JP2016098387A - Hydrogen production apparatus, hydrogen production method, and electric power storage system - Google Patents

Hydrogen production apparatus, hydrogen production method, and electric power storage system Download PDF

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JP2016098387A
JP2016098387A JP2014234433A JP2014234433A JP2016098387A JP 2016098387 A JP2016098387 A JP 2016098387A JP 2014234433 A JP2014234433 A JP 2014234433A JP 2014234433 A JP2014234433 A JP 2014234433A JP 2016098387 A JP2016098387 A JP 2016098387A
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hydrogen
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hydrogen storage
water vapor
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JP6415941B2 (en
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山田　和矢
Kazuya Yamada
和矢 山田
恒雄 大村
Tsuneo Omura
恒雄 大村
新一 牧野
Shinichi Makino
新一 牧野
久夫 渡邉
Hisao Watanabe
久夫 渡邉
斉二 藤原
Seiji Fujiwara
斉二 藤原
重夫 笠井
Shigeo Kasai
重夫 笠井
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Toshiba Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen production apparatus, a hydrogen production method, and an electric power storage system that can achieve high hydrogen production efficiency by reducing heat input for hydrogen production.SOLUTION: A hydrogen production apparatus 10 comprises: a first heating part 12 that heats supplied raw material water to generate steam and raises its temperature to a predetermined value; an electrolytic cell 17 that inputs the steam to generate hydrogen and oxygen by high-temperature steam electrolysis; a moisture separator 18 that inputs the generated hydrogen and electrolytically unreacted steam to separate the hydrogen and the steam at a temperature higher than a temperature required for a hydrogenation reaction of a hydrogen occluding material; and a hydrogenation reactor 21 that subjects a mixture of the separated hydrogen and the hydrogen occluding material to the hydrogenation reaction to occlude the hydrogen in the hydrogen occluding material.SELECTED DRAWING: Figure 1

Description

本発明の実施形態は、高温水蒸気電解により水素を製造・貯蔵する水素製造技術、貯蔵した水素を燃料として発電を行う電力貯蔵システムに関する。   Embodiments of the present invention relate to a hydrogen production technique for producing and storing hydrogen by high-temperature steam electrolysis, and an electric power storage system that generates electricity using the stored hydrogen as a fuel.

近年、水素をエネルギー媒体とした水素エネルギー社会の実現が注目されている。水素を製造する技術の一つとして、高温水蒸気電解法が広く知られている。この高温水蒸気電解法は、高温（通常、５００℃以上）の水蒸気を電気分解することにより水素及び酸素を生成する方法である。   In recent years, the realization of a hydrogen energy society using hydrogen as an energy medium has attracted attention. As one of techniques for producing hydrogen, a high temperature steam electrolysis method is widely known. This high temperature steam electrolysis method is a method of generating hydrogen and oxygen by electrolyzing high temperature (usually 500 ° C. or higher) water vapor.

高温水蒸気電解法を用いるメリットを具体的に説明する。水の電気分解に必要なエネルギー（ΔＨ）は次式（１）で表される。ここで、ΔＧはギブスエネルギー差、ＴΔＳは可逆反応熱を意味し、ΔＧは電気エネルギーで、ＴΔＳは熱エネルギーで与えられる。
ΔＨ＝ΔＧ＋ＴΔＳ （１） The advantages of using the high temperature steam electrolysis method will be specifically described. The energy (ΔH) required for water electrolysis is expressed by the following equation (1). Here, ΔG is the Gibbs energy difference, TΔS is the heat of reversible reaction, ΔG is the electric energy, and TΔS is the heat energy.
ΔH = ΔG + TΔS (1)

ΔＨは温度による変化が小さいのに対し、ΔＧは高温になるにつれて小さくなる。このため、高温環境下で水蒸気の電気分解を行うことにより、水の電気分解に比べて電気分解に必要な電気量を低減することができる。この性質により、室温での水の電気分解よりも３０％程度少ない電力で同じ水素製造量が得られるため、高いエネルギー効率で水素製造を行うことができる。   ΔH changes little with temperature, while ΔG decreases with increasing temperature. For this reason, by performing electrolysis of water vapor in a high temperature environment, the amount of electricity required for electrolysis can be reduced compared to electrolysis of water. Because of this property, the same hydrogen production amount can be obtained with about 30% less electric power than water electrolysis at room temperature, so that hydrogen production can be performed with high energy efficiency.

さらに、原料が水であるため、二酸化炭素を生じない再生可能エネルギーによる電力と二酸化炭素を生じない熱源を用いれば、全く二酸化炭素を排出せずに水素製造が可能となる。   Furthermore, since the raw material is water, hydrogen can be produced without exhausting any carbon dioxide by using electric power from renewable energy that does not produce carbon dioxide and a heat source that does not produce carbon dioxide.

また、製造した水素を一時的に貯蔵する方法としては、（１）圧縮して高圧水素ガスにする、（２）液化水素にする、（３）水素吸蔵材料に吸蔵する、という３つの水素貯蔵方法が知られている。これらのうち、水素吸蔵材料は一般的に水素を吸蔵するとき発熱して、水素を放出するときに吸熱する。
このため、水素を水素吸蔵材料に吸蔵する水素貯蔵方法は、熱エネルギーが水素製造に及ぼす寄与が大きい高温水蒸気電解法との組み合わせに適している。 In addition, there are three methods for temporarily storing the produced hydrogen: (1) compressing it into high-pressure hydrogen gas, (2) converting it into liquefied hydrogen, and (3) storing it in a hydrogen storage material. The method is known. Of these, the hydrogen storage material generally generates heat when storing hydrogen and absorbs heat when releasing hydrogen.
For this reason, the hydrogen storage method of storing hydrogen in the hydrogen storage material is suitable for combination with the high-temperature steam electrolysis method in which thermal energy greatly contributes to hydrogen production.

従来、高温水蒸気電解により水素を生成する水素製造装置において、水素製造に係るエネルギー効率を改善する様々な技術が検討されている。   Conventionally, in a hydrogen production apparatus that generates hydrogen by high-temperature steam electrolysis, various techniques for improving energy efficiency related to hydrogen production have been studied.

例えば、特許文献１には、水素吸蔵材料が水素を吸蔵する際の発熱を高温水蒸気電解の原料となる水蒸気の製造に利用して、高温水蒸気電解による水素製造のエネルギー効率を改善する技術が提案されている。
また、特許文献２には、水素吸蔵材料に吸蔵した水素を取り出すためには熱源として、固体酸化物型燃料電池（ＳＯＦＣ：Ｓｏｌｉｄ Ｏｘｉｄｅ Ｆｕｅｌ Ｃｅｌｌ）の排熱を利用する技術が提案されている。 For example, Patent Document 1 proposes a technique for improving the energy efficiency of hydrogen production by high-temperature steam electrolysis by utilizing the heat generated when the hydrogen storage material occludes hydrogen for the production of steam as a raw material for high-temperature steam electrolysis. Has been.
Patent Document 2 proposes a technique that uses exhaust heat of a solid oxide fuel cell (SOFC) as a heat source to extract hydrogen stored in the hydrogen storage material.

特開２０１３−１９９６７５号公報JP 2013-199675 A 特開２００５−２０３２６６号公報JP 2005-203266 A

ところで、高温水蒸気電解により水素を生成する際、生成された水素には電解未反応分の水蒸気が含まれる。このため、生成された水素を水素吸蔵材料に吸蔵させる場合、水素吸蔵材料の性能劣化を防止するため、水素と未反応分の水蒸気との混合ガスを冷却し、水蒸気を凝縮させて、混合ガスに含まれる水分を予め分離除去する必要がある。そして、水分除去後に、水素吸蔵材料の水素化反応に必要な温度まで水素を再度加熱して、生成した水素を水素吸蔵材料に吸蔵させる。   By the way, when hydrogen is generated by high-temperature steam electrolysis, the generated hydrogen includes water that is not electrolyzed. For this reason, when the produced hydrogen is stored in the hydrogen storage material, in order to prevent the performance of the hydrogen storage material from deteriorating, the mixed gas of hydrogen and unreacted water vapor is cooled, the water vapor is condensed, and the mixed gas It is necessary to separate and remove the water contained in the water in advance. Then, after removing the water, the hydrogen is heated again to a temperature necessary for the hydrogenation reaction of the hydrogen storage material, and the generated hydrogen is stored in the hydrogen storage material.

このように、水素と未反応分の水蒸気との混合ガスを一旦冷却した後に、水素化反応に必要な温度まで再加熱するプロセスが必要となるため、熱ロスが生じており、水素製造効率（水素製造量または製造水素の燃焼熱／投入する熱エネルギー）が低下するという問題があった。   In this way, a process of reheating the mixed gas of hydrogen and unreacted water vapor to a temperature required for the hydrogenation reaction after cooling is necessary, resulting in heat loss and hydrogen production efficiency ( There has been a problem in that the amount of hydrogen produced or the heat of combustion of the produced hydrogen / the heat energy to be input) decreases.

また、高温水蒸気電解により水素を製造・貯蔵して、この水素を燃料として発電するという、水素を媒介とした電力貯蔵システムにおいて、充放電効率（得られる電気量／外部から供給される電気量）を高くするためには、システムを構成する各要素で熱ロスを低減して、熱エネルギーを最大限有効に利用することが求められる。   Moreover, in a power storage system that uses hydrogen as a fuel to produce and store hydrogen by high-temperature steam electrolysis and generate electricity using this hydrogen as fuel, charge / discharge efficiency (amount of electricity obtained / amount of electricity supplied from the outside) In order to increase the power consumption, it is required to reduce the heat loss at each element constituting the system and use the heat energy most effectively.

本発明はこのような事情を考慮してなされたもので、水素製造に係る入熱を低減して、高い水素製造効率を実現する水素製造装置、水素製造方法及び電力貯蔵システムを提供することを目的とする。   The present invention has been made in consideration of such circumstances, and provides a hydrogen production apparatus, a hydrogen production method, and an electric power storage system that reduce heat input related to hydrogen production and achieve high hydrogen production efficiency. Objective.

本発明の実施形態に係る水素製造装置において、供給された原料水を加熱して水蒸気を発生させて、所定の温度まで昇温させる第１加熱部と、前記水蒸気を入力して、高温水蒸気電解により水素と酸素とを生成する電解セルと、生成された前記水素と電解未反応分の前記水蒸気とを入力して、水素吸蔵材料の水素化反応に必要な温度よりも高い温度で、前記水素と前記水蒸気とを分離する水分分離器と、分離された前記水素と前記水素吸蔵材料との混合物を水素化反応させて、前記水素を前記水素吸蔵材料に吸蔵させる水素化反応器と、を備えることを特徴とする。   In the hydrogen production apparatus according to the embodiment of the present invention, the supplied raw water is heated to generate steam to raise the temperature to a predetermined temperature, and the steam is input to perform high-temperature steam electrolysis The electrolytic cell for generating hydrogen and oxygen, and the generated hydrogen and the water vapor for unreacted electrolysis are input, and the hydrogen at a temperature higher than the temperature required for the hydrogenation reaction of the hydrogen storage material. And a water separator that separates the water vapor, and a hydrogenation reactor that causes a hydrogenation reaction of the separated mixture of the hydrogen and the hydrogen storage material to store the hydrogen in the hydrogen storage material. It is characterized by that.

本発明の実施形態に係る水素製造方法において、供給された原料水を加熱して水蒸気を発生させて、所定の温度まで昇温させるステップと、前記水蒸気を入力して、高温水蒸気電解により水素と酸素とを生成するステップと、生成された前記水素と電解未反応分の前記水蒸気とを入力して、水素吸蔵材料の水素化反応に必要な温度よりも高い温度で、前記水素と前記水蒸気とを分離するステップと、分離された前記水素と前記水素吸蔵材料との混合物を水素化反応させて、前記水素を前記水素吸蔵材料に吸蔵させるステップと、を含むことを特徴とする。   In the hydrogen production method according to the embodiment of the present invention, the supplied raw water is heated to generate water vapor, the temperature is raised to a predetermined temperature, the water vapor is input, and hydrogen is generated by high-temperature steam electrolysis. The step of generating oxygen, and the generated hydrogen and the unreacted water vapor are input, and the hydrogen and the water vapor are heated at a temperature higher than the temperature required for the hydrogenation reaction of the hydrogen storage material. And a hydrogenation reaction of the separated mixture of the hydrogen and the hydrogen storage material to store the hydrogen in the hydrogen storage material.

本発明の実施形態に係る電力貯蔵システムにおいて、供給された原料水を加熱して水蒸気を発生させて、所定の温度まで昇温させる第１加熱部と、前記水蒸気を入力して、高温水蒸気電解により水素と酸素とを生成する電解セルと、生成された前記水素と電解未反応分の前記水蒸気とを入力して、水素吸蔵材料の水素化反応に必要な温度よりも高い温度で、前記水素と前記水蒸気とを分離する水分分離器と、分離された前記水素と前記水素吸蔵材料との混合物を水素化反応させて、前記水素を前記水素吸蔵材料に吸蔵させる水素化反応器と、水素吸蔵後の前記水素吸蔵材料を入力して、所定の温度まで加熱する第２加熱部と、前記第２加熱部において加熱された水素吸蔵後の前記水素吸蔵材料を脱水素化反応させて、前記水素を脱離させる脱水素化反応器と、前記脱水素化反応器により脱離された前記水素と前記水素吸蔵材料とを入力して、前記水素と前記水素吸蔵材料とに分離する分離器と、前記分離器において分離された前記水素を入力して、燃料電池反応により発電する燃料電池セルと、を備えることを特徴とする。   In the power storage system according to the embodiment of the present invention, the supplied raw water is heated to generate water vapor to raise the temperature to a predetermined temperature, and the water vapor is input to perform high temperature steam electrolysis. The electrolytic cell for generating hydrogen and oxygen, and the generated hydrogen and the water vapor for unreacted electrolysis are input, and the hydrogen at a temperature higher than the temperature required for the hydrogenation reaction of the hydrogen storage material. A water separator for separating the water vapor from the water vapor; a hydrogenation reactor for hydrogenating the separated mixture of the hydrogen and the hydrogen storage material to store the hydrogen in the hydrogen storage material; and a hydrogen storage A second heating unit that inputs the subsequent hydrogen storage material and heats the hydrogen storage material to a predetermined temperature; and the hydrogen storage material after the hydrogen storage heated in the second heating unit is dehydrogenated to produce the hydrogen Detaching A hydrogenation reactor, a separator that inputs the hydrogen desorbed by the dehydrogenation reactor and the hydrogen storage material, and separates the hydrogen into the hydrogen storage material; and a separation in the separator A fuel cell that receives the generated hydrogen and generates power by a fuel cell reaction.

本発明の実施形態により、水素製造に係る入熱を低減して、高い水素製造効率を実現する水素製造装置、水素製造方法及び電力貯蔵システムが提供される。   According to the embodiments of the present invention, a hydrogen production apparatus, a hydrogen production method, and an electric power storage system that reduce heat input related to hydrogen production and realize high hydrogen production efficiency are provided.

第１実施形態に係る水素製造装置の構成図。The block diagram of the hydrogen production apparatus which concerns on 1st Embodiment. 第１実施形態に係る水素製造装置の変形例を示す構成図。The lineblock diagram showing the modification of the hydrogen production device concerning a 1st embodiment. 第２実施形態に係る水素製造装置の構成図。The block diagram of the hydrogen production apparatus which concerns on 2nd Embodiment. 本実施形態に係る電力貯蔵システムの構成図。The block diagram of the electric power storage system which concerns on this embodiment.

（第１実施形態）
以下、本実施形態を添付図面に基づいて説明する。
図１に示すように、第１実施形態に係る水素製造装置１０は、供給された原料水を加熱して水蒸気を発生させて、所定の温度まで昇温させる第１加熱部１２と、水蒸気を入力して、高温水蒸気電解により水素と酸素とを生成する電解セル１７と、生成された水素と電解未反応分の水蒸気とを入力して、水素吸蔵材料の水素化反応に必要な温度よりも高い温度で、水素と水蒸気とを分離する水分分離器１８と、分離された水素と水素吸蔵材料との混合物を水素化反応させて、水素を水素吸蔵材料に吸蔵させる水素化反応器２１と、を備える。なお、図１は、水素吸蔵材料として不飽和炭化水素を使用する場合の構成を示している。 (First embodiment)
Hereinafter, this embodiment is described based on an accompanying drawing.
As shown in FIG. 1, the hydrogen production apparatus 10 according to the first embodiment includes a first heating unit 12 that heats supplied raw water to generate water vapor to raise the temperature to a predetermined temperature, and water vapor. Input the electrolytic cell 17 that generates hydrogen and oxygen by high-temperature steam electrolysis, and the generated hydrogen and the water that has not been electrolyzed, and the temperature is higher than the temperature required for the hydrogenation reaction of the hydrogen storage material. A water separator 18 for separating hydrogen and water vapor at a high temperature, a hydrogenation reactor 21 for hydrogenating a mixture of the separated hydrogen and the hydrogen storage material, and storing the hydrogen in the hydrogen storage material, Is provided. In addition, FIG. 1 has shown the structure in the case of using unsaturated hydrocarbon as a hydrogen storage material.

水供給部１１には、高温水蒸気電解により水素と酸素とに分解される原料水５０が貯水されている。原料水５０は、ポンプ（図示省略）により吸引されて、第１加熱部１２に供給される。   The water supply unit 11 stores raw water 50 that is decomposed into hydrogen and oxygen by high-temperature steam electrolysis. The raw material water 50 is sucked by a pump (not shown) and supplied to the first heating unit 12.

第１加熱部１２は、直列に接続された熱交換器１３、１４、１５、及び１６を有しており、水供給部１１から供給された原料水５０を加熱して水蒸気を発生させて、所定の温度まで昇温させる。なお、所定の温度とは、高温水蒸気電解を行う最適な温度を意味しており、通常は５００℃以上、より望ましくは７００℃以上となる。第１加熱部１２は、原料水５０の蒸発、加熱を補助するための加熱器を備えても良い。なお、熱交換器１３〜１６の具体的な動作については後述する。   The first heating unit 12 includes heat exchangers 13, 14, 15, and 16 connected in series, and heats the raw water 50 supplied from the water supply unit 11 to generate water vapor, The temperature is raised to a predetermined temperature. The predetermined temperature means an optimum temperature for performing high-temperature steam electrolysis, and is usually 500 ° C. or higher, more preferably 700 ° C. or higher. The first heating unit 12 may include a heater for assisting evaporation and heating of the raw material water 50. In addition, specific operation | movement of the heat exchangers 13-16 is mentioned later.

電解セル１７は、固体酸化物電解質（図示省略）を中心に配置して、その両側に水素極と酸素極とが形成されている。第１加熱部１２から出力された高温の水蒸気５１は、電解セル１７の水素極側に導入されて、酸素極側には空気または水蒸気が導入される。   The electrolytic cell 17 is arranged around a solid oxide electrolyte (not shown), and a hydrogen electrode and an oxygen electrode are formed on both sides thereof. The high-temperature water vapor 51 output from the first heating unit 12 is introduced to the hydrogen electrode side of the electrolysis cell 17, and air or water vapor is introduced to the oxygen electrode side.

電解セル１７は、外部から入力電力１００の供給を受けて電気分解を行い、水素と酸素を生成する。そして、電解セル１７の水素極側からは、水素と電解未反応分の水蒸気との混合ガス５２が出力され、酸素極側からは酸素５３が出力される。なお、電解セル１７に供給する入力電力１００として、風力、水力、太陽光等の再生可能エネルギーを利用した電力源から供給しても良い。   The electrolysis cell 17 is supplied with input power 100 from the outside and performs electrolysis to generate hydrogen and oxygen. A mixed gas 52 of hydrogen and unreacted water vapor is output from the hydrogen electrode side of the electrolytic cell 17, and oxygen 53 is output from the oxygen electrode side. The input power 100 supplied to the electrolysis cell 17 may be supplied from a power source using renewable energy such as wind power, hydraulic power, and sunlight.

電解セル１７から出力された酸素５３は、第１加熱部１２の熱交換器１５、１３で原料水５０または水蒸気と熱交換を行った後に、外部に排出される。
一方、電解セル１７から出力された水素と水蒸気との混合ガス５２は、熱交換器１６で第１加熱部１２を流動する水蒸気と熱交換を行った後に、水分分離器１８に出力される。 The oxygen 53 output from the electrolysis cell 17 is exhausted to the outside after performing heat exchange with the raw water 50 or water vapor in the heat exchangers 15 and 13 of the first heating unit 12.
On the other hand, the mixed gas 52 of hydrogen and water vapor output from the electrolysis cell 17 is output to the water separator 18 after performing heat exchange with water vapor flowing through the first heating unit 12 in the heat exchanger 16.

水分分離器１８は、水素と電解未反応分の水蒸気との混合ガス５２を入力して、混合ガス５２を冷却すること無く、水素吸蔵材料の水素化反応に必要な温度よりも高い温度で、生成された水素５４と未反応分の水蒸気５５とに分離する。   The moisture separator 18 inputs a mixed gas 52 of hydrogen and water vapor that has not been electrolyzed, and cools the mixed gas 52 at a temperature higher than the temperature required for the hydrogenation reaction of the hydrogen storage material. The generated hydrogen 54 and unreacted water vapor 55 are separated.

高温の混合ガス５２から水分を分離する水分分離器１８として、５００℃程度の温度で水分分離性能を発揮するパラジウム膜やシリカ膜を適用する。水分は水素吸蔵材料の性能を阻害するため、事前に水分を分離除去することで、水素吸蔵材料の性能を長期間維持することができる。   As the water separator 18 that separates water from the high-temperature mixed gas 52, a palladium membrane or silica membrane that exhibits water separation performance at a temperature of about 500 ° C. is applied. Since moisture impedes the performance of the hydrogen storage material, the performance of the hydrogen storage material can be maintained for a long period of time by separating and removing the moisture in advance.

水素吸蔵材料の水素化反応に必要な温度は、使用される水素吸蔵材料により異なるものであるが、電解セル１７から出力された混合ガス５２は非常に高温であるため、余分な加熱をすること無く、混合ガス５２は水素吸蔵材料の水素化反応に必要な温度条件を満たす。   The temperature required for the hydrogenation reaction of the hydrogen storage material varies depending on the hydrogen storage material used. However, the mixed gas 52 output from the electrolysis cell 17 is very high temperature, so that extra heating is required. In addition, the mixed gas 52 satisfies the temperature condition necessary for the hydrogenation reaction of the hydrogen storage material.

水分分離器１８において分離された水蒸気５５は、電解セル１７に入力される水蒸気に合流され電気分解に用いられる。
一方、分離された水素５４は、不飽和炭化水素貯留槽１９から供給され、熱交換器２０を介して昇温された不飽和炭化水素５６（水素吸蔵材料）と合流、混合される。不飽和炭化水素として、トルエン、ベンゼン、ナフタレン等が例示される。 The water vapor 55 separated in the water separator 18 is merged with the water vapor input to the electrolysis cell 17 and used for electrolysis.
On the other hand, the separated hydrogen 54 is supplied from the unsaturated hydrocarbon storage tank 19 and joined and mixed with the unsaturated hydrocarbon 56 (hydrogen storage material) heated through the heat exchanger 20. Examples of the unsaturated hydrocarbon include toluene, benzene, naphthalene and the like.

水素化反応器２１は、水素化反応に適した触媒（例えば、白金、ニッケルなど）が充填されており、水素と不飽和炭化水素との混合ガス５７を入力する。そして、水素化反応により水素を不飽和炭化水素に吸蔵させて有機ハイドライド５８（水素吸蔵後の水素吸蔵材料）を生成する。なお、生成された有機ハイドライド５８には、未反応分の水素または不飽和炭化水素も含まれる。   The hydrogenation reactor 21 is filled with a catalyst (for example, platinum, nickel, etc.) suitable for the hydrogenation reaction, and receives a mixed gas 57 of hydrogen and unsaturated hydrocarbons. Then, hydrogen is occluded in the unsaturated hydrocarbon by a hydrogenation reaction to produce an organic hydride 58 (hydrogen occlusion material after occlusion of hydrogen). The produced organic hydride 58 includes unreacted hydrogen or unsaturated hydrocarbon.

生成された有機ハイドライド５８は、熱交換器（第１の熱交換器）１４で原料水５０と熱交換を行って、原料水５０を水蒸気に変換する。さらに、熱交換器２０において不飽和炭化水素５６と熱交換を行った後に、有機ハイドライド貯留槽２２に貯蔵される。   The generated organic hydride 58 exchanges heat with the raw water 50 in the heat exchanger (first heat exchanger) 14 to convert the raw water 50 into water vapor. Further, after heat exchange with the unsaturated hydrocarbon 56 in the heat exchanger 20, the heat is stored in the organic hydride storage tank 22.

このように、水素に含まれる未反応の水蒸気を分離する際に、外部冷却せず、水素吸蔵材料が水素を吸蔵する際の温度よりも高い温度で、水素に含まれる未反応の水蒸気を分離することにより、水素吸蔵前での水素の昇温を省略することができ、水素製造に係る熱ロスを低減することができる。   In this way, when unreacted water vapor contained in hydrogen is separated, the unreacted water vapor contained in hydrogen is separated at a temperature higher than the temperature at which the hydrogen storage material absorbs hydrogen without external cooling. By doing so, the temperature rise of hydrogen before hydrogen occlusion can be omitted, and the heat loss related to hydrogen production can be reduced.

未反応の水蒸気を冷却して凝縮分離した場合には、水素吸蔵材料に水素を吸蔵させるために再加熱が必要となるが、これが不要なシンプルな構成となり、投入エネルギーが少ないプロセスが可能となる。また、水素吸蔵時の反応熱を用いて高温水蒸気電解に用いる原料水５０の蒸発、加熱を行うことにより、水素製造効率をさらに向上させることができる。   When unreacted water vapor is cooled and condensed and separated, reheating is required to store hydrogen in the hydrogen storage material, but this is a simple configuration that does not require it, and a process with low input energy is possible. . Moreover, hydrogen production efficiency can be further improved by evaporating and heating the raw material water 50 used for high temperature steam electrolysis using the reaction heat at the time of hydrogen occlusion.

ここで、水素製造装置１０の物質収支及び熱収支を、プロセスシュミレータを用いて具体的に計算、評価した。なお、不飽和炭化水素としてトルエンを使用し、有機ハイドライド（水素吸蔵後の不飽和炭化水素）をメチルシクロヘキサンとする。   Here, the material balance and heat balance of the hydrogen production apparatus 10 were specifically calculated and evaluated using a process simulator. In addition, toluene is used as the unsaturated hydrocarbon, and the organic hydride (unsaturated hydrocarbon after occlusion of hydrogen) is methylcyclohexane.

計算条件は、原料水５０を温度２０℃、１ｋｍｏｌ／ｈで供給、トルエンを温度２０℃、６ｋｍｏｌ／ｈで供給する。また、電解セル１７における、高温水蒸気電解の運転温度を７５０℃、水蒸気利用率（水素生成量（水蒸気反応量）／供給水蒸気量）を８０％とする。なお、高温水蒸気電解への入力電力１００は前述の式（１）のΔＨ相当分とした。   The calculation conditions are that raw water 50 is supplied at a temperature of 20 ° C. and 1 kmol / h, and toluene is supplied at a temperature of 20 ° C. and 6 kmol / h. In addition, the operating temperature of the high-temperature steam electrolysis in the electrolytic cell 17 is set to 750 ° C., and the steam utilization rate (hydrogen generation amount (steam reaction amount) / supply steam amount) is set to 80%. Note that the input power 100 to the high-temperature steam electrolysis was set to be equivalent to ΔH in the above-described equation (1).

この条件で計算した結果、熱交換器２０出口の有機ハイドライド５８は、温度５４℃、メチルシクロヘキサン；０．２４ｋｍｏｌ／ｈ、トルエン；５．７６ｋｍｏｌ／ｈとなった。また、酸素５３が、温度２０℃、０．４ｋｍｏｌ／ｈとなった。   As a result of calculation under these conditions, the organic hydride 58 at the outlet of the heat exchanger 20 had a temperature of 54 ° C., methylcyclohexane; 0.24 kmol / h, toluene; 5.76 kmol / h. Moreover, oxygen 53 became temperature 20 degreeC and 0.4 kmol / h.

水分分離器１８で分離された水蒸気５５は、温度４８４℃、０．２ｋｍｏｌ／ｈであった。水素化反応器２１に供給される不飽和炭化水素と水素の混合ガス５７は、温度１３２℃、トルエン；６ｋｍｏｌ／ｈ、水素；０．８ｋｍｏｌ／ｈとなった。   The water vapor 55 separated by the water separator 18 had a temperature of 484 ° C. and 0.2 kmol / h. The unsaturated hydrocarbon and hydrogen mixed gas 57 supplied to the hydrogenation reactor 21 had a temperature of 132 ° C., toluene: 6 kmol / h, hydrogen: 0.8 kmol / h.

水素化反応器２１出口の有機ハイドライド５８は、温度１８７℃、メチルシクロヘキサン；０．２４ｋｍｏｌ／ｈ、トルエン；５．７６ｋｍｏｌ／ｈ、水素；０．０８ｋｍｏｌ／ｈであった。   The organic hydride 58 at the outlet of the hydrogenation reactor 21 had a temperature of 187 ° C., methylcyclohexane; 0.24 kmol / h, toluene; 5.76 kmol / h, hydrogen; 0.08 kmol / h.

熱交換器１４で原料水５０が水蒸気に変化し、熱交換器１４出口の水蒸気は、温度１８７℃、１ｋｍｏｌ／ｈとなった。   The raw water 50 was changed to water vapor in the heat exchanger 14, and the water vapor at the outlet of the heat exchanger 14 reached a temperature of 187 ° C. and 1 kmol / h.

なお、水素化反応器２１の出口の有機ハイドライド５８に含まれる水素０．０８ｋｍｏｌ／ｈは、熱交換器２０の下流で液相と分離して、水分分離器１８出口の水素５４に合流させている。   Note that 0.08 kmol / h of hydrogen contained in the organic hydride 58 at the outlet of the hydrogenation reactor 21 is separated from the liquid phase downstream of the heat exchanger 20 and merged with the hydrogen 54 at the outlet of the moisture separator 18. Yes.

また、熱交換器２０出口の有機ハイドライドの組成がモル分率でメチルシクロヘキサン；０．０４、トルエン；０．９６となっているが、この組成のままで不飽和炭化水素５６として供給すれば、メチルシクロヘキサンのモル分率を上げることができる。   In addition, the composition of the organic hydride at the outlet of the heat exchanger 20 is methylcyclohexane; 0.04, toluene; 0.96 in terms of mole fraction, but if this composition is supplied as unsaturated hydrocarbon 56, The mole fraction of methylcyclohexane can be increased.

以上の結果により、トルエンに水素が付加される際の反応熱により、水素化反応器２１の出口の有機ハイドライド５８が加熱され、その熱が熱交換器１４により原料水５０が水蒸気に変化する蒸発潜熱が賄うことができることが評価された。   As a result of the above, the organic hydride 58 at the outlet of the hydrogenation reactor 21 is heated by the reaction heat when hydrogen is added to toluene, and the heat is evaporated by the heat exchanger 14 so that the raw water 50 is changed to steam. It was evaluated that latent heat could be covered.

さらに、高温水蒸気電解への入力電力１００は、前述の式（１）のΔＨに相当する分が５５ｋＷ、熱交換器１６出口の水蒸気を７５０℃に昇温する顕熱として０．５ｋＷ、を合計して５５．５ｋＷと評価された。   Further, the input power 100 to the high-temperature steam electrolysis is a total of 55 kW corresponding to ΔH in the above formula (1) and 0.5 kW as sensible heat for raising the steam at the outlet of the heat exchanger 16 to 750 ° C. Was estimated to be 55.5 kW.

水素製造量が、０．８ｋｍｏｌ／ｈ（１７．９Ｎｍ３／ｈ）なので、水素製造の原単価は３．１ｋＷｈ／Ｎｍ３となった。水素化反応の反応熱を利用しない場合には、原料水の蒸発潜熱分（本条件では１１．３ｋＷ）を別途供給する必要があるが、本実施形態によれば削減可能となる。 Since the hydrogen production amount was 0.8 kmol / h (17.9 Nm 3 / h), the original unit price of hydrogen production was 3.1 kWh / Nm 3 . When the reaction heat of the hydrogenation reaction is not used, the latent heat of evaporation of the raw material water (11.3 kW in this condition) needs to be supplied separately, but according to this embodiment, it can be reduced.

図２は、第１実施形態に係る水素製造装置１０の変形例を示している。なお、図１と共通の構成又は機能を有する部分については、同一符号で示し、重複する説明を省略する。   FIG. 2 shows a modification of the hydrogen production apparatus 10 according to the first embodiment. Note that portions having the same configuration or function as those in FIG.

第１実施形態（図１）では、水分分離器１８において水素５４と電解未反応分の水蒸気５５とを分離した後に、水素５４と不飽和炭化水素５６とを混合させて水素化反応器２１に入力していた。   In the first embodiment (FIG. 1), after separating the hydrogen 54 and the unreacted water vapor 55 in the water separator 18, the hydrogen 54 and the unsaturated hydrocarbon 56 are mixed to form the hydrogenation reactor 21. I was typing.

一方、本変形例では、電解セル１７において生成された水素と電解未反応分の水蒸気との混合ガス５２を水分分離器１８に入力する前に、不飽和炭化水素５６と混合ガス５２とを合流させて、水素と不飽和炭化水素と混合させる。そして、水素と電解未反応分の水蒸気と不飽和炭化水素との混合ガス５９が水分分離器１８に入力される。   On the other hand, in this modified example, the unsaturated hydrocarbon 56 and the mixed gas 52 are merged before the mixed gas 52 of hydrogen generated in the electrolysis cell 17 and the electrolyzed unreacted water vapor is input to the moisture separator 18. And mixing with hydrogen and unsaturated hydrocarbons. Then, a mixed gas 59 of hydrogen, water vapor that is unreacted by electrolysis, and unsaturated hydrocarbons 59 is input to the water separator 18.

水分分離器１８は、混合ガス５９を入力して、混合ガス５９を冷却すること無く、水素吸蔵材料の水素化反応に必要な温度よりも高い温度で、混合ガス５９から水蒸気を分離する。そして、水蒸気が除去された、水素と不飽和炭化水素との混合ガス５７を水素化反応器２１に出力する。   The moisture separator 18 receives the mixed gas 59 and separates water vapor from the mixed gas 59 at a temperature higher than the temperature required for the hydrogenation reaction of the hydrogen storage material without cooling the mixed gas 59. Then, the mixed gas 57 of hydrogen and unsaturated hydrocarbons from which the water vapor has been removed is output to the hydrogenation reactor 21.

前述したプロセスシュミレーションと同様の条件で熱収支を計算、評価した場合、水分分離器１８での水分除去温度は１３２℃と評価された。この温度条件では、水分分離器１８として、モレキュラーシーブを充填した吸着塔で水分の吸着と脱着を交互に繰り返す圧力変動吸着（ＰＳＡ）法を適用することで、混合ガス５９から水蒸気を分離できる。   When the heat balance was calculated and evaluated under the same conditions as in the process simulation described above, the water removal temperature in the water separator 18 was evaluated as 132 ° C. Under this temperature condition, water vapor can be separated from the mixed gas 59 by applying a pressure fluctuation adsorption (PSA) method in which adsorption and desorption of moisture are alternately repeated in an adsorption tower packed with molecular sieves as the moisture separator 18.

また、合金系や無機系の材料を水素化反応器２１に充填させて、水素化吸蔵材料として使用しても良い。合金系や無機系の材料を水素化吸蔵材料として使用する場合、水素化反応器２１を熱交換器１４と兼用する構成が可能となる。また、熱媒を介して水素化反応により発生する熱エネルギーを熱交換器１４に輸送する構成も可能となる。   Alternatively, an alloy or inorganic material may be filled in the hydrogenation reactor 21 and used as a hydrogenation storage material. When an alloy-based or inorganic material is used as the hydrogenation storage material, a configuration in which the hydrogenation reactor 21 is also used as the heat exchanger 14 is possible. Moreover, the structure which transports the heat energy which generate | occur | produces by hydrogenation reaction to the heat exchanger 14 via a heat medium is also attained.

（第２実施形態）
図３は、第２実施形態に係る水素製造装置１０の構成図である。なお、第１実施形態と共通の構成又は機能を有する部分については、同一符号で示し、重複する説明を省略する。なお、第２実施形態では、水素化反応器２１内に、水素吸蔵材料として合金系または無機系の材料が充填されているものとする。 (Second Embodiment)
FIG. 3 is a configuration diagram of the hydrogen production apparatus 10 according to the second embodiment. In addition, about the part which has a structure or function common to 1st Embodiment, it shows with the same code | symbol and the overlapping description is abbreviate | omitted. In the second embodiment, it is assumed that the hydrogenation reactor 21 is filled with an alloy-based or inorganic material as a hydrogen storage material.

ヒートポンプ２３は、第１加熱部１２と水素化反応器２１との間に設けられており、循環する冷媒を圧縮及び膨張させて熱エネルギーを移動させるものである。このヒートポンプ２３は、冷媒を介して水素化反応器２１において水素化反応の際に生じる熱エネルギーを、第１加熱部１２に供給された原料水５０に伝達させる。   The heat pump 23 is provided between the first heating unit 12 and the hydrogenation reactor 21 and moves heat energy by compressing and expanding the circulating refrigerant. The heat pump 23 transmits thermal energy generated during the hydrogenation reaction in the hydrogenation reactor 21 to the raw water 50 supplied to the first heating unit 12 via the refrigerant.

なお、図３では、水素化反応の際に生じる熱エネルギーを、熱交換器１４を流動する原料水５０に伝達させる構成が示されているが、本構成に限定されるものでは無く、第１加熱部１２を流動する原料水５０または水蒸気に伝達出来れば良い。   FIG. 3 shows a configuration in which the heat energy generated during the hydrogenation reaction is transmitted to the raw material water 50 flowing through the heat exchanger 14, but is not limited to this configuration. What is necessary is just to be able to transmit to the raw material water 50 or water vapor | steam which flows through the heating part 12. FIG.

第１実施形態で示したプロセスシュミレーションと同様の条件下で、ＣＯＰ５のヒートポンプ２３を使用して熱収支を評価した場合、原料水５０の蒸発潜熱分（第１実施形態の条件では１１．３ｋＷ）を１／６に削減することが評価された。ヒートポンプ２３を用いることにより、水素吸蔵材料の反応熱を効率よく利用でき原単位の低減が可能となる。   When the heat balance is evaluated using the heat pump 23 of the COP5 under the same conditions as the process simulation shown in the first embodiment, the latent heat of vaporization of the raw water 50 (11.3 kW under the conditions of the first embodiment) Was evaluated to be reduced to 1/6. By using the heat pump 23, the reaction heat of the hydrogen storage material can be used efficiently, and the basic unit can be reduced.

（第３実施形態）
図４は、本実施形態に係る電力貯蔵システム４０の構成図である。 (Third embodiment)
FIG. 4 is a configuration diagram of the power storage system 40 according to the present embodiment.

電力貯蔵システム４０は、高温水蒸気電解により生成した水素を不飽和炭化水素に吸蔵させて有機ハイドライドとして貯留する。そして、貯留している水素を用いて燃料電池反応により発電を行うシステムである。なお、高温水蒸気電解により生成した水素を不飽和炭化水素に吸蔵させて有機ハイドライドとして貯留するまでの構成は、第１実施形態（図１）と同様となるため説明を省略する。   The power storage system 40 stores hydrogen generated by high-temperature steam electrolysis in an unsaturated hydrocarbon and stores it as an organic hydride. And it is a system which generates electric power by fuel cell reaction using the stored hydrogen. In addition, since it is the same as that of 1st Embodiment (FIG. 1), the structure until it occludes the hydrogen produced | generated by high temperature steam electrolysis in an unsaturated hydrocarbon and stores it as an organic hydride is abbreviate | omitted description.

第２加熱部２４は、熱交換器２５、２６、２７、及び補助加熱器２８を有しており、有機ハイドライド貯留槽２２に貯留された有機ハイドライド６０を入力する。そして、有機ハイドライド６０の脱水素化に必要な温度まで昇温させる。なお、補助加熱器２８は、熱交換器２５〜２７からの入熱だけでは不足する場合に、有機ハイドライド６０を昇温させるための補助的な加熱器である。   The second heating unit 24 includes heat exchangers 25, 26, 27 and an auxiliary heater 28, and inputs the organic hydride 60 stored in the organic hydride storage tank 22. Then, the temperature is raised to a temperature necessary for dehydrogenation of the organic hydride 60. The auxiliary heater 28 is an auxiliary heater for raising the temperature of the organic hydride 60 when only the heat input from the heat exchangers 25 to 27 is insufficient.

脱水素化反応器２９は、有機ハイドライド６０の脱水素化に適した触媒（例えば、白金、ニッケルなど）が充填されており、第２加熱部２４において昇温された有機ハイドライド６０を脱水素化させて、有機ハイライドから水素を脱離させる。   The dehydrogenation reactor 29 is filled with a catalyst (for example, platinum, nickel, etc.) suitable for dehydrogenation of the organic hydride 60, and dehydrogenates the organic hydride 60 heated in the second heating unit 24. To desorb hydrogen from the organic halide.

水素の脱離により生成された水素と不飽和炭化水素の混合ガス６１は、熱交換器（第２の熱交換器）２６で有機ハイドライド６０と熱交換した後に、分離器３０に出力される。   The mixed gas 61 of hydrogen and unsaturated hydrocarbon generated by the desorption of hydrogen is exchanged with the organic hydride 60 by the heat exchanger (second heat exchanger) 26 and then output to the separator 30.

分離器３０は、脱水素化反応器２９により脱離された水素と不飽和炭化水素を入力して、水素と不飽和炭化水素とに分離する。分離器３０は、１００℃〜１５０℃程度の温度で性能を発揮するポリイミド膜を適用する。   The separator 30 inputs the hydrogen and unsaturated hydrocarbons desorbed by the dehydrogenation reactor 29 and separates them into hydrogen and unsaturated hydrocarbons. The separator 30 applies a polyimide membrane that exhibits performance at a temperature of about 100 ° C to 150 ° C.

分離された不飽和炭化水素６３は、熱交換器（第３の熱交換器）２５で有機ハイドライド６０と熱交換した後に、不飽和炭化水素貯留槽１９に回収される。一方、水素６２は、熱交換器３１を介して燃料電池セル３３に出力される。   The separated unsaturated hydrocarbon 63 is recovered in the unsaturated hydrocarbon storage tank 19 after exchanging heat with the organic hydride 60 in the heat exchanger (third heat exchanger) 25. On the other hand, the hydrogen 62 is output to the fuel cell 33 via the heat exchanger 31.

燃料電池セル３３は、電解セル１７と同様、固体酸化物電解質を中心に配置して、その両側に水素極と酸素極とが形成されている。燃料電池セル３３の水素極側には水素６２が導入され、酸素極側には窒素及と酸素の混合ガス６４が導入される。そして、燃料電池セル３３は、水素極及び酸素極に導入された供給ガスを用いて燃料電池反応を行い、出力電力１０１を生成する。   Similar to the electrolytic cell 17, the fuel battery cell 33 is arranged around a solid oxide electrolyte, and a hydrogen electrode and an oxygen electrode are formed on both sides thereof. Hydrogen 62 is introduced to the hydrogen electrode side of the fuel battery cell 33, and a mixed gas 64 of nitrogen and oxygen is introduced to the oxygen electrode side. The fuel cell 33 performs a fuel cell reaction using the supply gas introduced into the hydrogen electrode and the oxygen electrode to generate output power 101.

燃料電池反応の際に水素極側から出力される水蒸気６６は、熱交換器２７で有機ハイドライド６０と熱交換を行い、さらに熱交換器３１で分離器３０から出力された水素６２と熱交換を行った後に、外部に排出される。
一方、酸素極側から出力される窒素６５は、熱交換器３２で燃料電池セル３３に供給される窒素及と酸素の混合ガス６４と熱交換を行った後に、外部に排出される。 The water vapor 66 output from the hydrogen electrode side during the fuel cell reaction exchanges heat with the organic hydride 60 in the heat exchanger 27 and further exchanges heat with the hydrogen 62 output from the separator 30 in the heat exchanger 31. After going, it is discharged outside.
On the other hand, the nitrogen 65 output from the oxygen electrode side is exhausted to the outside after performing heat exchange with the mixed gas 64 of nitrogen and oxygen supplied to the fuel cell 33 by the heat exchanger 32.

なお、第２加熱部２４は、燃料電池セル３３において発電時に生じるジュール熱を用いて、有機ハイドライド６０を加熱しても良い。   Note that the second heating unit 24 may heat the organic hydride 60 using Joule heat generated during power generation in the fuel battery cell 33.

このように、電力貯蔵システム４０は、第１実施形態（図１）で示した水素製造・貯蔵方法と、貯蔵された水素を燃料として発電する際に各要素において発生する熱エネルギーを有効に利用するエネルギー自立型の発電方法と、を組み合わせて構成することにより、高い充放電効率を実現することができる。   In this way, the power storage system 40 effectively uses the hydrogen production / storage method shown in the first embodiment (FIG. 1) and the thermal energy generated in each element when generating electricity using the stored hydrogen as fuel. High charge / discharge efficiency can be realized by combining the energy self-supporting power generation method.

ここで、電力貯蔵システム４０の熱収支及び物質収支を具体的に計算、評価する。なお、高温水蒸気電解により水素を有機ハイドライドとして貯蔵するまでの構成については第１実施形態で示した条件と同様なものとして、貯蔵した水素を燃料にして発電して電力を得るプロセスについて計算、評価する。   Here, the heat balance and material balance of the power storage system 40 are specifically calculated and evaluated. In addition, about the structure until it stores hydrogen as an organic hydride by high temperature steam electrolysis, it is the same as the conditions shown in the first embodiment, and calculation and evaluation are performed on the process of generating electricity by using the stored hydrogen as fuel. To do.

まず、計算条件として、水素吸蔵済みの有機ハイドライド６０を温度２０℃、メチルシクロヘキサン０．２８ｋｍｏｌ／ｈ、トルエン０．０５ｋｍｏｌ／ｈで供給する。
一方、燃料電池セル３３には、酸素と窒素の混合ガス６４を温度２０℃、酸素０．４ｋｍｏｌ／ｈ、窒素１．６ｋｍｏｌ／ｈで供給する。また、燃料電池セル３３の運転温度８５０℃、水素利用率（水蒸気生成量／水素供給量）１００％とする。 First, as calculation conditions, the hydrogenated organic hydride 60 is supplied at a temperature of 20 ° C., methylcyclohexane 0.28 kmol / h, and toluene 0.05 kmol / h.
On the other hand, the fuel cell 33 is supplied with a mixed gas 64 of oxygen and nitrogen at a temperature of 20 ° C., oxygen of 0.4 kmol / h, and nitrogen of 1.6 kmol / h. The operating temperature of the fuel battery cell 33 is 850 ° C., and the hydrogen utilization rate (water vapor generation amount / hydrogen supply amount) is 100%.

この条件下で計算した結果、熱交換器２５出口の不飽和炭化水素６３が、温度２２℃、メチルシクロヘキサン０．０１ｋｍｏｌ／ｈ、トルエンが０．３２ｋｍｏｌ／ｈとなった。
また、熱交換器３１出口の水蒸気６６が、温度１１４℃、０．８ｋｍｏｌ／ｈとなり、熱交換器３２出口の窒素６５が温度６８℃、１．６ｋｍｏｌ／ｈとなった。 As a result of calculation under these conditions, the unsaturated hydrocarbon 63 at the outlet of the heat exchanger 25 had a temperature of 22 ° C., methylcyclohexane 0.01 kmol / h, and toluene 0.32 kmol / h.
Further, the water vapor 66 at the outlet of the heat exchanger 31 became a temperature of 114 ° C. and 0.8 kmol / h, and the nitrogen 65 at the outlet of the heat exchanger 32 became a temperature of 68 ° C. and 1.6 kmol / h.

また、脱水素反応に必要な吸熱分に対する不足分として１１．２ｋＷの補助加熱を要する。この不足分は、燃料電池セル３３で発電する際に生じるジュール熱で賄うことにより、外部からの加熱は不要となる。   In addition, 11.2 kW of auxiliary heating is required as a shortage of the endothermic component necessary for the dehydrogenation reaction. This shortage is covered by Joule heat generated when power is generated by the fuel battery cell 33, so that no external heating is required.

前述の式（１）を燃料電池反応に当てはめると、ΔＧが得られる理論電力となる。実際には、ΔＧからセルのジュール熱として失われる分を差し引いたものが得られる出力電力１０１となる。本条件では出力電力１０１は入力電力１００の約６５％となった   When the above equation (1) is applied to the fuel cell reaction, ΔG is obtained as the theoretical power. Actually, the output power 101 is obtained by subtracting the amount lost as the Joule heat of the cell from ΔG. Under this condition, the output power 101 is about 65% of the input power 100.

以上述べた各実施形態の水素製造装置によれば、高温水蒸気電解により生成された水素と電解未反応分の水蒸気とを分離する際に、水素吸蔵材料の水素化反応に必要な温度より高い温度で分離することで、水素製造時の入熱を低減して、高い水素製造効率を実現することができる。   According to the hydrogen production apparatus of each embodiment described above, a temperature higher than the temperature required for the hydrogenation reaction of the hydrogen storage material when separating the hydrogen generated by high-temperature steam electrolysis and the unreacted water vapor from the electrolysis. By separating at, it is possible to reduce heat input during hydrogen production and achieve high hydrogen production efficiency.

本発明のいくつかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその変形は、発明の範囲や要旨に含まれるとともに、特許請求の範囲に記載された発明とその均等の範囲に含まれる。   Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

例えば、本実施形態に係る電力貯蔵システム（図４）では、水素を燃料とする発電プロセスに固体酸化物型の燃料電池セル３３を適用したが、水素を単独で燃料にして燃焼し燃焼ガスでガスタービンを駆動する発電あるいは天然ガス等、他の燃料に混合して燃焼し燃焼ガスでガスタービンを駆動する発電プロセスを適用することも可能である。
さらには、水素を単独またはほかの燃料に混合して燃焼し燃焼ガスを二酸化炭素等の媒体と混合してガスタービンを駆動する発電プロセスを適用することも可能である。 For example, in the power storage system (FIG. 4) according to the present embodiment, the solid oxide fuel cell 33 is applied to a power generation process using hydrogen as a fuel. It is also possible to apply a power generation process for driving a gas turbine with combustion gas after being mixed with other fuels such as power generation for driving a gas turbine or natural gas.
Furthermore, it is also possible to apply a power generation process in which hydrogen is mixed alone or mixed with another fuel and burned, and the combustion gas is mixed with a medium such as carbon dioxide to drive the gas turbine.

１０…水素製造装置、１１…水供給部、１２…第１加熱部、１３、１４、１５、１６…熱交換器、１７…電解セル、１８…水分分離器、１９…不飽和炭化水素貯留槽、２０…熱交換器、２１…水素化反応器、２２…有機ハイドライド貯蔵槽、２３…ヒートポンプ、２４…第２加熱部、２５、２６，２７…熱交換器、２８…補助加熱器、２９…脱水素化反応器、３０…分離器、３１…熱交換器、３２…熱交換器、３３…燃料電池セル、４０…電力貯蔵システム、５０…原料水、５１…水蒸気、５２…水素と水蒸気の混合ガス、５３…酸素、５４…水素、５５…水蒸気、５６…不飽和炭化水素、５７…不飽和炭化水素と水素の混合ガス、５８…有機ハイドライド、５９…水素と不飽和炭化水素と水蒸気の混合ガス、６０…有機ハイドライド、６１…不飽和炭化水素と水素の混合ガス、６２…水素、６３…不飽和炭化水素、６４…酸素と窒素の混合ガス、６５…窒素、６６…水蒸気、１００…入力電力、１０１…出力電力。 DESCRIPTION OF SYMBOLS 10 ... Hydrogen production apparatus, 11 ... Water supply part, 12 ... 1st heating part, 13, 14, 15, 16 ... Heat exchanger, 17 ... Electrolytic cell, 18 ... Moisture separator, 19 ... Unsaturated hydrocarbon storage tank 20 ... heat exchanger, 21 ... hydrogenation reactor, 22 ... organic hydride storage tank, 23 ... heat pump, 24 ... second heating unit, 25, 26, 27 ... heat exchanger, 28 ... auxiliary heater, 29 ... Dehydrogenation reactor, 30 ... separator, 31 ... heat exchanger, 32 ... heat exchanger, 33 ... fuel cell, 40 ... power storage system, 50 ... raw water, 51 ... steam, 52 ... hydrogen and steam Mixed gas, 53 ... oxygen, 54 ... hydrogen, 55 ... steam, 56 ... unsaturated hydrocarbon, 57 ... mixed gas of unsaturated hydrocarbon and hydrogen, 58 ... organic hydride, 59 ... hydrogen, unsaturated hydrocarbon and steam Mixed gas, 60 ... Organic hydride, 61 A mixed gas of unsaturated hydrocarbons and hydrogen, 62 ... hydrogen, 63 ... unsaturated hydrocarbons, 64 ... mixed gas of oxygen and nitrogen, 65 ... nitrogen, 66 ... steam, 100 ... input power, 101 ... output power.

Claims (10)

供給された原料水を加熱して水蒸気を発生させて、所定の温度まで昇温させる第１加熱部と、
前記水蒸気を入力して、高温水蒸気電解により水素と酸素とを生成する電解セルと、
生成された前記水素と電解未反応分の前記水蒸気とを入力して、水素吸蔵材料の水素化反応に必要な温度よりも高い温度で、前記水素と前記水蒸気とを分離する水分分離器と、
分離された前記水素と前記水素吸蔵材料との混合物を水素化反応させて、前記水素を前記水素吸蔵材料に吸蔵させる水素化反応器と、を備えることを特徴とする水素製造装置。 A first heating unit for heating the supplied raw water to generate water vapor and raising the temperature to a predetermined temperature;
An electrolytic cell that inputs the water vapor and generates hydrogen and oxygen by high-temperature steam electrolysis;
A water separator that separates the hydrogen and the water vapor at a temperature higher than the temperature required for the hydrogenation reaction of the hydrogen storage material by inputting the generated hydrogen and the water vapor of the electrolytically unreacted part;
A hydrogen production apparatus comprising: a hydrogenation reactor that causes a hydrogenation reaction of the separated mixture of the hydrogen and the hydrogen storage material, and stores the hydrogen in the hydrogen storage material. 前記第１加熱部は、水素吸蔵後の前記水素吸蔵材料と前記原料水との間で熱交換させる第１の熱交換器を有することを特徴とする請求項１に記載の水素製造装置。   2. The hydrogen production apparatus according to claim 1, wherein the first heating unit includes a first heat exchanger that exchanges heat between the hydrogen storage material after storing hydrogen and the raw water. 前記水分分離器において前記水素と電解未反応分の前記水蒸気とを分離する前に、前記水素吸蔵材料と前記水素とを混合させることを特徴とする請求項１または請求項２に記載の水素製造装置。   3. The hydrogen production according to claim 1, wherein the hydrogen storage material and the hydrogen are mixed before the hydrogen and the unreacted water vapor are separated in the moisture separator. apparatus. 循環する冷媒を圧縮及び膨張させて熱エネルギーを移動させるヒートポンプをさらに備えて、
前記ヒートポンプは、前記冷媒を介して前記水素化反応の際に生じる熱エネルギーを前記原料水に伝達させることを特徴とする請求項１から請求項３のいずれか一項に記載の水素製造装置。 It further includes a heat pump that compresses and expands the circulating refrigerant to move the heat energy,
The hydrogen production apparatus according to any one of claims 1 to 3, wherein the heat pump transmits thermal energy generated during the hydrogenation reaction to the raw water through the refrigerant. 前記水素吸蔵材料は、不飽和炭化水素であることを特徴とする請求項１から請求項４のいずれか一項に記載の水素製造装置。   The hydrogen production apparatus according to any one of claims 1 to 4, wherein the hydrogen storage material is an unsaturated hydrocarbon. 供給された原料水を加熱して水蒸気を発生させて、所定の温度まで昇温させるステップと、
前記水蒸気を入力して、高温水蒸気電解により水素と酸素とを生成するステップと、
生成された前記水素と電解未反応分の前記水蒸気とを入力して、水素吸蔵材料の水素化反応に必要な温度よりも高い温度で、前記水素と前記水蒸気とを分離するステップと、
分離された前記水素と前記水素吸蔵材料との混合物を水素化反応させて、前記水素を前記水素吸蔵材料に吸蔵させるステップと、を含むことを特徴とする水素製造方法。 Heating the supplied raw water to generate water vapor and raising the temperature to a predetermined temperature;
Inputting the steam and generating hydrogen and oxygen by high-temperature steam electrolysis;
Separating the hydrogen and the water vapor at a temperature higher than the temperature required for the hydrogenation reaction of the hydrogen storage material by inputting the generated hydrogen and the water vapor of the electrolytically unreacted part;
A hydrogenation reaction of the separated mixture of the hydrogen and the hydrogen storage material to store the hydrogen in the hydrogen storage material. 供給された原料水を加熱して水蒸気を発生させて、所定の温度まで昇温させる第１加熱部と、
前記水蒸気を入力して、高温水蒸気電解により水素と酸素とを生成する電解セルと、
生成された前記水素と電解未反応分の前記水蒸気とを入力して、水素吸蔵材料の水素化反応に必要な温度よりも高い温度で、前記水素と前記水蒸気とを分離する水分分離器と、
分離された前記水素と前記水素吸蔵材料との混合物を水素化反応させて、前記水素を前記水素吸蔵材料に吸蔵させる水素化反応器と、
水素吸蔵後の前記水素吸蔵材料を入力して、所定の温度まで加熱する第２加熱部と、
前記第２加熱部において加熱された水素吸蔵後の前記水素吸蔵材料を脱水素化反応させて、前記水素を脱離させる脱水素化反応器と、
前記脱水素化反応器により脱離された前記水素と前記水素吸蔵材料とを入力して、前記水素と前記水素吸蔵材料とに分離する分離器と、
前記分離器において分離された前記水素を入力して、燃料電池反応により発電する燃料電池セルと、を備えることを特徴とする電力貯蔵システム。 A first heating unit for heating the supplied raw water to generate water vapor and raising the temperature to a predetermined temperature;
An electrolytic cell that inputs the water vapor and generates hydrogen and oxygen by high-temperature steam electrolysis;
A water separator that separates the hydrogen and the water vapor at a temperature higher than the temperature required for the hydrogenation reaction of the hydrogen storage material by inputting the generated hydrogen and the water vapor of the electrolytically unreacted part;
A hydrogenation reactor that causes a hydrogenation reaction of the separated mixture of the hydrogen and the hydrogen storage material, and stores the hydrogen in the hydrogen storage material;
A second heating unit for inputting the hydrogen storage material after hydrogen storage and heating it to a predetermined temperature;
A dehydrogenation reactor for desorbing the hydrogen by dehydrogenating the hydrogen storage material after the hydrogen storage heated in the second heating unit;
A separator that inputs the hydrogen desorbed by the dehydrogenation reactor and the hydrogen storage material and separates the hydrogen and the hydrogen storage material;
And a fuel cell that receives the hydrogen separated in the separator and generates power by a fuel cell reaction. 前記第２加熱部は、前記脱水素化反応器により脱離された前記水素と水素吸蔵後の前記水素吸蔵材料との間で熱交換させる第２の熱交換器を有することを特徴とする請求項７に記載の電力貯蔵システム。   The second heating unit includes a second heat exchanger that exchanges heat between the hydrogen desorbed by the dehydrogenation reactor and the hydrogen storage material after hydrogen storage. Item 8. The power storage system according to Item 7. 前記第２加熱部は、前記分離器により分離された前記水素吸蔵材料と水素吸蔵後の前記水素吸蔵材料との間で熱交換させる第３の熱交換器を有することを特徴とする請求項７または請求項８に記載の電力貯蔵システム。   The second heating unit includes a third heat exchanger that exchanges heat between the hydrogen storage material separated by the separator and the hydrogen storage material after hydrogen storage. Or the electric power storage system of Claim 8. 前記第２加熱部は、前記燃料電池セルにおいて発電時に生じるジュール熱を用いて、水素吸蔵後の前記水素吸蔵材料を加熱することを特徴とする請求項７から請求項９のいずれか一項に記載の電力貯蔵システム。   The said 2nd heating part heats the said hydrogen storage material after hydrogen storage using the Joule heat which arises at the time of electric power generation in the said fuel cell, The any one of Claims 7-9 characterized by the above-mentioned. The power storage system described.
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