示す構成図The block diagram which shows the example of the hydrogen generation system in Embodiment 2 of this invention 実施の形態２の水素生成システムにおいて、熱が回収される際の制御部による処理の流れを示すフローチャートThe flowchart which shows the flow of a process by the control part when heat is collect | recovered in the hydrogen production system of Embodiment 2. FIG. 本発明の実施の形態３における水素生成システムの例を示す構成図Configuration diagram showing an example of a hydrogen generation system according to Embodiment 3 of the present invention 実施の形態３の水素生成システムにおいて、熱が回収される際の制御部による処理の流れを示すフローチャートThe flowchart which shows the flow of a process by the control part when heat is collect | recovered in the hydrogen production system of Embodiment 3. FIG. 本発明の実施の形態４における水素生成システムの例を示す構成図Configuration diagram showing an example of a hydrogen generation system according to Embodiment 4 of the present invention 実施の形態４の水素生成システムにおいて、熱が回収される際の制御部による処理の流れを示すフローチャートIn the hydrogen generation system of Embodiment 4, the flowchart which shows the flow of a process by the control part when heat | fever is collect | recovered.

以下、本発明の実施の形態について、図面を参照しながら説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.

（実施の形態１）
図１は、本発明の実施の形態１における水素生成システムを構成する、水素生成デバイス１００の一構成例を示す。 (Embodiment 1)
FIG. 1 shows a configuration example of a hydrogen generation device 100 constituting the hydrogen generation system according to Embodiment 1 of the present invention.

水素生成デバイス１００は、半導体電極（第１電極）１０１と、対極（第２電極）１０２と、半導体電極１０１と対極１０２とを電気的に接続する外部回路１０３と、を備える。これらは、筐体１０４の内部に収容されている。半導体電極１０１は、光触媒として機能する光触媒性半導体を含んでいればよい。例えば、半導体電極１０１は、導電基板と、当該導電基板上に設けられた、光触媒として機能する光触媒性半導体の層と、によって形成されることができる。半導体電極１０１に含まれる光触媒性半導体は、必ずしも単相の半導体である必要はなく、複数種類の半導体からなる複合体でもよい。対極１０２は、金属及び炭素材料等の導体物質から形成されていてもよいし、導電基材に金属が担持された構造を有していてもよい。ここで、外部回路１０３は、必ずしも設けられなくてもよい。半導体電極１０１と対極１０２とが直接接している場合等、外部回路１０３を用いずに半導体電極１０１と対極１０２との電気的な接続が得られる場合は、外部回路１０３を設ける必要はない。また、半導体電極１０１と対極１０２との間には、バイアスを印加できるような機構が設けられていてもよい。 The hydrogen generation device 100 includes a semiconductor electrode (first electrode) 101, a counter electrode (second electrode) 102, and an external circuit 103 that electrically connects the semiconductor electrode 101 and the counter electrode 102. These are housed inside the housing 104. The semiconductor electrode 101 should just contain the photocatalytic semiconductor which functions as a photocatalyst. For example, the semiconductor electrode 101 can be formed by a conductive substrate and a layer of a photocatalytic semiconductor provided on the conductive substrate and functioning as a photocatalyst. The photocatalytic semiconductor contained in the semiconductor electrode 101 is not necessarily a single-phase semiconductor, and may be a composite composed of a plurality of types of semiconductors. The counter electrode 102 may be formed of a conductive substance such as a metal and a carbon material, or may have a structure in which a metal is supported on a conductive base material. Here, the external circuit 103 is not necessarily provided. When the semiconductor electrode 101 and the counter electrode 102 can be electrically connected without using the external circuit 103, such as when the semiconductor electrode 101 and the counter electrode 102 are in direct contact with each other, it is not necessary to provide the external circuit 103. Further, a mechanism capable of applying a bias may be provided between the semiconductor electrode 101 and the counter electrode 102.

水素生成デバイス１００の筐体１０４の内部には、少なくとも分解に用いられる水を含んだ電解液（後述の第１電解液１０６及び第２電解液１０７）が、さらに収容されている。筐体１０４の内部は、電解液を循環させるための循環経路（図示せず）と連通している。したがって、電解液は、筐体１０４の内部を流通している。電解液は、水素生成を効率的に行なうために、支持電解質、酸化還元材料、犠牲試薬及びｐH調整材料等を含んでいてもよい。 In the housing 104 of the hydrogen generation device 100, an electrolytic solution containing at least water used for decomposition (a first electrolytic solution 106 and a second electrolytic solution 107 described later) is further accommodated. The inside of the housing 104 communicates with a circulation path (not shown) for circulating the electrolytic solution. Therefore, the electrolytic solution circulates inside the housing 104. The electrolytic solution may contain a supporting electrolyte, a redox material, a sacrificial reagent, a pH adjusting material, and the like in order to efficiently generate hydrogen.

筐体１０４の半導体電極１０１側の面の一部は、太陽光を透過する部材で構成されている。また、筐体１０４は、例えば図１に示すように半導体電極１０１が効率的に太陽光を受光することが可能となるような角度、もしくは、例えば建築物の屋根等の設置する面の勾配に合わせて設置されることが望ましい。 Part of the surface of the housing 104 on the semiconductor electrode 101 side is formed of a member that transmits sunlight. Further, the housing 104 has an angle at which the semiconductor electrode 101 can efficiently receive sunlight as shown in FIG. 1, for example, or a slope of a surface on which a roof of a building is installed, for example. It is desirable to install them together.

筐体１０４において、半導体電極１０１と対極１０２との間には、セパレータ１０５が配置されている。このセパレータ１０５は、筐体１０４内部を、半導体電極１０１側の領域と対極１０２側の領域とに分離している。セパレータ１０５によって、前記電解液は、半導体電極１０１の表面と接する第１電解液１０６と、対極１０２の表面と接する第２電解液１０７とに分割される。セパレータ１０５は、電解液に含まれるイオンは透過するが、気体は遮断するような材質からなっていることが好ましい。セパレータ１０５で筐体１０４内を半導体電極１０１側の領域と対極１０２側の領域とに分離することにより、生成した水素ガスおよび酸素ガスが混合することが防止される。 In the housing 104, a separator 105 is disposed between the semiconductor electrode 101 and the counter electrode 102. The separator 105 separates the inside of the housing 104 into a region on the semiconductor electrode 101 side and a region on the counter electrode 102 side. The separator 105 divides the electrolyte into a first electrolyte 106 in contact with the surface of the semiconductor electrode 101 and a second electrolyte 107 in contact with the surface of the counter electrode 102. The separator 105 is preferably made of a material that transmits ions contained in the electrolytic solution but blocks gas. By separating the inside of the housing 104 into a region on the semiconductor electrode 101 side and a region on the counter electrode 102 side by the separator 105, mixing of the generated hydrogen gas and oxygen gas is prevented.

第１電解液１０６は、第１電解液導入口１０８より筐体１０４の内部に導入される。半導体電極１０１に含まれる光触媒性半導体がｎ型半導体の場合、半導体電極１０１に太陽光が照射されると、第１電解液導入口１０８より導入された第１電解液１０６中の水の一部は、半導体電極１０１上で以下の反応式（１）の反応に用いられる。その結果、酸素が生成する。一方、励起された電子は、半導体電極１０１を構成する導電基板及び外部回路１０３を伝導して、対極１０２上で以下の反応式（２）の反応に用いられる。その結果、水素が生成する。この時、半導体電極１０１により吸収されなかった光、特に赤外光、及び、光が半導体電極１０１により吸収されたものの、反応式（１）の化学反応に使われなかった場合に放出される熱エネルギーにより、第１電解液１０６は加熱される。第１電解液１０６は流動しており、第１電解液導出口１０９から筐体１０４の外部に導出される。 The first electrolytic solution 106 is introduced into the housing 104 from the first electrolytic solution inlet 108. When the photocatalytic semiconductor contained in the semiconductor electrode 101 is an n-type semiconductor, a part of the water in the first electrolytic solution 106 introduced from the first electrolytic solution introduction port 108 when the semiconductor electrode 101 is irradiated with sunlight. Is used for the reaction of the following reaction formula (1) on the semiconductor electrode 101. As a result, oxygen is generated. On the other hand, the excited electrons are conducted through the conductive substrate constituting the semiconductor electrode 101 and the external circuit 103 and used for the reaction of the following reaction formula (2) on the counter electrode 102. As a result, hydrogen is generated. At this time, light that is not absorbed by the semiconductor electrode 101, particularly infrared light, and heat that is emitted when the light is absorbed by the semiconductor electrode 101 but is not used in the chemical reaction of the reaction formula (1). The first electrolyte solution 106 is heated by the energy. The first electrolytic solution 106 is flowing and is led out of the housing 104 from the first electrolytic solution outlet 109.

４ｈ⁺＋２Ｈ₂Ｏ → Ｏ₂↑＋４Ｈ⁺ （１）
４ｅ^-＋４Ｈ⁺ → ２Ｈ₂↑ （２） 4h ⁺ + 2H ₂ O → O ₂ ↑ + 4H ⁺ (1)
^{^{_{4e - + 4H + → 2H 2}}} ↑ (2)

半導体電極１０１上で発生した酸素は、第１電解液１０６と共に、第１電解液導出口１０９から筐体１０４の外部へ導出される。なお、筐体１０４に酸素を導出する機構を別途設けて、この機構を利用して、半導体電極１０１上で発生した酸素を筐体１０４の外部に導出することも可能である。 Oxygen generated on the semiconductor electrode 101 is led out of the housing 104 from the first electrolyte outlet 109 together with the first electrolyte 106. Note that a mechanism for deriving oxygen can be separately provided in the housing 104, and oxygen generated on the semiconductor electrode 101 can be derived outside the housing 104 by using this mechanism.

一方、対極１０２と接する第２電解液１０７は、第２電解液導入口１１０から、筐体１０４の内部に導入される。導入された第２電解液１０７中の水の一部は、対極１０２上で反応式（２）の反応に用いられる。その結果、水素が生成する。第２電解液１０７は流動しており、第２電解液導出口１１１から筐体１０４の外部へと導出される。 On the other hand, the second electrolytic solution 107 in contact with the counter electrode 102 is introduced into the housing 104 from the second electrolytic solution introduction port 110. A part of the water in the introduced second electrolytic solution 107 is used for the reaction of the reaction formula (2) on the counter electrode 102. As a result, hydrogen is generated. The second electrolytic solution 107 is flowing and is led out of the housing 104 from the second electrolytic solution outlet 111.

対極１０２上で発生した水素は、第２電解液１０７と共に、第２電解液導出口１１１から筐体１０４の外部へ導出される。なお、筐体１０４に水素を導出する機構を別途設けて、この機構を利用して、対極１０２上で発生した水素を筐体１０４の外部に導出することも可能である。 Hydrogen generated on the counter electrode 102 is led out of the housing 104 from the second electrolyte solution outlet 111 together with the second electrolyte 107. Note that a mechanism for deriving hydrogen can be separately provided in the housing 104, and hydrogen generated on the counter electrode 102 can be derived outside the housing 104 by using this mechanism.

また、半導体電極１０１に含まれる光触媒性半導体がｐ型半導体の場合、半導体電極１０１上では反応式(２)の反応により水素が、対極１０２上では反応式（１）の反応により酸素が、それぞれ発生する。 Further, when the photocatalytic semiconductor contained in the semiconductor electrode 101 is a p-type semiconductor, hydrogen is formed on the semiconductor electrode 101 by the reaction of the reaction formula (2), and oxygen is formed on the counter electrode 102 by the reaction of the reaction formula (1). Occur.

図２Ａに、実施の形態１における水素生成システムの構成を示す。 FIG. 2A shows the configuration of the hydrogen generation system according to Embodiment 1.

水素生成システムを構成する水素生成デバイス１００の説明は前述したので省略する。以下、半導体電極１０１を構成する光触媒性半導体がｎ型半導体である場合について説明する。 Since the description of the hydrogen generation device 100 constituting the hydrogen generation system has been described above, it will be omitted. Hereinafter, a case where the photocatalytic semiconductor constituting the semiconductor electrode 101 is an n-type semiconductor will be described.

なお、図２Ａには図示されていないが、本実施の形態の水素生成システムには制御部が設けられている。この制御部は、本システムの全体を制御するものであって、本システムを構成する各部分を制御できる。この制御部は、本発明の特徴部分である、第１電解液１０６の温度情報に応じて熱交換が行われるか否かの判断（詳細は後述する）も行う。 Although not shown in FIG. 2A, the hydrogen generation system of the present embodiment is provided with a control unit. This control unit controls the entire system, and can control each part constituting the system. This control unit also determines whether or not heat exchange is performed according to the temperature information of the first electrolytic solution 106, which is a characteristic part of the present invention (details will be described later).

本実施の形態の水素生成システムには、第１電解液１０６を水素生成デバイス１００の外に導出し、且つ水素生成デバイス１００内に再び導入する第１電解液循環経路（第１循環経路）２０１が設けられている。したがって、水素生成デバイス１００の第１電解液１０６は、第１電解液導出口１０９から筐体１０４の外部へ導出されて、第１電解液循環経路２０１を流通して、第１電解液導入口１０８から再び筐体１０４内部へ導入される。 In the hydrogen generation system of the present embodiment, the first electrolyte solution 106 is led out of the hydrogen generation device 100 and introduced again into the hydrogen generation device 100 (first circulation route) 201. Is provided. Accordingly, the first electrolytic solution 106 of the hydrogen generation device 100 is led out of the housing 104 from the first electrolytic solution outlet 109 and flows through the first electrolytic solution circulation path 201 to be supplied to the first electrolytic solution inlet port. It is again introduced into the housing 104 from 108.

第１電解液循環経路２０１上には、第１電解液１０６を循環させるためのポンプ２０２と、第１電解液循環経路２０１を流れる第１電解液１０６の温度を計測するための第１温度計測装置（第１電解液１０６の温度を計測する手段）２０３が設置されている。 On the first electrolyte circulation path 201, a pump 202 for circulating the first electrolyte 106 and a first temperature measurement for measuring the temperature of the first electrolyte 106 flowing through the first electrolyte circulation path 201. An apparatus (means for measuring the temperature of the first electrolytic solution 106) 203 is installed.

第１電解液循環経路２０１上には第１熱交換器２０４が設置されている。第１温度計測装置２０３により計測された第１電解液１０１の温度が所定の温度以上の場合に、第１熱交換器２０４において、第１電解液循環経路２０１の第１電解液１０６と第１水流ライン（第１液体経路）２０５の水（第１液体）との熱交換が行われる。第１水流ライン２０５上には、弁２０６が設置されており、第１水流ライン２０５の水量を制御することができる。本実施の形態の水素生成システムでは、前記制御部は、第１温度計測装置２０３から第１電解液１０６の温度の情報を受け、それを所定の温度と比較する。そして、第１電解液１０６の温度が所定の温度以上であれば、弁２０６を制御して弁２０６を開き、第１水流ライン２０５に水を流すことによって、熱交換を実施する。この熱交換により、第１電解液循環経路２０１を流れる第１電解液１０６が冷却され、第１水流ライン２０５を流れる水が加熱される。 A first heat exchanger 204 is installed on the first electrolyte circulation path 201. When the temperature of the first electrolytic solution 101 measured by the first temperature measuring device 203 is equal to or higher than a predetermined temperature, the first electrolytic solution 106 and the first electrolytic solution 106 in the first electrolytic solution circulation path 201 are used in the first heat exchanger 204. Heat exchange with water (first liquid) in the water flow line (first liquid path) 205 is performed. A valve 206 is installed on the first water flow line 205, and the amount of water in the first water flow line 205 can be controlled. In the hydrogen generation system of the present embodiment, the control unit receives information on the temperature of the first electrolytic solution 106 from the first temperature measurement device 203 and compares it with a predetermined temperature. And if the temperature of the 1st electrolyte solution 106 is more than predetermined temperature, the valve 206 will be controlled, the valve 206 will be opened, and heat exchange will be implemented by flowing water through the 1st water flow line 205. FIG. By this heat exchange, the first electrolyte 106 flowing through the first electrolyte circulation path 201 is cooled, and the water flowing through the first water flow line 205 is heated.

なお、所定の温度は、工場出荷時に設定されていてもよいし、季節や天気、外気温や日射量等の動作環境に応じて動的に設定されてもよい。また、外部のサーバー等の装置からの通知により設定されてもよい。 The predetermined temperature may be set at the time of shipment from the factory, or may be dynamically set according to the operating environment such as season, weather, outside temperature, and solar radiation. Further, it may be set by a notification from an apparatus such as an external server.

なお、第１温度計測装置２０３は、第１電解液１０６の温度を計測できればよい。したがって、第１温度計測装置２０３は、水素生成デバイス１００の内部に設置されていてもよいし、第１熱交換器２０４の内部に設置されていてもよいし、そのいずれでもない第１循環経路２０１上に設置されていてもよい。 The first temperature measuring device 203 only needs to be able to measure the temperature of the first electrolytic solution 106. Therefore, the first temperature measurement device 203 may be installed inside the hydrogen generation device 100, may be installed inside the first heat exchanger 204, or neither of them is the first circulation path. 201 may be installed.

第１温度計測装置２０３により計測された第１電解液１０６の温度が所定の温度未満の場合には、弁２０６が操作されて第１水流ライン２０５を流れる水量を減量する、好ましくはほぼゼロにすることによって、第１熱交換器２０４において実質的な熱交換が行われないようにする。これにより、第１電解液循環経路２０１を流れる第１電解液１０６は、十分に温度が上昇していない段階で第１熱交換器２０４において熱を大幅に失うことがなく、水素生成デバイス１００において獲得した熱を所定の温度に到達するまで蓄積することが可能となる。その結果、第１水流ライン２０５を介して、高温の湯を得ることができる。 When the temperature of the first electrolyte solution 106 measured by the first temperature measuring device 203 is lower than a predetermined temperature, the valve 206 is operated to reduce the amount of water flowing through the first water flow line 205, preferably to substantially zero. By doing so, substantial heat exchange is not performed in the first heat exchanger 204. As a result, the first electrolyte 106 flowing through the first electrolyte circulation path 201 does not lose much heat in the first heat exchanger 204 at a stage where the temperature has not sufficiently increased. The acquired heat can be stored until a predetermined temperature is reached. As a result, hot water can be obtained via the first water flow line 205.

第１水流ライン２０５の水量の制御は、弁２０６を設置しなくても、例えばポンプ等の動力源を第１水流ライン２０５上に設置し、その出力を制御することによっても行うことができる。 Control of the amount of water in the first water flow line 205 can be performed by installing a power source such as a pump on the first water flow line 205 and controlling its output without installing the valve 206.

半導体電極１０１上で発生し、第１電解液導出口１０９から水素生成デバイス１００の外部へと導出された酸素は、第１循環経路２０１上に設けられた第１気液分離装置２０７により、第１電解液循環経路２０１を流れる第１電解液１０６から分離され、除去される。 Oxygen generated on the semiconductor electrode 101 and led out from the first electrolyte outlet 109 to the outside of the hydrogen generation device 100 is converted by the first gas-liquid separator 207 provided on the first circulation path 201 into the first. The first electrolyte solution 106 flowing through the one electrolyte solution circulation path 201 is separated and removed.

一方、対極１０２上で発生した水素は、第２電解液導出口１１１から第２電解液１０７と共に水素生成デバイス１００の外部へ導出された後、第２電解液循環経路２０８を流通し、第２気液分離装置２０９において第２電解液１０７から分離される。 On the other hand, the hydrogen generated on the counter electrode 102 is led out of the hydrogen generating device 100 together with the second electrolyte 107 from the second electrolyte outlet 111, and then flows through the second electrolyte circulation path 208, and the second electrolyte It is separated from the second electrolyte 107 in the gas / liquid separator 209.

第２電解液循環経路２０８を流れる第２電解液１０７は、水素が除去された後、第２電解液導入口１１０から再び水素生成デバイス１００に導入される。第２電解液循環経路２０８上には、第２電解液１０７を流動させる動力源として、ポンプ２１０が設置されている。 The second electrolyte 107 flowing through the second electrolyte circulation path 208 is again introduced into the hydrogen generation device 100 from the second electrolyte introduction port 110 after the hydrogen is removed. A pump 210 is installed on the second electrolyte circulation path 208 as a power source for causing the second electrolyte 107 to flow.

また、第２電解液循環経路２０８は、必ずしも直接第２電解液導入口１１０に連結されている必要はなく、一度、第１電解液循環２０１と合流した後、再び分岐して第２電解液導入口１１０と連結する構成となっていてもよい。 Further, the second electrolyte circulation path 208 is not necessarily connected directly to the second electrolyte introduction port 110, and once merged with the first electrolyte circulation 201, the second electrolyte circulation path 208 is branched again. It may be configured to be connected to the introduction port 110.

次に、本実施の形態の水素生成システムにおいて、第１電解液１０６の熱が回収される際の前記制御部による処理の流れを、図２Ｂに示されたフローチャートに沿って説明する。なお、ここでは、第１電解液１０６の温度が所定の温度未満の場合には、第１熱交換器２０４における熱交換が行われない例について説明する。 Next, in the hydrogen generation system of the present embodiment, the flow of processing by the control unit when the heat of the first electrolytic solution 106 is recovered will be described along the flowchart shown in FIG. 2B. Here, an example in which heat exchange in the first heat exchanger 204 is not performed when the temperature of the first electrolyte solution 106 is lower than a predetermined temperature will be described.

制御部は、まず第１温度計測装置２０３から第１電解液１０６の温度の情報を取得する（Ｓ１１）。次に、取得した第１電解液１０６の温度と所定の温度とを比較する（Ｓ１２）。第１電解液１０６の温度が所定の温度未満の場合は、第１水流ライン２０５の弁２０６は開かれずに、第１熱交換器２０４における熱交換は行われない。一方、第１電解液１０６の温度が所定の温度以上の場合、制御部は第１水流ライン２０５の弁２０６を開く（Ｓ１３）。これにより、第１熱交換器２０４において、第１電解液循環経路２０１の第１電解液１０６と第１水流ラインの水との間で熱交換が行われる。 First, the control unit acquires information on the temperature of the first electrolytic solution 106 from the first temperature measurement device 203 (S11). Next, the acquired temperature of the first electrolytic solution 106 is compared with a predetermined temperature (S12). When the temperature of the 1st electrolyte solution 106 is less than predetermined temperature, the valve 206 of the 1st water flow line 205 is not opened, but the heat exchange in the 1st heat exchanger 204 is not performed. On the other hand, when the temperature of the 1st electrolyte solution 106 is more than predetermined temperature, a control part opens the valve 206 of the 1st water flow line 205 (S13). Thereby, in the 1st heat exchanger 204, heat exchange is performed between the 1st electrolyte solution 106 of the 1st electrolyte circulation path 201, and the water of a 1st water flow line.

本実施の形態の水素生成システムでは、第１熱交換器２０１における熱交換の実施の有無の制御が、第１水流ライン２０５の弁２０６の開閉という、簡素な構成によって行われる。したがって、本実施の形態の水素生成システムは、効率の良い熱の回収を非常に簡素な構成によって実現できる。 In the hydrogen generation system of the present embodiment, the control of whether or not heat exchange is performed in the first heat exchanger 201 is performed by a simple configuration in which the valve 206 of the first water flow line 205 is opened and closed. Therefore, the hydrogen generation system of the present embodiment can achieve efficient heat recovery with a very simple configuration.

（実施の形態２）
実施の形態２の水素生成システムにおいて、水素生成デバイス１００の構成は、実施の形態１の場合と同様である。したがって、ここではその説明を省略する。 (Embodiment 2)
In the hydrogen generation system of the second embodiment, the configuration of the hydrogen generation device 100 is the same as that of the first embodiment. Therefore, the description thereof is omitted here.

図３Ａに、実施の形態２の水素生成システムの構成例を示す。図３Ａにおいて、図１および図２Ａと同じ構成要素については同じ符号を用い、説明は省略する。なお、図３Ａには図示されていないが、本実施の形態の水素生成システムにも、実施の形態１と同様に、制御部が設けられている。この制御部は、本システムの全体を制御するものであって、本システムを構成する各部分を制御できる。この制御部は、本発明の特徴部分である、第１電解液１０６の温度情報に応じて熱交換が行われるか否かの判断（詳細は後述する）も行う。 FIG. 3A shows a configuration example of the hydrogen generation system according to the second embodiment. In FIG. 3A, the same components as those in FIGS. 1 and 2A are denoted by the same reference numerals, and description thereof is omitted. Although not shown in FIG. 3A, the hydrogen generation system of the present embodiment is also provided with a control unit as in the first embodiment. This control unit controls the entire system, and can control each part constituting the system. This control unit also determines whether or not heat exchange is performed according to the temperature information of the first electrolytic solution 106, which is a characteristic part of the present invention (details will be described later).

本実施の形態の水素生成システムは、第１電解液循環経路２０１上に、第１熱交換器２０４を経由しない第１バイパスライン２１１が設けられた構成を有する。第１バイパスライン２１１上には弁２１２が設けられている。第１電解液循環経路２０１上であって、且つ第１バイパスライン２１１が分岐した後の経路上には、弁２１３が設けられている。 The hydrogen generation system of the present embodiment has a configuration in which a first bypass line 211 that does not pass through the first heat exchanger 204 is provided on the first electrolyte circulation path 201. A valve 212 is provided on the first bypass line 211. A valve 213 is provided on the first electrolyte circulation path 201 and on the path after the first bypass line 211 branches.

第１温度計測装置２０３により計測された第１電解液１０６の温度が所定の温度以上である場合、前記制御部は、第１バイパスライン２１１上の弁２１２を閉め、第１電解液循環経路２０１上の弁２１３を開ける。これにより、第１電解液循環経路２０１を流れる第１電解液１０６は、第１熱交換器２０４において、第１水流ライン２０５を流れる水と熱交換を行う。その結果、第１電解液循環経路２０１の第１電解液１０６は冷却されて、第１水流ライン２０５の水は加熱される。 When the temperature of the first electrolytic solution 106 measured by the first temperature measuring device 203 is equal to or higher than a predetermined temperature, the control unit closes the valve 212 on the first bypass line 211 and the first electrolytic solution circulation path 201. Open the upper valve 213. Thus, the first electrolyte 106 flowing through the first electrolyte circulation path 201 exchanges heat with the water flowing through the first water flow line 205 in the first heat exchanger 204. As a result, the first electrolyte 106 in the first electrolyte circulation path 201 is cooled, and the water in the first water flow line 205 is heated.

一方、第１温度計測装置２０３により計測された第１電解液１０６の温度が所定の温度未満の場合には、前記制御部は、弁２１２を開けて、弁２１３を閉める。これにより、第１電解液循環経路２０１を流れる第１電解液１０６は、第１熱交換器２０４を経由しないので、第１熱交換器２０４で冷却されることはない。これにより、第１電解液循環経路２０１を流れる第１電解液１０６は、十分に温度が上昇していない段階で第１熱交換器２０４において熱を失うことがなく、水素生成デバイス１００において獲得した熱を所定の温度に到達するまで蓄積することが可能となる。その結果、第１水流ライン２０５を介して、高温の湯を得ることができる。ここで、第１バイパスライン２１１と熱交換器２０４側の流路との切り替えを、弁２１２と弁２１３とを用いる方法以外の方法で行うことも可能である。例えば、第１バイパスライン２１１と熱交換器２０４側の流路との分岐点に、三方コックを設けて、流路を切り替えてもよい。 On the other hand, when the temperature of the first electrolytic solution 106 measured by the first temperature measuring device 203 is lower than a predetermined temperature, the control unit opens the valve 212 and closes the valve 213. Accordingly, the first electrolyte 106 flowing through the first electrolyte circulation path 201 does not pass through the first heat exchanger 204 and is not cooled by the first heat exchanger 204. Thereby, the first electrolyte 106 flowing through the first electrolyte circulation path 201 is acquired in the hydrogen generation device 100 without losing heat in the first heat exchanger 204 when the temperature is not sufficiently increased. Heat can be accumulated until a predetermined temperature is reached. As a result, hot water can be obtained via the first water flow line 205. Here, switching between the first bypass line 211 and the flow path on the heat exchanger 204 side can be performed by a method other than the method using the valve 212 and the valve 213. For example, a three-way cock may be provided at a branch point between the first bypass line 211 and the flow path on the heat exchanger 204 side to switch the flow path.

なお、気液分離装置２０７は、第１電解液循環経路２０１上であって、第１バイパスライン２１１が合流した後に設置されていることが望ましい。 The gas-liquid separator 207 is preferably installed on the first electrolyte circulation path 201 after the first bypass line 211 has joined.

次に、本実施の形態の水素生成システムにおいて、第１電解液１０６の熱が回収される際の前記制御部による処理の流れを、図３Ｂに示されたフローチャートに沿って説明する。 Next, in the hydrogen generation system of the present embodiment, the flow of processing by the control unit when the heat of the first electrolytic solution 106 is recovered will be described along the flowchart shown in FIG. 3B.

制御部は、まず第１温度計測装置２０３から第１電解液１０６の温度の情報を取得する（Ｓ２１）。次に、取得した第１電解液１０６の温度と所定の温度とを比較する（Ｓ２２）。第１電解液１０６の温度が所定の温度未満の場合は、制御部は、弁２１２を開き、弁２１３を閉じる（Ｓ２３）。したがって、第１熱交換器２０４における熱交換は行われない。一方、第１電解液１０６の温度が所定の温度以上の場合、制御部は、弁２１２を閉じて、弁２１３を開く（Ｓ２４）。これにより、第１熱交換器２０４において、第１電解液循環経路２０１の第１電解液１０６と第１水流ラインの水との間で熱交換が行われる。 The control unit first acquires information on the temperature of the first electrolytic solution 106 from the first temperature measurement device 203 (S21). Next, the acquired temperature of the first electrolytic solution 106 is compared with a predetermined temperature (S22). When the temperature of the 1st electrolyte solution 106 is less than predetermined temperature, a control part opens the valve 212 and closes the valve 213 (S23). Therefore, heat exchange in the first heat exchanger 204 is not performed. On the other hand, when the temperature of the 1st electrolyte solution 106 is more than predetermined temperature, a control part closes valve 212 and opens valve 213 (S24). Thereby, in the 1st heat exchanger 204, heat exchange is performed between the 1st electrolyte solution 106 of the 1st electrolyte circulation path 201, and the water of a 1st water flow line.

本実施の形態の水素生成システムでは、第１熱交換器２０１における熱交換の実施の有無の制御が、第１バイパスライン２１１と、第１バイパスライン２１１上に設けられた弁２１２と、第１電解液循環経路２０１上の弁２１３とを利用して行われる。これにより、効率の良い熱の回収という効果に加え、例えば諸事情により第１水流ライン２０５の水流を止めることができない場合でも、第１熱交換器２０１における熱交換の実施の有無を制御できるという効果も得られる。 In the hydrogen generation system of the present embodiment, whether or not heat exchange is performed in the first heat exchanger 201 is controlled by the first bypass line 211, the valve 212 provided on the first bypass line 211, and the first This is performed using the valve 213 on the electrolyte circulation path 201. Thereby, in addition to the effect of efficient heat recovery, for example, even if the water flow in the first water flow line 205 cannot be stopped due to various circumstances, it is possible to control whether heat exchange is performed in the first heat exchanger 201. An effect is also obtained.

（実施の形態３）
実施の形態３の水素生成システムにおいて、水素生成デバイス１００の構成は、実施の形態１の場合と同様である。したがって、ここではその説明を省略する。 (Embodiment 3)
In the hydrogen generation system according to the third embodiment, the configuration of the hydrogen generation device 100 is the same as that in the first embodiment. Therefore, the description thereof is omitted here.

図４Ａに、実施の形態３の水素生成システムの構成例を示す。図４Ａにおいて、図１、図２Ａ及び図３Ａと同じ構成要素については同じ符号を用い、説明は省略する。なお、図４Ａには図示されていないが、本実施の形態の水素生成システムにも、実施の形態１と同様に、制御部が設けられている。この制御部は、本システムの全体を制御するものであって、本システムを構成する各部分を制御できる。この制御部は、本発明の特徴部分である、第１電解液１０６の温度情報に応じて熱交換が行われるか否かの判断（詳細は後述する）も行う。 FIG. 4A shows a configuration example of the hydrogen generation system according to the third embodiment. 4A, the same components as those in FIGS. 1, 2A, and 3A are denoted by the same reference numerals, and description thereof is omitted. Although not shown in FIG. 4A, the hydrogen generation system of the present embodiment is also provided with a control unit as in the first embodiment. This control unit controls the entire system, and can control each part constituting the system. This control unit also determines whether or not heat exchange is performed according to the temperature information of the first electrolytic solution 106, which is a characteristic part of the present invention (details will be described later).

本実施の形態の水素生成システムは、水素生成デバイス１００において生成した水素を電気エネルギーに変換するための燃料電池３０１が設けられた構成を有する。第２気液分離装置２０９からは水素ライン３０２が分岐しており、得られた水素は燃料電池３０１に供給される。水素ライン３０２上には、水素を貯蔵するための設備、及び、水素を高圧にするための圧縮機構等が設置されていてもよい。 The hydrogen generation system of the present embodiment has a configuration in which a fuel cell 301 for converting hydrogen generated in the hydrogen generation device 100 into electric energy is provided. A hydrogen line 302 is branched from the second gas-liquid separator 209, and the obtained hydrogen is supplied to the fuel cell 301. On the hydrogen line 302, equipment for storing hydrogen, a compression mechanism for increasing the pressure of hydrogen, and the like may be installed.

燃料電池３０１には、燃料電池３０１の運転時に発生する余分の熱を回収して、燃料電池３０１を冷却するための、第２熱交換器３０３が設けられている。この第２熱交換器３０３と第１熱交換器２０４との間で液体を循環させる循環経路（第２循環経路）３０５が設けられている。すなわち、この第２循環経路３０５は、第１熱交換器２０４において、第１電解液１０６から熱を受け取る第１液体が流れる第１液体経路によって形成されている。この第１液体が燃料電池３０１を冷却する液体としても機能し、第２循環経路を循環する。 The fuel cell 301 is provided with a second heat exchanger 303 for recovering excess heat generated during operation of the fuel cell 301 and cooling the fuel cell 301. A circulation path (second circulation path) 305 for circulating the liquid between the second heat exchanger 303 and the first heat exchanger 204 is provided. That is, the second circulation path 305 is formed by a first liquid path through which the first liquid that receives heat from the first electrolytic solution 106 flows in the first heat exchanger 204. This first liquid also functions as a liquid for cooling the fuel cell 301 and circulates in the second circulation path.

第１温度計測装置２０３により計測された第１電解液１０６の温度が所定の温度以上の場合、第２循環経路２０５を流れる第１液体は、第１熱交換器２０４において第１電解液１０６からの熱で加熱され、さらに、第２熱交換器３０３において加熱される。第２循環経路３０５上には、第１熱交換器２０４よりも上流側で且つ第２熱交換器３０３よりも下流側に設けられた第３熱交換器３０４が設けられている。第３熱交換器３０４は、第２循環経路３０５を流れる第１液体と、第３水流ライン（第２液体経路）の水（第２液体）との熱交換によって、第１液体を冷却し、第３水流ラインの水を加熱する。したがって、第２熱交換器３０３を通過した第１液体は、第３熱交換器３０４において冷却され、その後再び第１熱交換器２０４において加熱される。 When the temperature of the first electrolytic solution 106 measured by the first temperature measuring device 203 is equal to or higher than a predetermined temperature, the first liquid flowing through the second circulation path 205 is transferred from the first electrolytic solution 106 in the first heat exchanger 204. Then, the second heat exchanger 303 is further heated. On the 2nd circulation path 305, the 3rd heat exchanger 304 provided in the upstream from the 1st heat exchanger 204 and the downstream from the 2nd heat exchanger 303 is provided. The third heat exchanger 304 cools the first liquid by heat exchange between the first liquid flowing through the second circulation path 305 and the water (second liquid) in the third water flow line (second liquid path). Heat the water in the third stream line. Therefore, the first liquid that has passed through the second heat exchanger 303 is cooled in the third heat exchanger 304 and then heated again in the first heat exchanger 204.

ただし、本実施の形態の水素生成システムの場合、第１熱交換器２０４において熱交換を行うか否かの判断には、第１電解液１０６と所定の温度との大小関係に加えて、燃料電池３０３側の循環経路（第２循環経路）３０５を流れる第１液体の温度も考慮する必要がある。第１熱交換器２０４における熱交換は、第２循環経路３０５上において、第１熱交換器２０４よりも上流側であって、且つ第３熱交換器３０４よりも下流側の第１液体の温度が、第１電解液１０６の温度よりも低い場合に行われる。 However, in the case of the hydrogen generation system of the present embodiment, in determining whether heat exchange is performed in the first heat exchanger 204, in addition to the magnitude relationship between the first electrolyte 106 and a predetermined temperature, fuel It is also necessary to consider the temperature of the first liquid flowing through the circulation path (second circulation path) 305 on the battery 303 side. The heat exchange in the first heat exchanger 204 is the temperature of the first liquid on the second circulation path 305 on the upstream side of the first heat exchanger 204 and on the downstream side of the third heat exchanger 304. Is performed when the temperature is lower than the temperature of the first electrolytic solution 106.

第２循環経路３０５上には、第２循環経路３０５を流れる第１液体を循環させるためのポンプ３０６が設置されている。なお、第２循環経路３０５を流れる第１液体は、水に限定されるものではなく、不凍液、その他の熱媒でもよい。 A pump 306 for circulating the first liquid flowing through the second circulation path 305 is installed on the second circulation path 305. The first liquid flowing through the second circulation path 305 is not limited to water, and may be an antifreeze liquid or other heat medium.

第１温度計測装置２０３により計測された第１電解液１０６の温度が所定の温度未満の場合に、第３熱交換器３０４において冷却された、第２循環経路３０５を流れる第１液体が、第１熱交換器２０４において熱交換を行なわないようにするために、第２バイパスライン３０７が設けられている。 When the temperature of the first electrolytic solution 106 measured by the first temperature measuring device 203 is lower than a predetermined temperature, the first liquid that flows in the second circulation path 305 cooled in the third heat exchanger 304 is the first liquid. A second bypass line 307 is provided to prevent heat exchange in the one heat exchanger 204.

第２循環経路３０５上であって、且つ第２バイパスライン３０７が分岐した後の経路上に、弁３０８が設けられている。第２バイパスライン上には、弁３０９が設けられている。 A valve 308 is provided on the second circulation path 305 and on the path after the second bypass line 307 branches. A valve 309 is provided on the second bypass line.

第１温度計測装置２０３により計測された第１電解液１０６の温度が所定の温度以上の場合には、前記制御部は、弁３０８を開け、弁３０９を閉める。これにより、第１熱交換器２０４で熱交換が行われる。 When the temperature of the first electrolyte solution 106 measured by the first temperature measuring device 203 is equal to or higher than a predetermined temperature, the control unit opens the valve 308 and closes the valve 309. Thereby, heat exchange is performed by the first heat exchanger 204.

一方、第１温度計測装置２０３により計測された第１電解液１０６の温度が所定の温度未満の場合には、前記制御部は、弁３０８を閉め、弁３０９を開ける。これにより、第１熱交換器２０４において熱交換が行われない。 On the other hand, when the temperature of the first electrolytic solution 106 measured by the first temperature measuring device 203 is lower than a predetermined temperature, the control unit closes the valve 308 and opens the valve 309. Thereby, heat exchange is not performed in the first heat exchanger 204.

第３熱交換器３０４において、第２循環経路３０５と熱交換を行ない、加熱される第３水流ライン３１０上には、貯湯槽３１１が設置されている。第３水流ライン３１０を流れる水は、貯湯槽３１１中の低温域部から供給され、第３熱交換器３０４において加熱され、貯湯槽３１１中の高温域部に供給される。 In the 3rd heat exchanger 304, the hot water storage tank 311 is installed on the 3rd water flow line 310 which heat-exchanges with the 2nd circulation path 305, and is heated. The water flowing through the third water flow line 310 is supplied from the low temperature region in the hot water storage tank 311, heated in the third heat exchanger 304, and supplied to the high temperature region in the hot water storage tank 311.

貯湯槽３１１には、使用されて減少した湯を補うため、もしくは貯湯槽３１１の低温域部の温度が上がりすぎた場合の冷却のために、市水ライン３１２が連結されている。これにより、必要に応じて、貯湯槽３１１の低温域部に市水が供給される。 A city water line 312 is connected to the hot water storage tank 311 in order to make up for hot water that has been used and reduced, or for cooling when the temperature of the low temperature region of the hot water storage tank 311 increases excessively. Thereby, city water is supplied to the low temperature region of the hot water tank 311 as necessary.

第３水流ライン３１０を流れる水の動力源として、第３水流ライン３１０上には、ポンプ３１３が設置されている。 A pump 313 is installed on the third water flow line 310 as a power source of water flowing through the third water flow line 310.

また、第２循環経路３０５の第１液体が燃料電池３０１の冷却機能を損なわないようにするため、第２循環経路３０５上にも、第２温度計測装置３１４が設置される。第２温度計測装置３１４によって測定された第１液体の温度に応じて、第３水流ライン３１０を流れる水の流量を制御する、又は、市水ライン３１２から市水を供給する、等による第３熱交換器３０４における熱交換効率を制御する機構をさらに設けてもよい。 In order to prevent the first liquid in the second circulation path 305 from impairing the cooling function of the fuel cell 301, the second temperature measurement device 314 is also installed on the second circulation path 305. According to the temperature of the 1st liquid measured by the 2nd temperature measuring device 314, the flow volume of the water which flows through the 3rd water flow line 310 is controlled, or city water is supplied from the city water line 312, etc. A mechanism for controlling the heat exchange efficiency in the heat exchanger 304 may be further provided.

また、第２温度計測装置３１４によって計測された第１液体の温度に応じて、第２循環経路３０５を流れる第１液体の流量制御などにより、第１熱交換器２０４における熱交換効率を制御して、第２循環経路３０５を流れる第１液体の温度制御を行なう機構をさらに設けてもよい。 Further, the heat exchange efficiency in the first heat exchanger 204 is controlled by controlling the flow rate of the first liquid flowing through the second circulation path 305 according to the temperature of the first liquid measured by the second temperature measuring device 314. Thus, a mechanism for controlling the temperature of the first liquid flowing through the second circulation path 305 may be further provided.

また、第１温度計測装置２０３で計測された第１電解液１０６の温度と比較する所定の温度は、燃料電池３０１の温度情報により決定することが望ましい。第２循環経路３０５の第１液体は、燃料電池３０１の冷却に用いられる。したがって、前記所定の温度を燃料電池３０１の温度よりも低い温度に設定することにより、燃料電池３０１の冷却機能を損なうことなく、第１電解液１０６の熱を第２循環経路３０５を介して回収することが可能となる。 In addition, the predetermined temperature to be compared with the temperature of the first electrolytic solution 106 measured by the first temperature measuring device 203 is preferably determined based on the temperature information of the fuel cell 301. The first liquid in the second circulation path 305 is used for cooling the fuel cell 301. Therefore, by setting the predetermined temperature to a temperature lower than the temperature of the fuel cell 301, the heat of the first electrolytic solution 106 is recovered via the second circulation path 305 without impairing the cooling function of the fuel cell 301. It becomes possible to do.

次に、本実施の形態の水素生成システムにおいて、第１電解液１０６の熱が回収される際の前記制御部による処理の流れを、図４Ｂに示されたフローチャートに沿って説明する。 Next, in the hydrogen generation system of the present embodiment, the flow of processing by the control unit when the heat of the first electrolytic solution 106 is recovered will be described along the flowchart shown in FIG. 4B.

制御部は、まず、第２温度計測装置３１４から、第２循環経路３０５を流れる第１液体の温度の情報を取得する（Ｓ３１）。制御部は、次に、第１温度計測装置２０３から第１電解液１０６の温度の情報を取得する（Ｓ３２）。次に、取得した第１液体の温度と、第１電解液１０６の温度とを比較する（Ｓ３３）。第１電解液１０６の温度が第１液体の温度よりも高い場合は、第１電解液１０６の温度と所定の温度とを比較する（Ｓ３４）。第１電解液１０６の温度が所定の温度以上の場合、制御部は、弁３０９を閉じて、弁３０８を開く（Ｓ３５）。これにより、第１熱交換器２０４において、第１電解液循環経路２０１の第１電解液１０６と第２循環経路３０５の第１液体との間で熱交換が行われる。一方、Ｓ３３において第１液体の温度が第１電解液１０６の温度以上である場合と、Ｓ３４において第１電解液１０６の温度が所定の温度未満の場合は、制御部は、弁３０９を開き、弁３０８を閉じる（Ｓ３６）。すなわち、第１熱交換器２０４における熱交換は行われない。 First, the control unit acquires information on the temperature of the first liquid flowing through the second circulation path 305 from the second temperature measurement device 314 (S31). Next, the control unit acquires information on the temperature of the first electrolytic solution 106 from the first temperature measuring device 203 (S32). Next, the obtained temperature of the first liquid is compared with the temperature of the first electrolyte 106 (S33). When the temperature of the first electrolytic solution 106 is higher than the temperature of the first liquid, the temperature of the first electrolytic solution 106 is compared with a predetermined temperature (S34). When the temperature of the 1st electrolyte solution 106 is more than predetermined temperature, a control part closes valve 309 and opens valve 308 (S35). Thereby, in the first heat exchanger 204, heat exchange is performed between the first electrolyte 106 in the first electrolyte circulation path 201 and the first liquid in the second circulation path 305. On the other hand, when the temperature of the first liquid is equal to or higher than the temperature of the first electrolytic solution 106 in S33 and when the temperature of the first electrolytic solution 106 is lower than the predetermined temperature in S34, the control unit opens the valve 309, The valve 308 is closed (S36). That is, heat exchange in the first heat exchanger 204 is not performed.

（実施の形態４）
実施の形態４の水素生成システムにおいて、水素生成デバイス１００の構成は、実施の形態１の場合と同様である。したがって、ここではその説明を省略する。 (Embodiment 4)
In the hydrogen generation system according to the fourth embodiment, the configuration of the hydrogen generation device 100 is the same as that in the first embodiment. Therefore, the description thereof is omitted here.

図５Ａに、実施の形態４の水素生成システムの構成例を示す。図５Ａにおいて、図１、図２Ａ、図３Ａ及び図４Ａと同じ構成要素については同じ符号を用い、説明は省略する。なお、図５Ａには図示されていないが、本実施の形態の水素生成システムにも、実施の形態１と同様に、制御部が設けられている。この制御部は、本システムの全体を制御するものであって、本システムを構成する各部分を制御できる。この制御部は、本発明の特徴部分である、第１電解液１０６の温度情報に応じて熱交換が行われるか否かの判断（詳細は後述する）も行う。 FIG. 5A shows a configuration example of the hydrogen generation system according to the fourth embodiment. 5A, the same reference numerals are used for the same components as those in FIGS. 1, 2A, 3A, and 4A, and descriptions thereof are omitted. Although not shown in FIG. 5A, the hydrogen generation system of the present embodiment is also provided with a control unit as in the first embodiment. This control unit controls the entire system, and can control each part constituting the system. This control unit also determines whether or not heat exchange is performed according to the temperature information of the first electrolytic solution 106, which is a characteristic part of the present invention (details will be described later).

本実施の形態の水素生成システムにおいても、実施の形態３と同様に、水素生成デバイス１００において生成した水素を電気エネルギーに変換するための燃料電池３０１が設けられている。第２気液分離装置２０９からは水素ライン３０２が分岐しており、得られた水素は燃料電池３０１に供給される。水素ライン３０２上には、水素を貯蔵するための設備、および水素を高圧にするための圧縮機構など、が設置されていてもよい。 Also in the hydrogen generation system of the present embodiment, a fuel cell 301 for converting the hydrogen generated in the hydrogen generation device 100 into electric energy is provided as in the third embodiment. A hydrogen line 302 is branched from the second gas-liquid separator 209, and the obtained hydrogen is supplied to the fuel cell 301. On the hydrogen line 302, equipment for storing hydrogen, a compression mechanism for increasing the pressure of hydrogen, and the like may be installed.

第１温度計測装置２０３により計測された第１電解液１０６の温度が所定の温度以上だった場合、前記制御部は、第１バイパスライン２１１上の弁２１２を閉め、第１電解液循環経路２０１上の弁２１３を開ける。これにより、第１電解液循環経路２０１を流れる第１電解液１０６は、第１熱交換器２０４において、第２循環経路３０５を流れる第１液体と熱交換を行う。その結果、第１電解液循環経路２０１の第１電解液１０６は冷却されて、第２循環経路３０５の第１液体は加熱される。 When the temperature of the first electrolytic solution 106 measured by the first temperature measuring device 203 is equal to or higher than a predetermined temperature, the control unit closes the valve 212 on the first bypass line 211 and the first electrolytic solution circulation path 201. Open the upper valve 213. Thereby, the first electrolyte 106 flowing through the first electrolyte circulation path 201 exchanges heat with the first liquid flowing through the second circulation path 305 in the first heat exchanger 204. As a result, the first electrolyte 106 in the first electrolyte circulation path 201 is cooled, and the first liquid in the second circulation path 305 is heated.

一方、第１温度計測装置２０３により計測された第１電解液１０６の温度が所定の温度に達していない場合には、前記制御部は、弁２１２を開けて、弁２１３を閉める。これにより、第１電解液循環経路２０１を流れる第１電解液１０６は、第１熱交換器２０４を経由しないので、第１熱交換器２０４で冷却されることはない。これにより、第１電解液循環経路２０１を流れる第１電解液１０６は、十分に温度が上昇していない段階で第１熱交換器２０４において熱を失うことがなく、水素生成デバイス１００において獲得した熱を所定の温度に到達するまで蓄積することが可能となる。その結果、第１水流ライン２０５を介して、高温の湯を得ることができる。 On the other hand, when the temperature of the first electrolytic solution 106 measured by the first temperature measuring device 203 has not reached a predetermined temperature, the control unit opens the valve 212 and closes the valve 213. Accordingly, the first electrolyte 106 flowing through the first electrolyte circulation path 201 does not pass through the first heat exchanger 204 and is not cooled by the first heat exchanger 204. Thereby, the first electrolyte 106 flowing through the first electrolyte circulation path 201 is acquired in the hydrogen generation device 100 without losing heat in the first heat exchanger 204 when the temperature is not sufficiently increased. Heat can be accumulated until a predetermined temperature is reached. As a result, hot water can be obtained via the first water flow line 205.

ただし、本実施の形態の水素生成システムの場合、第１熱交換器２０４において熱交換を行うか否かの判断は、第１電解液１０６と所定の温度との大小関係に加えて、燃料電池３０３側の循環経路（第２循環経路）３０５を流れる第１液体の温度も考慮する必要がある。第１熱交換器２０４における熱交換は、第２循環経路３０５上において、第１熱交換器２０４よりも上流側であって、且つ第３熱交換器３０４よりも下流側の第１液体の温度が、第１電解液１０６の温度よりも低い場合に行われる。 However, in the case of the hydrogen generation system according to the present embodiment, whether or not heat exchange is performed in the first heat exchanger 204 is determined in addition to the magnitude relationship between the first electrolyte 106 and a predetermined temperature. It is also necessary to consider the temperature of the first liquid flowing through the circulation path (second circulation path) 305 on the 303 side. The heat exchange in the first heat exchanger 204 is the temperature of the first liquid on the second circulation path 305 on the upstream side of the first heat exchanger 204 and on the downstream side of the third heat exchanger 304. Is performed when the temperature is lower than the temperature of the first electrolytic solution 106.

第２循環経路２０５を流れる第１液体は、第１熱交換器２０４を経由した後、第２熱交換器３０３において加熱される。第２循環経路３０５上には、第１熱交換器２０４よりも上流側で且つ第２熱交換器３０３よりも下流側に設けられた第３熱交換器３０４が設けられている。第３熱交換器３０４は、第２循環経路３０５を流れる第１液体と、第３水流ライン（第２液体経路）の水（第２液体）との熱交換によって、第１液体を冷却し、第３水流ラインの水を加熱する。したがって、第２熱交換器３０３を通過した第１液体は、第３熱交換器３０４において冷却され、その後再び第１熱交換器２０４において加熱される。 The first liquid flowing in the second circulation path 205 is heated in the second heat exchanger 303 after passing through the first heat exchanger 204. On the 2nd circulation path 305, the 3rd heat exchanger 304 provided in the upstream from the 1st heat exchanger 204 and the downstream from the 2nd heat exchanger 303 is provided. The third heat exchanger 304 cools the first liquid by heat exchange between the first liquid flowing through the second circulation path 305 and the water (second liquid) in the third water flow line (second liquid path). Heat the water in the third stream line. Therefore, the first liquid that has passed through the second heat exchanger 303 is cooled in the third heat exchanger 304 and then heated again in the first heat exchanger 204.

第２循環経路３０５上には、第２循環経路３０５を流れる第１液体を循環させるためのポンプ３０６が設置されている。第２循環経路３０５を流れる第１液体は、水に限定されるものではなく、不凍液、その他の熱媒でもよい。 A pump 306 for circulating the first liquid flowing through the second circulation path 305 is installed on the second circulation path 305. The first liquid flowing through the second circulation path 305 is not limited to water, and may be an antifreeze liquid or other heat medium.

また、第２温度計測装置３１４によって測定された第１液体の温度に応じて、第２循環経路３０５を流れる第１液体の流量制御などにより、第１熱交換器２０４における熱交換効率を制御して、第２循環経路３０５を流れる第１液体の温度制御を行なう機構をさらに設けてもよい。 Further, the heat exchange efficiency in the first heat exchanger 204 is controlled by controlling the flow rate of the first liquid flowing through the second circulation path 305 according to the temperature of the first liquid measured by the second temperature measuring device 314. Thus, a mechanism for controlling the temperature of the first liquid flowing through the second circulation path 305 may be further provided.

次に、本実施の形態の水素生成システムにおいて、第１電解液１０６の熱が回収される際の前記制御部による処理の流れを、図５Ｂに示されたフローチャートに沿って説明する。 Next, in the hydrogen generation system of the present embodiment, the flow of processing by the control unit when the heat of the first electrolyte 106 is recovered will be described along the flowchart shown in FIG. 5B.

制御部は、まず、第２温度計測装置３１４から、第２循環経路３０５を流れる第１液体の温度の情報を取得する（Ｓ４１）。制御部は、次に、第１温度計測装置２０３から第１電解液１０６の温度の情報を取得する（Ｓ４２）。次に、取得した第１液体の温度と、第１電解液１０６の温度とを比較する（Ｓ４３）。第１電解液１０６の温度が第１液体よりも高い場合は、第１電解液１０６の温度と所定の温度とを比較する（Ｓ４４）。第１電解液１０６の温度が所定の温度以上の場合、制御部は、弁２１２を閉じて、弁２１３を開く（Ｓ４５）。これにより、第１熱交換器２０４において、第１電解液循環経路２０１の第１電解液１０６と第２循環経路３０５の第１液体との間で熱交換が行われる。一方、Ｓ４３において第１液体の温度が第１電解液１０６の温度以上である場合と、Ｓ４４において第１電解液１０６の温度が所定の温度未満の場合は、制御部は、弁２１２を開き、弁２１３を閉じる（Ｓ４６）。すなわち、第１熱交換器２０４における熱交換は行われない。 First, the control unit acquires information on the temperature of the first liquid flowing through the second circulation path 305 from the second temperature measurement device 314 (S41). Next, the control unit acquires information on the temperature of the first electrolytic solution 106 from the first temperature measurement device 203 (S42). Next, the obtained temperature of the first liquid is compared with the temperature of the first electrolytic solution 106 (S43). When the temperature of the first electrolytic solution 106 is higher than that of the first liquid, the temperature of the first electrolytic solution 106 is compared with a predetermined temperature (S44). When the temperature of the 1st electrolyte solution 106 is more than predetermined temperature, a control part closes valve 212 and opens valve 213 (S45). Thereby, in the first heat exchanger 204, heat exchange is performed between the first electrolyte 106 in the first electrolyte circulation path 201 and the first liquid in the second circulation path 305. On the other hand, when the temperature of the first liquid is equal to or higher than the temperature of the first electrolytic solution 106 in S43 and when the temperature of the first electrolytic solution 106 is lower than the predetermined temperature in S44, the control unit opens the valve 212, The valve 213 is closed (S46). That is, heat exchange in the first heat exchanger 204 is not performed.

本発明にかかる水素生成システムは、太陽光照射により水を分解することにより得られる水素エネルギーのみならず、太陽光により加熱された循環水から熱エネルギーを回収し、高温の温水を得ることが可能となるため、太陽エネルギーを高い効率で利用することが可能であり、家庭用のみならず、業務用の発電システム等としても有用である。 The hydrogen generation system according to the present invention can recover not only hydrogen energy obtained by decomposing water by sunlight irradiation but also heat energy from circulating water heated by sunlight to obtain high-temperature hot water. Therefore, it is possible to use solar energy with high efficiency, and it is useful not only for home use but also as a power generation system for business use.

１００水素生成デバイス
１０１半導体電極（第１電極）
１０２対極（第２電極）
１０３外部回路
１０４筐体
１０５セパレータ
１０６第１電解液
１０７第２電解液
１０８第１電解液導入口
１０９第１電解液導出口
１１０第２電解液導入口
１１１第２電解液導出口
２０１第１電解液循環経路（第１循環経路）
２０２ポンプ
２０３第１温度計測装置
２０４第１熱交換器
２０５第１水流ライン（第１液体経路）
２０６弁
２０７第１気液分離装置
２０８第２電解液循環経路
２０９第２気液分離装置
２１０ポンプ
２１１第１バイパスライン
２１２弁
２１３弁
３０１燃料電池
３０２水素ライン
３０３第２熱交換器
３０４第３熱交換器
３０５第２循環経路
３０６ポンプ
３０７第２バイパスライン
３０８弁
３０９弁
３１０第３水流ライン（第２液体経路）
３１１貯湯槽
３１２市水ライン
３１３ポンプ
３１４第２温度計測装置 100 Hydrogen generation device 101 Semiconductor electrode (first electrode)
102 Counter electrode (second electrode)
DESCRIPTION OF SYMBOLS 103 External circuit 104 Case 105 Separator 106 1st electrolyte 107 Second electrolyte 108 First electrolyte inlet 109 First electrolyte outlet 110 Second electrolyte inlet 111 Second electrolyte outlet 201 First electrolysis Liquid circulation path (first circulation path)
202 Pump 203 First temperature measuring device 204 First heat exchanger 205 First water flow line (first liquid path)
206 Valve 207 First gas-liquid separator 208 Second electrolyte circulation path 209 Second gas-liquid separator 210 Pump 211 First bypass line 212 Valve 213 Valve 301 Fuel cell 302 Hydrogen line 303 Second heat exchanger 304 Third heat Exchanger 305 Second circulation path 306 Pump 307 Second bypass line 308 Valve 309 Valve 310 Third water flow line (second liquid path)
311 Hot water tank 312 City water line 313 Pump 314 Second temperature measuring device

Claims

A first electrode containing a photocatalytic semiconductor; a second electrode electrically connected to the first electrode; an electrolyte containing water in contact with a surface of the first electrode and a surface of the second electrode; A separator disposed between the first electrode and the second electrode and dividing the electrolytic solution into a first electrolytic solution in contact with the surface of the first electrode and a second electrolytic solution in contact with the surface of the second electrode; A housing for housing the first electrode, the second electrode, the electrolytic solution, and the separator, and the water is decomposed by irradiating the photocatalytic semiconductor of the first electrode with light. A hydrogen generation device for generating hydrogen;
A mechanism for leading the first electrolytic solution out of the hydrogen generating device and reintroducing the first electrolytic solution into the hydrogen generating device, and circulating the first electrolytic solution using the first circulating route; ,
A first heat exchanger provided on the first circulation path;
Means for measuring the temperature of the first electrolyte solution;
With
When the measured temperature of the first electrolytic solution is equal to or higher than a predetermined temperature, in the first heat exchanger, the first electrolytic solution in the first circulation path and the first liquid in the first liquid path Heat exchange is performed, the first electrolyte is cooled and the first liquid is heated;
Hydrogen generation system.

When the measured temperature of the first electrolytic solution is lower than the predetermined temperature, in the first heat exchanger, the first electrolytic solution and the first liquid route in the first circulation path are substantially set. Heat exchange with the first liquid is not performed,
The hydrogen generation system according to claim 1.

The means for measuring the temperature of the first electrolyte solution is provided on the first circulation path;
The hydrogen generation system according to claim 1 or 2.

A fuel cell;
A mechanism for supplying hydrogen generated in the hydrogen generator to the fuel cell;
The hydrogen generation system according to any one of claims 1 to 3, further comprising:

A second heat exchanger that heats the first liquid by heat exchange with the fuel cell on the first liquid path and downstream of the first heat exchanger;
The hydrogen generation system according to claim 4.

Means for measuring the temperature of the first liquid upstream of the first heat exchanger in the first liquid path;
Controlling the heat exchange efficiency in the first heat exchanger according to the measured temperature of the first liquid,
The hydrogen generation system according to claim 5.

Control of heat exchange efficiency in the first heat exchanger is performed by adjusting the flow rate of the first liquid in the first liquid path.
The hydrogen generation system according to claim 6.

The first liquid path forms a second circulation path for circulating the first liquid between the first heat exchanger and the second heat exchanger;
A mechanism that includes the second circulation path and circulates the first liquid using the second circulation path;
On the second circulation path, provided upstream of the first heat exchanger and downstream of the second heat exchanger, the first liquid and the second liquid of the second circulation path A third heat exchanger that cools the first liquid by heat exchange with a second liquid in a path and heats the second liquid;
Further equipped with,
The hydrogen generation system according to any one of claims 5 to 7.

A hot water storage tank for storing hot water obtained by using heat of the second liquid heated by the third heat exchanger;
The hydrogen generation system according to claim 8.

The hot water tank is provided on the second liquid path,
The hydrogen generation system according to claim 9.

Means for measuring the temperature of the first liquid in the second circulation path;
Controlling the heat exchange efficiency in the third heat exchanger according to the measured temperature of the first liquid,
The hydrogen generation system according to any one of claims 8 to 10.

Control of heat exchange efficiency in the third heat exchanger is performed by adjusting the flow rate of the second liquid in the second liquid path,
The hydrogen generation system according to claim 11.

Control of heat exchange efficiency in the third heat exchanger is performed by supplying cold water to the second liquid path.
The hydrogen generation system according to claim 11.

The predetermined temperature of the first electrolyte is determined by temperature information of the fuel cell;
The hydrogen generation system according to any one of claims 4 to 13.

Means for measuring the temperature of the first liquid upstream of the first heat exchanger in the first liquid path;
When the measured temperature of the first electrolytic solution is higher than the measured temperature of the first liquid and equal to or higher than the predetermined temperature, the first heat exchanger includes the first circulation path. Heat exchange between the first electrolyte and the first liquid in the first liquid path is performed to cool the first electrolyte and heat the first liquid;
The hydrogen generation system according to any one of claims 5 to 14.