JPS6124155A - Power generating system using fuel cell - Google Patents

Power generating system using fuel cell

Info

Publication number
JPS6124155A
JPS6124155A JP59146310A JP14631084A JPS6124155A JP S6124155 A JPS6124155 A JP S6124155A JP 59146310 A JP59146310 A JP 59146310A JP 14631084 A JP14631084 A JP 14631084A JP S6124155 A JPS6124155 A JP S6124155A
Authority
JP
Japan
Prior art keywords
fuel cell
fuel gas
gas
carbon dioxide
fuel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP59146310A
Other languages
Japanese (ja)
Other versions
JPH0542783B2 (en
Inventor
Mitsuya Matsumura
光家 松村
Yoichi Mizumoto
水本　洋一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Electric Corp
Original Assignee
Mitsubishi Electric Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Electric Corp filed Critical Mitsubishi Electric Corp
Priority to JP59146310A priority Critical patent/JPS6124155A/en
Publication of JPS6124155A publication Critical patent/JPS6124155A/en
Publication of JPH0542783B2 publication Critical patent/JPH0542783B2/ja
Granted legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
    • H01M8/2495—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies of fuel cells of different types
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

PURPOSE:To increase power generating efficiency by combining a phosphoric acid type fuel cell and a fused carbonate type fuel cell to operate a system without increasing the fuel utilization factor and feeding the discharged fuel gas mainly consisting of separated hydrogen to a fuel gas system. CONSTITUTION:The fuel gas 19 discharged from a phosphoric acid type fuel cell 2b is recycled to the fuel gas system of the phosphoric acid type fuel cell 2b as the discharged fuel gas 17a mainly consisting of hydrogen after the gas 22 mainly consisting of carbon dioxide required to maintain the system material balance is separated in a carbon dioxide separator 6. On the other hand, the gas 22 mainly consisting of the carbon dioxide separated and removed in the carbon dioxide separator 6 is fed to the oxidation gas side of a fused carbonate type fuel cell 2a. Accordingly, the discharged fuel gas 17a recycled from the carbon dioxide separator 6 is made to approach almost pure hydrogen, thereby the hydrogen concentration in the fuel gas fed to the phosphoric acid type fuel cell 2b can be increased, and the cell characteristic can be improved.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、燃料電池発電システムに関し、特にその発
電効率の改善に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fuel cell power generation system, and particularly to improving the power generation efficiency thereof.

〔従来の技術〕[Conventional technology]

従来の代えば溶融炭酸塩形燃料電池を用いた発電システ
ムのシステム構成として第２図に示すもＯカアッタ。（
ＧＲＩ　Ｒｅｐｏｒｔ　ＦＯＲ−８５２２−２に記載さ
れている。）図において（１）は燃料ガス系に配置され
た燃料処理装置、　（２ａ）は単数または複数の電池積
層体よりなる溶融炭酸塩形燃料電池、（荀は酸化ガス系
に配置された空気供給装置、（４）は熱交換器、（５）
は温度湿度調節装置、（６）は溶融炭酸塩形燃料電池（
２ａ）で未反応の燃料ガスを二酸化炭−素を主要成分と
するガスと、水素を主要成分とする排出燃料ガスとに梅
離する二酸化炭素分離装置である。The system configuration of a power generation system using a conventional molten carbonate fuel cell is shown in FIG. 2. (
It is described in GRI Report FOR-8522-2. ) In the figure, (1) is a fuel processing device placed in the fuel gas system, (2a) is a molten carbonate fuel cell consisting of one or more cell stacks, and (Xun is an air supply placed in the oxidizing gas system). The device, (4) is a heat exchanger, (5)
(6) is a molten carbonate fuel cell (
This is a carbon dioxide separation device that separates the unreacted fuel gas in step 2a) into a gas containing carbon dioxide as a main component and an exhaust fuel gas containing hydrogen as a main component.

次に動作について説明する。外部から供給された炭化水
素を主成分とする燃料（ロ）とシステム内の排熱により
発生させたスチーム＠は燃料処理装置（１）上に供給さ
れ、そこで水素及び一酸化炭素を主要成分とした燃居ガ
ス（至）に変質される。変質された燃料ガス（至）は二
酸化炭素分離装置（６）からりサイクｐされる未使用の
排出燃料ガスぐっと混合され溶融炭酸塩形燃料電池（２
ａ）の燃料ガス系に供給される。Next, the operation will be explained. The fuel containing hydrocarbons as the main component (b) supplied from the outside and the steam @ generated by the exhaust heat within the system are supplied onto the fuel processing device (1), where they are treated with hydrogen and carbon monoxide as the main components. It is transformed into combustion gas. The altered fuel gas is thoroughly mixed with the unused exhaust fuel gas that is cycled from the carbon dioxide separator (6) and then sent to the molten carbonate fuel cell (2).
It is supplied to the fuel gas system in a).

一方空完供給装置（３）によりシステムからの排出ガス
（ハ）の排熱を利用して空気に）を所定の圧力に昇圧し
た後、二酸化炭素分離装置（６）から分離供給される二
酸化炭素を主要成分とするガス（イ）と混合し、酸化ガ
ス翰として溶融炭酸塩形燃料電池（２ａ）の酸化ガス系
に供給する。On the other hand, after increasing the pressure of the exhaust gas (c) from the system to air using the exhaust heat of the exhaust gas (c) by the empty supply device (3), the carbon dioxide is separated and supplied from the carbon dioxide separator (6). is mixed with gas (a) whose main component is , and supplied as an oxidizing gas to the oxidizing gas system of the molten carbonate fuel cell (2a).

ここで溶融炭酸塩形燃料電池（２ａ）は、例えば６５０
“Ｃ付近の温度で動作する燃料電池で、燃料ガス−側電
極及び酸化ガス側電極においてそれぞれ電気化学反応を
行わせしめ、全体として燃料ガスの持つ化学エネルギー
を電気エネルギーとそれに伴う熱エネルギーとに変換す
る。　　″ 溶融炭酸塩形燃料電池（２ａ）より排出された酸化ガス
は排出ガス（ハ）として系外へ除去される。また燃料ガ
スＱ４は熱交換器（４）で適当な温度に調節され、温度
湿度調節装置で６）で余剰の水（ト）が除去された後、
二酸化炭素分離装置（６）に燃料ガスＤＩとして供給さ
れる。二酸化炭素分離装置（６）は水素・一酸化炭素・
二酸化炭素・スチームを主成分とする燃料ガスの循環系
から物質収支を保つために必要な量の二酸化炭素を１選
択的に分離除去する装置である。具体的には例えば二酸
化炭素を選択的に吸収するアミン水溶液や炭酸塩水溶液
を吸収媒体とする吸収分離装置が現在利用可能である。Here, the molten carbonate fuel cell (2a) is, for example, 650
“In a fuel cell that operates at a temperature around C, an electrochemical reaction is carried out at the fuel gas side electrode and the oxidizing gas side electrode, and the chemical energy of the fuel gas as a whole is converted into electrical energy and associated thermal energy. ``The oxidizing gas discharged from the molten carbonate fuel cell (2a) is removed from the system as exhaust gas (c). Further, the fuel gas Q4 is adjusted to an appropriate temperature in a heat exchanger (4), and excess water (g) is removed in a temperature/humidity control device (6).
It is supplied to the carbon dioxide separator (6) as fuel gas DI. The carbon dioxide separator (6) separates hydrogen, carbon monoxide,
This is a device that selectively separates and removes the amount of carbon dioxide necessary to maintain mass balance from the circulation system of fuel gas whose main components are carbon dioxide and steam. Specifically, for example, absorption separation devices that use an amine aqueous solution or a carbonate aqueous solution as an absorption medium that selectively absorbs carbon dioxide are currently available.

このようなシステム構成では溶融炭酸塩形燃料電池（２
ａ）で未利用の燃料ガスは二酸化炭素分離装置（６）を
通して水素を主要成分とする排出燃料ガス（ロ）として
リサイクルされ、溶融炭酸塩形燃料電池（２ａ）で再利
用されているため、・燃料処理装置（１）として溶融炭
酸塩形燃料電池（２ａ）で副生ずる熱を反応熱として利
用するものを採用することにより、システムの燃料利用
率を原理上１００％とすることが可能であり、発電効率
の向上が期待できる。In such a system configuration, molten carbonate fuel cells (2
The unused fuel gas in a) is recycled as exhaust fuel gas (b) containing hydrogen as the main component through the carbon dioxide separator (6) and reused in the molten carbonate fuel cell (2a). - By adopting a fuel processing device (1) that utilizes the heat produced by the molten carbonate fuel cell (2a) as reaction heat, it is possible in principle to make the fuel utilization rate of the system 100%. Therefore, it can be expected to improve power generation efficiency.

〔発明が解決しよう止する問題点〕[Problems that the invention cannot solve]

しかしこのように二酸化炭素分離装置（６）で分離され
た水素を主要成分とする排出燃料ガス（財）を溶融炭酸
塩形燃料電池（２ａ）の燃料ガス系に供給するため、熱
交換器（４）で加熱し高温状態、例えば４００°０以上
に保持する場合には１、高温にすることにより下式（１
）に示す反応が活発になるため一方的に二酸化炭素のみ
を燃料ガスから分離除去した場合には炭素析出が起こる
。However, in order to supply the exhaust fuel gas whose main component is hydrogen separated by the carbon dioxide separator (6) to the fuel gas system of the molten carbonate fuel cell (2a), a heat exchanger ( 4) When heating and maintaining it at a high temperature, for example 400°0 or higher, the following formula (1
) becomes active, so if only carbon dioxide is unilaterally separated and removed from the fuel gas, carbon precipitation occurs.

ｇ　００−＋ＣＯ１＋Ｏ↓　　　−（１）この炭素の析
出を避けるためには循環して−いる燃料ガス中に炭素の
析出を防ぐに十分な量の二酸化炭素を保持していること
が不可欠であり、従ってシステムの燃料ガス中に含まれ
ている水素濃度は燃料ガスのりサイクｐのない場合に比
べて相対的に低下し、燃料ガスをリサイクルすることに
より溶融炭酸塩形燃料電池（２ａ）の電池特性が低下す
るという問題が発生する。g 00-+CO1+O↓ -(1) In order to avoid this carbon precipitation, it is essential to retain a sufficient amount of carbon dioxide in the circulating fuel gas to prevent carbon precipitation. Therefore, the hydrogen concentration contained in the fuel gas of the system is relatively reduced compared to the case without the fuel gas cycle p, and by recycling the fuel gas, the cell characteristics of the molten carbonate fuel cell (2a) are improved. A problem arises in that the value decreases.

一方二酸化炭素分離装置（６）として現在利用可能なも
のは先に述べたようにアミン類や炭酸塩の水溶液を二酸
化炭素の吸収媒体とする二酸化炭素吸収装置であり、そ
の操作温度は０〜１２０℃である。On the other hand, the currently available carbon dioxide separator (6) is a carbon dioxide absorption device that uses an aqueous solution of amines or carbonates as the carbon dioxide absorption medium, as described above, and its operating temperature is 0 to 120°C. It is ℃.

従ってこのように二酸化炭素分離装置（６）で父離後の
排出燃料ガスａカを溶融炭酸塩形燃料電池（２ａ）の燃
料ガス系にリサイクルする場合には排出燃料ガスαのを
溶融炭酸塩形燃料電池（２ａ）の動作温度、例えば６６
０℃付近の温度まで予熱を行う必要があるため、大き、
な熱交換器を８換とし、また熱経済的にも不利である。Therefore, when the carbon dioxide separator (6) recycles the exhaust fuel gas a after father's separation into the fuel gas system of the molten carbonate fuel cell (2a), the exhaust fuel gas α is converted into molten carbonate. The operating temperature of the type fuel cell (2a), for example 66
Because it is necessary to preheat to a temperature around 0℃,
The heat exchanger is 8 exchangers, which is also disadvantageous in terms of thermoeconomics.

従来の燃料電池発電システムは以上のように構成されて
いるので、循環する燃料ガスを再加熱せねばならず、一
酸化炭素を含んだ燃料ガスの再加熱による炭素析出を避
けるために循環する燃料ガス中に十分な量の二酸化炭素
を保持することが必要となり、電池特性が低下し、発電
効率を高くできないという欠点があった。Since the conventional fuel cell power generation system is configured as described above, the circulating fuel gas must be reheated, and the circulating fuel must be reheated to avoid carbon deposition due to reheating of the fuel gas containing carbon monoxide. This has the disadvantage that it is necessary to retain a sufficient amount of carbon dioxide in the gas, which deteriorates battery characteristics and makes it impossible to increase power generation efficiency.

この発明は、かか名聞照点を解決するためになされたも
ので、高い発電効率で長期に安定して運転が可能な燃料
電池発電システムを提供することを目的とする。This invention was made in order to solve this problem, and aims to provide a fuel cell power generation system that can operate stably over a long period of time with high power generation efficiency.

〔間°照点を解決するための手段〕[Means for resolving the gap]

゛この発明に係る燃料電池発電システムは、燃料ガス系
より燃料ガスが供給されると共に、酸化ガス系より酸化
ガスが供給され電気化学反応を起す溶融炭酸塩形燃料電
池、この溶融炭酸塩形燃料電池より排出された燃料ガス
中の一酸化炭素を二酸化炭素′に変成する一酸化炭素変
成装置、この一酸化炭素変成装置より排出された燃料ガ
スが燃料ガス系より供給されると共に１酸化ガスが供給
され電気化学反応を起すリン酸形燃料電池、及びこのリ
ン酸形燃料電池より排出された燃料ガスから、二酸化炭
素を主要成分とするガスと水素を主要成分とする排出燃
料ガスに分離する二酸化炭素分離装置を備え、分離した
二酸化炭素を主要成分とする上記ガスを上記溶融炭酸塩
形燃料電池の酸化ガス系に供給し、水素を主要成分とす
る上記排出燃料ガスを燃料電池の燃料ガス系に供給する
ようにしたものである。゛The fuel cell power generation system according to the present invention includes a molten carbonate fuel cell in which fuel gas is supplied from a fuel gas system and oxidizing gas is supplied from an oxidizing gas system to cause an electrochemical reaction, and the molten carbonate fuel A carbon monoxide shift device converts carbon monoxide in the fuel gas discharged from the battery into carbon dioxide.The fuel gas discharged from this carbon monoxide shift device is supplied from the fuel gas system, and the monoxide gas is Dioxide is supplied to a phosphoric acid fuel cell that causes an electrochemical reaction, and the fuel gas discharged from the phosphoric acid fuel cell is separated into a gas whose main component is carbon dioxide and an exhaust fuel gas whose main component is hydrogen. A carbon separator is provided, the separated gas containing carbon dioxide as a main component is supplied to the oxidizing gas system of the molten carbonate fuel cell, and the exhaust fuel gas containing hydrogen as a main component is supplied to the fuel gas system of the fuel cell. It was designed to be supplied to

〔問題点を解決するための手段の作用〕この発明におけ
る一酸化炭素変成装置により、溶融炭酸塩形燃料電池よ
り排出された燃料ガス中の一酸化炭素を二酸化炭素に変
成するので、二酸化炭素分離装置において燃料ガスから
二酸化炭素を主要成分とするガスを分離除去しても、燃
料ガス中には一酸化炭素が含まれていないため、炭素が
析出しない。さらに、リン酸形燃料電池を備えることに
より、溶融炭酸塩形燃料電池における燃料利用率を、高
くせずにシステムを運転できると共に、分離された水素
を主要成分とする排出燃料ガスを燃料電池の燃料ガス系
に供給し〜燃料ガス中の水素の濃度を相対的に高くする
ことができ、高い発電効率で安定した運転をすることが
できる燃料電池発電システムが得られる。[Operation of the means for solving the problem] The carbon monoxide conversion device of the present invention converts carbon monoxide in the fuel gas discharged from the molten carbonate fuel cell into carbon dioxide, so that carbon dioxide separation is possible. Even if the gas containing carbon dioxide as a main component is separated and removed from the fuel gas in the device, carbon does not precipitate because the fuel gas does not contain carbon monoxide. Furthermore, by including a phosphoric acid fuel cell, the system can be operated without increasing the fuel utilization rate in the molten carbonate fuel cell, and the exhaust fuel gas containing separated hydrogen as a main component can be used in the fuel cell. The hydrogen concentration in the fuel gas supplied to the fuel gas system can be made relatively high, and a fuel cell power generation system capable of stable operation with high power generation efficiency can be obtained.

〔実施例〕〔Example〕

以下１との発明の一実施例を図について説明する。第１
図において従来例と同様、（１）は燃料ガス系に配置さ
れた燃料処理装置、（２ａ）は溶融炭酸塩形燃料電池、
（３）は酸化ガス系に配置された空気供給装置、（４）
は熱交換器、（５）は温度湿度調節装置、（６）は二酸
化炭素分離装置である。さらＩζ（７）は溶融炭酸′塩
形燃料電池（ｍａ’＋からの燃料ガスα◆中の一酸化炭
素を二酸化炭素に変成する一酸化炭素変成装置である。An embodiment of the invention referred to in item 1 will be described below with reference to the drawings. 1st
In the figure, as in the conventional example, (1) is a fuel processing device placed in the fuel gas system, (2a) is a molten carbonate fuel cell,
(3) is an air supply device placed in the oxidizing gas system; (4)
is a heat exchanger, (5) is a temperature/humidity controller, and (6) is a carbon dioxide separator. Furthermore, Iζ(7) is a carbon monoxide conversion device that converts carbon monoxide in the fuel gas α◆ from a molten carbonate fuel cell (ma'+) into carbon dioxide.

（２ｂ）は単数又は複数の電池積層体よりなるリン酸形
燃料電池で２ある。(2b) is a phosphoric acid fuel cell 2 consisting of one or more cell stacks.

次にこのようなシステムの動作について説明する。゛外
部から供給された炭化水素を主成分とする燃料（ロ）と
システム内の排熱たとえばリン酸形燃料電池（２ｂ）の
副生熱により発生させたスチーム（２）は燃料処理装置
（１）に供給され、そこで水素及び一酸化炭素を主要成
分とした燃料ガス（至）に変質される。Next, the operation of such a system will be explained. ``The steam (2) generated from the fuel (b) whose main component is hydrocarbons supplied from the outside and the exhaust heat within the system, such as the by-product heat of the phosphoric acid fuel cell (2b), is transferred to the fuel processing device (1). ), where it is transformed into a fuel gas containing hydrogen and carbon monoxide as main components.

変質された燃料ガス替は溶融炭酸塩形燃料電池（２ａ）
の燃料ガス系に供給されると共に酸化ガス系より酸化ガ
ス輪が供給され、燃料ガ・ス曽の一部が燃料として利用
された後、熱交換器（４）を経て一酸化炭素変成装置（
７）に供給される。一酸化炭素変成装置（７）はリン酸
形燃料電池（２ｂ）に対して有害な物質である一酸化炭
素を二酸化炭素に変成することにより燃料ガスＱ４中か
ら一酸化炭素を除去する装置である。賛成されて、水素
・二酸化炭素・水より成る燃料ガス（ハ）は温度湿度調
節装置（５）において水（ロ）が除かれ、適当な温度・
湿度に調節された後、例えば二酸化炭素分離装置（６）
からりサイクμされる水素を主要成分とする燃料ガス（
ｔｙａ）と混合され、リン酸形燃料電池（２ｂ）の燃料
ガス系に供給される。Altered fuel gas replacement is molten carbonate fuel cell (2a)
At the same time, the oxidizing gas ring is supplied from the oxidizing gas system, and after a part of the fuel gas is used as fuel, it passes through the heat exchanger (4) to the carbon monoxide shift device (
7). The carbon monoxide conversion device (7) is a device that removes carbon monoxide from the fuel gas Q4 by converting carbon monoxide, which is a harmful substance to the phosphoric acid fuel cell (2b), into carbon dioxide. . After approval, the fuel gas (c) consisting of hydrogen, carbon dioxide, and water is heated to an appropriate temperature and temperature by removing water (b) in the temperature and humidity control device (5).
After the humidity has been adjusted, e.g. carbon dioxide separator (6)
Fuel gas whose main component is hydrogen (
tya) and supplied to the fuel gas system of the phosphoric acid fuel cell (2b).

リン酸形燃料電池（２ｂ）では燃料ガスと共に酸化ガス
が空気供給装置（，１）より供給され′て電気化学反応
を起す、リン酸形燃料電池（２ｂ）から排出された燃料
ガス０呻は、二酸化炭素分離装置（６）においてシステ
ムの物質収支を保つ上で必要な二酸化炭素を主成分とす
ゐガス（２）が分離され後、水素を主要成分とする排出
燃料ガス（１７ａ）としてリン酸形燃料電池（２ｂ）の
燃料ガス系にリサイクルされる。一方上記二酸化炭素分
離装置（６）で分離除去された二酸化炭素を主要成分と
するガスに）は溶融炭酸塩形燃料電池（２ａ）の酸化ガ
ス側に供給される。　　　。In the phosphoric acid fuel cell (2b), oxidizing gas is supplied from the air supply device (1) along with the fuel gas to cause an electrochemical reaction.The fuel gas discharged from the phosphoric acid fuel cell (2b) is After the carbon dioxide separator (6) separates the gas (2) mainly composed of carbon dioxide, which is necessary to maintain the mass balance of the system, it is released as exhaust fuel gas (17a) mainly composed of hydrogen. It is recycled into the fuel gas system of the acid fuel cell (2b). On the other hand, the gas containing carbon dioxide as a main component separated and removed by the carbon dioxide separator (6) is supplied to the oxidizing gas side of the molten carbonate fuel cell (2a). .

このようにこのシステムにおいては二酸化炭素分離装置
（６）に供給される燃料ガス（２）中には一酸化炭素を
殆ど含んでいないため、原理上、式（１）に基ずく炭素
析出を考慮する必要がなく、燃料ガス（６）から自由に
二酸化炭素を分離除去する事が一可能となる・従って二
酸化炭素分離装置（６）からりサイク〃される排出燃料
ガス（１７ａ）をほぼ純粋な水素に′まで近づける事に
よりリン酸形燃料電池（２ｂ）に供給される燃料ガス中
の水素濃度を高くでき、電池特性の向上が得られる。ま
たリン酸形燃料電池（２ｂ）の動作温度は約２００℃と
溶融炭酸塩形燃料電池（２ａ）と比べて低温動作のため
、燃料ガスの再加熱負荷は小さくてすむ。In this way, in this system, the fuel gas (2) supplied to the carbon dioxide separator (6) contains almost no carbon monoxide, so in principle, carbon precipitation based on equation (1) is taken into account. Therefore, it is possible to freely separate and remove carbon dioxide from the fuel gas (6). Therefore, the exhaust fuel gas (17a) recycled from the carbon dioxide separator (6) can be converted into almost pure By bringing hydrogen closer to '', the hydrogen concentration in the fuel gas supplied to the phosphoric acid fuel cell (2b) can be increased, and the cell characteristics can be improved. Furthermore, since the operating temperature of the phosphoric acid fuel cell (2b) is about 200° C., which is lower than that of the molten carbonate fuel cell (2a), the load for reheating the fuel gas is small.

他方このシステムにおいてはリン酸形燃料電池（２ｂ）
で消費される燃料ガスも溶融炭酸塩形燃料電池（２ａ）
を通過せしめているため、全体としての燃料利用率を一
定に保ちながら溶融炭酸塩形燃料電池（２ａ）の燃料利
用率を低く保て・るため、第８図の燃料利用率（＠に対
する平均単セル電圧（至）の特性曲線に示されるように
電池特性の向上が得られる。On the other hand, in this system, a phosphoric acid fuel cell (2b)
The fuel gas consumed in the molten carbonate fuel cell (2a)
, the fuel utilization rate of the molten carbonate fuel cell (2a) can be kept low while keeping the overall fuel utilization rate constant. As shown in the characteristic curve of single cell voltage (to), the battery characteristics can be improved.

このようにこのシステムにおいては電池特性を向上させ
ながら燃料利用率を原理上１００％にまで高めることが
実現でき、大巾な発電効率の向上が得られる。更に二酸
化炭素の一方的な除去に伴う炭素析出はシステムの構成
上問題とならないため長期にわたり安定した運転が可能
となる。　”−例として二酸化炭素分離装置（６）にお
いて二酸化炭素を主要成分とするガス（２）が、温度湿
度調節装置（６）において水（２）が、それぞれシステ
ム内の物質収支をとる上で必要な量だけ分離除去され１
更に燃料処理装置（１）として溶融炭酸塩形燃料電池（
２ａ）で副生ずる熱を利用する形成のものを採用し１ま
た溶融炭酸塩ｉ燃料電池（２ａ）・リン酸形燃料電池（
２ｂ）各々の反応量の比を１：１と仮定すると、本実施
例の発電システムの発電効率は６８−６７９ｂ程度とカ
リ、従来のシステムにおいて報告されている５Ｇ　−５
５％程度に対して大巾な向上が得られる。In this way, in this system, it is possible to increase the fuel utilization rate to 100% in principle while improving the battery characteristics, resulting in a significant improvement in power generation efficiency. Furthermore, carbon deposition due to the unilateral removal of carbon dioxide does not pose a problem in the system configuration, allowing stable operation over a long period of time. ”-For example, gas (2) whose main component is carbon dioxide in the carbon dioxide separator (6) and water (2) in the temperature and humidity control device (6) are necessary to maintain the mass balance within the system. is separated and removed by 1
Furthermore, a molten carbonate fuel cell (
In 2a), a type of formation that utilizes the heat produced by the process is adopted.
2b) Assuming that the ratio of each reaction amount is 1:1, the power generation efficiency of the power generation system of this example is about 68-679b, which is higher than the 5G -5 reported in the conventional system.
A large improvement can be obtained compared to about 5%.

なお、上記実施例では燃料処理装置（１）と溶融炭酸塩
形燃料電池（２ａ）が独立して設けられている場合につ
いて説・明したが、両者の機能を併せ持した内部リホー
ミング型溶融炭酸塩形燃料電池を両者のかわりに設けて
もよい。また上記実施例では二酸化炭素分離装置（６）
において二酸化炭素が分離される場合について説明した
が、二酸化炭素と水が同時に分離されてもよい。また上
記実施例では二酸化°炭素分離装置（６）で分離された
水素を主要成分とする排出燃料ガス（１７ａ）をリン酸
燃料電池（２ｂ）の燃料ガス系にリサイクルしているが
、リン酸形燃料電池（２ｂ）の燃料ガス系の上流であれ
ば任意の位置にリサイクμしてよく、また第１図に示す
排出燃料ガス（１７ｂ）のように溶融炭酸塩形燃料電池
（２ａ）の燃料ガス系にリサイクルしてもよい。In the above embodiment, the fuel processing device (1) and the molten carbonate fuel cell (2a) are provided independently. Carbonate fuel cells may be provided in place of both. In the above embodiment, the carbon dioxide separator (6)
Although the case in which carbon dioxide is separated has been described, carbon dioxide and water may be separated at the same time. Furthermore, in the above embodiment, the exhaust fuel gas (17a) whose main component is hydrogen separated by the carbon dioxide separator (6) is recycled to the fuel gas system of the phosphoric acid fuel cell (2b). It may be recycled to any position upstream of the fuel gas system of the molten carbonate fuel cell (2b), and it can also be recycled to any position upstream of the fuel gas system of the molten carbonate fuel cell (2a), as shown in Figure 1. It may be recycled into the fuel gas system.

さらに、溶融炭酸塩形燃料電池（２ａ）に燃料男ス（至
）を供給する燃料処理装置（１）として溶融炭酸塩形燃
料電池（２ａ）で副生する熱を反応熱として利用する燃
料処理装置を設けてもよい。Furthermore, as a fuel processing device (1) that supplies fuel to the molten carbonate fuel cell (2a), a fuel processing device (1) that uses the heat by-produced in the molten carbonate fuel cell (2a) as reaction heat. A device may also be provided.

〔発明の効果〕〔Effect of the invention〕

以上のように、この発明によれば、燃料ガス系より燃料
ガスが供給されると共に、酸化ガス系より酸化ガスが供
給され電気化学反応を起す溶融炭酸塩形燃料電池、この
溶融炭酸塩形燃料電池より排出された燃料ガス中の一酸
化炭素を二酸化炭素に変成する一酸化炭素変成装置、こ
の一酸化炭素変成装置より排出された燃料ガスが燃料ガ
ス系より供給されると共に、酸化ガスが供給され電気化
学反応を起すリン酸形燃料電池、及びこのリン酸形燃料
電池より排出された燃料ガスから、二酸化炭素を主要成
分とするガスと水素を主要成分とする排出燃料ガスに分
離する二酸化炭素分離装置を備え、分離した二酸化炭素
を主要成分とする上記ガスを上記溶融炭酸塩形燃料電池
の酸化ガス系に供給し、水素を主要成分とする上記排出
燃料ガスを上記燃料電池の燃料ガス系に供給することに
より、電池特性を向上させながら全体としての燃料利用
率を高くでき、大巾に発電効率を向上させ、かつ炭素を
析出させずに二酸化炭素を分離して、長期に安定した運
転が行なえる燃料電池発電システムが得られる効果があ
る。As described above, the present invention provides a molten carbonate fuel cell in which a fuel gas is supplied from a fuel gas system and an oxidizing gas is supplied from an oxidizing gas system to cause an electrochemical reaction; A carbon monoxide shift device converts carbon monoxide in the fuel gas discharged from the battery into carbon dioxide.The fuel gas discharged from the carbon monoxide shift device is supplied from the fuel gas system, and oxidizing gas is also supplied. The carbon dioxide is separated from the phosphoric acid fuel cell that causes an electrochemical reaction and the fuel gas discharged from the phosphoric acid fuel cell into a gas whose main component is carbon dioxide and an exhaust fuel gas whose main component is hydrogen. A separation device is provided, the separated gas containing carbon dioxide as a main component is supplied to the oxidizing gas system of the molten carbonate fuel cell, and the exhaust fuel gas containing hydrogen as a main component is supplied to the fuel gas system of the fuel cell. By supplying carbon dioxide to the fuel, the overall fuel utilization rate can be increased while improving battery characteristics, greatly improving power generation efficiency, and separating carbon dioxide without depositing carbon, resulting in stable operation over a long period of time. This has the effect of providing a fuel cell power generation system that can perform

【図面の簡単な説明】[Brief explanation of drawings]

第１図はこの発明の一実施例によ乞燃料電池発電システ
ムを示す構成図、第２図は従来の溶融炭酸塩形燃料電池
発電システムを示す構成図、第８図は燃料電池の燃料利
用特性の一例を示す特性図である。 （２ａ）・・・溶融炭酸塩形燃料電池、（２ｂ）・・・
リン酸形燃料、電池、（６）・・・二酸化炭素分離装置
、（７）・・・一酸化炭素変成装置、０３　、　Ｑ４　
、　（１７ａ）　、　（１７ｂ）　、　０１　、　Ｑｌ
・・・燃料ガス、に）、＠・・・酸化ガス。 なお、図中、同一符号は同一、又は相当部分を示す。Fig. 1 is a block diagram showing a fuel cell power generation system according to an embodiment of the present invention, Fig. 2 is a block diagram showing a conventional molten carbonate fuel cell power generation system, and Fig. 8 is a block diagram showing fuel cell power generation system. FIG. 3 is a characteristic diagram showing an example of characteristics. (2a)... Molten carbonate fuel cell, (2b)...
Phosphoric acid fuel, battery, (6)...carbon dioxide separation device, (7)...carbon monoxide conversion device, 03, Q4
, (17a), (17b), 01, Ql
...Fuel gas, ni), @...Oxidizing gas. In addition, in the figures, the same reference numerals indicate the same or equivalent parts.

Claims (3)

【特許請求の範囲】[Claims] （１）燃料ガス系より燃料ガスが供給されると共に、酸
化ガス系より酸化ガスが供給され電気化学反応を起す溶
融炭酸塩形燃料電池、この溶融炭酸塩形燃料電池より排
出された燃料ガス中の一酸化炭素を二酸化炭素に変成す
る一酸化炭素変成装置、この一酸化炭素変成装置より排
出された燃料ガスが燃料ガス系より供給されると共に、
酸化ガスが供給され電気化学反応を起すリン酸形燃料電
池、及びこのリン酸形燃料電池より排出された燃料ガス
から、二酸化炭素を主要成分とするガスと水素を主要成
分とする排出燃料ガスに分離する二酸化炭素分離装置を
備え、分離した二酸化炭素を主要成分とする上記ガスを
上記溶融炭酸塩形燃料電池の酸化ガス系に供給し、水素
を主要成分とする上記排出燃料ガスを上記燃料電池の燃
料ガス系に供給することを特徴とする溶融炭酸塩形燃料
電池発電システム。(1) A molten carbonate fuel cell in which fuel gas is supplied from the fuel gas system and oxidizing gas is supplied from the oxidizing gas system to cause an electrochemical reaction; in the fuel gas discharged from the molten carbonate fuel cell. A carbon monoxide shift device that converts carbon monoxide into carbon dioxide, fuel gas discharged from this carbon monoxide shift device is supplied from a fuel gas system, and
A phosphoric acid fuel cell is supplied with oxidizing gas to cause an electrochemical reaction, and the fuel gas discharged from the phosphoric acid fuel cell is converted into gas containing carbon dioxide as the main component and exhaust fuel gas containing hydrogen as the main component. A carbon dioxide separator is provided to separate the gas, which supplies the separated gas containing carbon dioxide as a main component to the oxidizing gas system of the molten carbonate fuel cell, and supplies the exhaust fuel gas containing hydrogen as a main component to the fuel cell. A molten carbonate fuel cell power generation system characterized by supplying fuel gas to a fuel gas system. （２）二酸化炭素分離装置で分離した水素を主要成分と
する排出燃料ガスをリン酸形燃料電池の燃料ガス系に供
給するようにした特許請求の範囲第１項記載の燃料電池
発電システム。(2) The fuel cell power generation system according to claim 1, wherein the exhaust fuel gas whose main component is hydrogen separated by the carbon dioxide separator is supplied to the fuel gas system of the phosphoric acid fuel cell. （３）二酸化炭素分離装置で分離した水素を主要成分と
する排出燃料ガスを溶融炭酸塩形燃料電池の燃料ガス系
に供給するようにした特許請求の範囲第１項記載の燃料
電池発電システム。(3) The fuel cell power generation system according to claim 1, wherein the exhaust fuel gas whose main component is hydrogen separated by the carbon dioxide separator is supplied to the fuel gas system of the molten carbonate fuel cell.
JP59146310A 1984-07-13 1984-07-13 Power generating system using fuel cell Granted JPS6124155A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59146310A JPS6124155A (en) 1984-07-13 1984-07-13 Power generating system using fuel cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59146310A JPS6124155A (en) 1984-07-13 1984-07-13 Power generating system using fuel cell

Publications (2)

Publication Number Publication Date
JPS6124155A true JPS6124155A (en) 1986-02-01
JPH0542783B2 JPH0542783B2 (en) 1993-06-29

Family

ID=15404782

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59146310A Granted JPS6124155A (en) 1984-07-13 1984-07-13 Power generating system using fuel cell

Country Status (1)

Country Link
JP (1) JPS6124155A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04115466A (en) * 1990-09-05 1992-04-16 Kawasaki Heavy Ind Ltd Method of fuel cell generation
JP2002319428A (en) * 2001-04-19 2002-10-31 Ishikawajima Harima Heavy Ind Co Ltd Molten carbonate fuel cell power generating device
WO2003094273A1 (en) * 2002-05-02 2003-11-13 Mitsubishi Heavy Industries, Ltd. Fuel cell power generation system and method for operating the same
JP2017183199A (en) * 2016-03-31 2017-10-05 東京瓦斯株式会社 Fuel cell system

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04115466A (en) * 1990-09-05 1992-04-16 Kawasaki Heavy Ind Ltd Method of fuel cell generation
JP2002319428A (en) * 2001-04-19 2002-10-31 Ishikawajima Harima Heavy Ind Co Ltd Molten carbonate fuel cell power generating device
WO2003094273A1 (en) * 2002-05-02 2003-11-13 Mitsubishi Heavy Industries, Ltd. Fuel cell power generation system and method for operating the same
CN100336259C (en) * 2002-05-02 2007-09-05 三菱重工业株式会社 Fuel cell power generation system and method for operating the same
US7387650B2 (en) 2002-05-02 2008-06-17 Mitsubishi Heavy Industries, Ltd. Fuel cell power generation system and method for operating the same
JP2017183199A (en) * 2016-03-31 2017-10-05 東京瓦斯株式会社 Fuel cell system

Also Published As

Publication number Publication date
JPH0542783B2 (en) 1993-06-29

Similar Documents

Publication Publication Date Title
EP0376219B1 (en) Electric power producing system using molten carbonate type fuel cell
KR102143864B1 (en) System to capture CO2 from fuel cells
US4902586A (en) Once through molten carbonate fuel cell system
JPS61114478A (en) Fuel cell device
JPH03225770A (en) Fuel battery power plant
JP2002319428A (en) Molten carbonate fuel cell power generating device
JPH02183967A (en) Power generating system for fused carbonate type fuel cell
JP5618680B2 (en) Solid oxide fuel cell system
JP7364831B2 (en) Power generation system using cascaded fuel cells and related methods
JPS6359229B2 (en)
JPS6124155A (en) Power generating system using fuel cell
US20230352702A1 (en) Hydrogen Generation Using a Fuel Cell System with an Rep
JPH0845526A (en) Multistage reaction type fuel cell
JPH0527229B2 (en)
JPH04334870A (en) Fused carbonate type fuel cell generating set
JPH03216964A (en) Power generating method for molten carbonate fuel cell
JPS62184771A (en) Fuel cell power generating system
JPH01183073A (en) Operation suspending method for fuel cell power generating system
JP2751526B2 (en) Molten carbonate fuel cell power generator
JPH04101364A (en) Fuel cell
JPS6280970A (en) Power generating method of fuel cell
JPH03236166A (en) Power generating method for molten carbonate fuel cell
JPS6124171A (en) Power generating system using fused carbonate type fuel cell
JP2819734B2 (en) Molten carbonate fuel cell power generator
JP2017004743A (en) Fuel cell system