JPH01187775A - Fuel battery with fusion carbonate - Google Patents

Fuel battery with fusion carbonate

Info

Publication number
JPH01187775A
JPH01187775A JP63010745A JP1074588A JPH01187775A JP H01187775 A JPH01187775 A JP H01187775A JP 63010745 A JP63010745 A JP 63010745A JP 1074588 A JP1074588 A JP 1074588A JP H01187775 A JPH01187775 A JP H01187775A
Authority
JP
Japan
Prior art keywords
gas
cathode
carbon dioxide
exhaust gas
supplied
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.)
Pending
Application number
JP63010745A
Other languages
Japanese (ja)
Inventor
Chiyuuhei Asakawa
浅川　仲平
Takao Watanabe
隆夫 渡辺
Yoshiyuki Isaki
慶之 伊崎
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.)
Central Research Institute of Electric Power Industry
Original Assignee
Central Research Institute of Electric Power Industry
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 Central Research Institute of Electric Power Industry filed Critical Central Research Institute of Electric Power Industry
Priority to JP63010745A priority Critical patent/JPH01187775A/en
Publication of JPH01187775A publication Critical patent/JPH01187775A/en
Pending legal-status Critical Current

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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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

PURPOSE:To raise the partial pressure of carbon dioxide gas at a cathode and raise the electromotive force by furnishing a gas separating device in the cathode exhaust gas system of a molten carbonate type fuel battery, separating the carbon dioxide gas in the cathode exhaust gas and circulating is back to the cathode. CONSTITUTION:A cooling apparatus 2 and gas separating devices 3, 4 are furnished on the cathode exhaust gas system 6 of a fuel battery body 1, and the carbon dioxide gas 4 in the cathode exhaust gas 6 is collected and supplied to a catalyzer combustor 5 for production of carbon dioxide gas, where it is mixed with CO2 contained in the gas 7 in the anode exhaust gas system 7 or produced from the same gas and the air 8 as oxidating gas supplied by a compressor 8, and the mixture gas 5 of oxidating gas and CO2 gas in the amount enough to perform reaction is supplied to the cathode 1c to serve reuse. Circulating the carbon dioxide gas in the cathode exhaust gas back to the cathode will raise the partial pressure of the carbon dioxide gas at the cathode to lead to raising of the electromotive force of battery.

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は燃料電池、特に電解質に炭酸塩を使用した溶融
炭酸塩型燃料電池の改良に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to fuel cells, and particularly to improvements in molten carbonate fuel cells using carbonate as an electrolyte.

（従来の技術） これからの発電装：Ｗとして注目され、研究開発が進め
られている燃料電池は、天然ガスや石炭などの燃料が持
っている化学エネルギーを直接、連続的に電気エネルギ
ーに変換するものであり、従来の発電方法に比ベカルノ
ー効率の制限を受けず、高い総合効率が得られることか
ら将来の発電装置として期待されている。中でも溶融炭
酸塩型燃料電池は発電効率が高いので実用化に向けての
開発が望まれている。(Conventional technology) Future power generation systems: Fuel cells, which are attracting attention as W and are being researched and developed, directly and continuously convert the chemical energy contained in fuels such as natural gas and coal into electrical energy. This method is expected to be used as a future power generation device because it achieves high overall efficiency without being limited by Carnot efficiency compared to conventional power generation methods. Among these, molten carbonate fuel cells have high power generation efficiency, so their development for practical use is desired.

この燃料電池は、一対の電極と電解質がら構成される単
電池を多数直列に接続して集合電池とし、さらに集合電
池を組合せて燃料電池本体とし、アノードに燃料ガスを
、カソードに酸化剤ガスを人々供給することによって電
力を取り出すように組成されており、更に電解質として
炭酸リチウム（Ｌｉ２ＣＯａ　）や炭酸カリウム（に２
　Ｃｈ　）等の炭酸塩を使用する溶融炭酸塩型の場合、
燃料カスと酸化剤ガスとの反応のキャリヤーとして炭酸
イオン（Ｃｈ　２）が使用されている。そして現状の溶
融炭酸塩型燃料電池にあっては、カソードに供給される
Ｃ０２ガスは、電池反応に必要な分たけがカソードにお
いて消費され、余よりは排気カスとして電池外部に排出
されてしまう。This fuel cell consists of a large number of single cells, each consisting of a pair of electrodes and an electrolyte, connected in series to form an aggregate battery.The aggregate batteries are further combined to form the fuel cell main body, and fuel gas is supplied to the anode and oxidant gas to the cathode. It has a composition that extracts electricity by supplying it to people, and it also uses lithium carbonate (Li2COa) and potassium carbonate (Ni2COa) as electrolytes.
In the case of molten carbonate type using carbonates such as Ch),
Carbonate ions (Ch2) are used as carriers for the reaction between fuel scum and oxidant gas. In the current molten carbonate fuel cell, the amount of CO2 gas supplied to the cathode that is necessary for the cell reaction is consumed at the cathode, and the rest is exhausted to the outside of the cell as exhaust gas.

（発明が解決しようとする課題） したがって、従来の溶融炭酸塩型燃料電池では、電解質
中の炭酸イオンが発電反応に消費されるためカソード側
の炭酸カスの分圧が低下し、電池の起電力か上がらない
欠点がある。(Problem to be Solved by the Invention) Therefore, in conventional molten carbonate fuel cells, the carbonate ions in the electrolyte are consumed in the power generation reaction, so the partial pressure of carbonate scum on the cathode side decreases, causing the electromotive force of the battery to decrease. There is a drawback that it does not improve.

そこで、本発明は、カソードの炭酸ガスの分圧を高め、
起電力を高め得る溶融炭酸塩型燃料電池を提供すること
を目的とする。Therefore, the present invention increases the partial pressure of carbon dioxide gas at the cathode,
An object of the present invention is to provide a molten carbonate fuel cell that can increase electromotive force.

（課題を解決するための手段） かかる目的を達成するため、本発明の溶融炭酸塩型燃料
電池は、溶融炭酸塩型燃料電池のカソード排ガス系統に
ガス分離装置を設け、カソード排ガス中の炭酸ガスを分
能してカソードに再循環させるようにしている。(Means for Solving the Problems) In order to achieve the above object, the molten carbonate fuel cell of the present invention is provided with a gas separation device in the cathode exhaust gas system of the molten carbonate fuel cell, so that carbon dioxide in the cathode exhaust gas is separated. is separated and recirculated to the cathode.

（作用） したがっ−Ｃ１現状の溶融炭酸塩型燃料電池においては
排気カスとして電池外部に排出されていたカソード排ガ
ス系の００２ガスを回収してカソードで再利用し、カソ
ードにおけるＣ０２の分圧を高めることかできる。(Function) Therefore -C1 In the current molten carbonate fuel cell, the 002 gas in the cathode exhaust gas system, which is discharged outside the cell as exhaust gas, is recovered and reused at the cathode, increasing the partial pressure of C02 at the cathode. I can do it.

（実施例） 以下、本発明の構成を図面に示す実施例に基づいて詳細
に説明する。(Example) Hereinafter, the configuration of the present invention will be described in detail based on an example shown in the drawings.

本発明の溶融炭酸塩型燃料電池の一実施例を原理図に示
す、この溶融炭酸塩型燃料電池は、燃焼電池本ｋｌのカ
ソード排ガス系６に冷却器２とガス分離装置３，４を設
け、カソード排ガス■中の炭酸ガス■を回収して炭酸ガ
ス生成用触媒燃焼器５に供給し、該触媒燃焼器５におい
てアノード排ガス系７のガス■に含まれあるいは該ガス
から生成されるＣ０２及びコンプレッサ８によって供給
される酸化剤ガスとしての空気■と混合され、反応に必
要な充分な量の酸化剤ガスとＣ０２ガスの混合ガス■と
してカソードＩＣに供給され、再使用するように設けら
れている。尚、ガス分離装置３゜４としては例えば）膜
分離装置が用いられ、脱水、炭酸ガス（ＣＯ２）分離が
行なわれる。また、図中符号１ｂは電解質である。An embodiment of the molten carbonate fuel cell of the present invention is shown in the principle diagram. This molten carbonate fuel cell is equipped with a cooler 2 and gas separation devices 3 and 4 in the cathode exhaust gas system 6 of the combustion cell main kl. , the carbon dioxide gas (■) in the cathode exhaust gas (■) is recovered and supplied to the carbon dioxide gas generating catalytic combustor 5, and in the catalytic combustor 5, CO2 and CO2 contained in or generated from the gas (■) of the anode exhaust gas system 7 are recovered. It is mixed with air as an oxidizing gas supplied by the compressor 8, and supplied to the cathode IC as a mixed gas of sufficient oxidizing gas and CO2 gas necessary for the reaction, and is provided for reuse. There is. For example, a membrane separator is used as the gas separator 3.4 to perform dehydration and carbon dioxide (CO2) separation. Further, the reference numeral 1b in the figure is an electrolyte.

この燃料電池では、燃料電池本体１のカソード１ｃから
排出される排ガス■は、冷却器２において膜分離に支障
のない温度的１００〜１５０℃に冷却される。そして、
第１段目の１摸分離装置３において水分■が除かれ、第
２段目の膜分離装置４において００２（炭酸ガス）■が
分離され、残りの排ガス■は外部に排出される。分離さ
れたＣ０２■は触媒燃焼器５に送られる。また、アノー
ド１ａより排出されるカス■及びコンプレッサー８を介
して供給される空気（酸化剤ガス）■も触媒燃焼器５に
送られる。アノード１ａから排出されるガス■に含まれ
る未反応の燃料ガス（＋１２　、　ＧＯ）は、Ｃ０２生
戒用触媒燃焼器５において酸化されてＣＯ２となり、膜
分雛装置３，４において分離されたＣＯ２■と共に酸化
剤ガス■と００２の混合ガス■としてカソードｌｃに供
給される。In this fuel cell, exhaust gas (1) discharged from the cathode 1c of the fuel cell main body 1 is cooled in the cooler 2 to a temperature of 100 to 150°C that does not interfere with membrane separation. and,
Water (1) is removed in the first-stage first-stage separation device 3, 002 (carbon dioxide) (2) is separated in the second-stage membrane separation device 4, and the remaining exhaust gas (2) is discharged to the outside. The separated C02■ is sent to the catalytic combustor 5. Further, the scum (2) discharged from the anode 1a and the air (oxidizing gas) (2) supplied via the compressor 8 are also sent to the catalytic combustor 5. Unreacted fuel gas (+12, GO) contained in the gas discharged from the anode 1a is oxidized to CO2 in the CO2 bioreactor catalytic combustor 5, and CO2 is separated in the membrane separation devices 3 and 4. Together with (2), the oxidant gas (2) and a mixed gas (2) of 002 are supplied to the cathode lc.

尚、上述の実施例は好適な実施例の一つではあるが、こ
れに限定されるものではなく、本発明の要旨を逸脱しな
い範囲において種々変形実施可能である０例えば、本実
施例においては、アノードｌａで排出されるガス中の反
応によって生成するＣ０２、未反応分として残っている
＋１２及びＣＯを００２生成用触媒燃焼器５に供給して
酸化させ、Ｃ０２を補充するようにしているが、カソー
ド排ガス系６から回収する炭酸ガス■だけで足りる場合
にはこの限りでない、また、ガス分離装置３，４から回
収されたＣＯ２ガスはそのまま直接カソード１ｃに供給
されることもある。例えば、後述するように高温のカソ
ード排ガスからＣＯ２ガスを回収するような場合、ある
いは曲の加熱源ないしカソード排ガスの廃熱を利用して
電池反応に好適な温度に調整してから供給するような場
合である。また、本実施例ではカソード排出口に冷却器
を設け、排出ガスを約２００〜１５０”Ｃに冷却し、冷
却された排ガスをガス分離装置に導きＣ０２ガスを回収
するようにしているが、高温ガスのまま使用可能なガス
分離装置を採用する場合には冷却の必要はない。Although the above embodiment is one of the preferred embodiments, it is not limited thereto, and various modifications can be made without departing from the gist of the present invention.For example, in this embodiment, , C02 generated by the reaction in the gas discharged at the anode la, +12 and CO remaining as unreacted components are supplied to the catalytic combustor 5 for 002 generation and oxidized to replenish C02. This is not the case if only the carbon dioxide gas (2) recovered from the cathode exhaust gas system 6 is sufficient.Also, the CO2 gas recovered from the gas separation devices 3, 4 may be directly supplied to the cathode 1c as is. For example, as described below, CO2 gas may be recovered from high-temperature cathode exhaust gas, or CO2 gas may be supplied after adjusting the temperature to a suitable temperature for battery reaction using a music heating source or the waste heat of cathode exhaust gas. This is the case. In addition, in this embodiment, a cooler is provided at the cathode outlet to cool the exhaust gas to about 200 to 150"C, and the cooled exhaust gas is guided to the gas separation device to recover the C02 gas. When using a gas separation device that can be used as a gas, there is no need for cooling.

（発明の効果） 以上の説明より明らかなように、本発明によれば、未使
用のまま排出されてしまうカソード排ガス中の炭酸ガス
をガス分離装置により分離回収してカソードに再循環さ
せることによりカソードの炭酸ガス分圧を高めるように
しているので、従来のものより電池電圧を約１００〜１
５０ｎＶ程度高めることができるし、燃料電池の発電効
率を約１０％程度向上させることが期待できる。(Effects of the Invention) As is clear from the above description, according to the present invention, carbon dioxide gas in the cathode exhaust gas that is discharged unused is separated and recovered by a gas separation device and recirculated to the cathode. Since the partial pressure of carbon dioxide gas at the cathode is increased, the battery voltage can be lowered by approximately 100 to 1
It can be increased by about 50 nV, and it is expected that the power generation efficiency of the fuel cell will be improved by about 10%.

このことは、溶融炭酸塩型燃料電池の主な電池反応及び
ネルンストの式によって理解できる。即ち、溶融炭酸塩
型燃料電池の主な電池反応は、カソード（則（ｃ）　　
　！４０ｔ＋ＣＯｚ＋２ｅ　　−ＣＯｘ”−・・曲　■
（ａ）　　Ｈ！＋ＣＯ，ト　−＊　　Ｃｏ、＋Ｈ，Ｏ＋
２ｅ　　−・−−−−■であり、■、■の反応に対応す
る起電力Ｅ　（Ｖ）は、ネルンストの式、 で与えられる。尚、 ＰＩＩｚＯ（ａ）　・ＰＣＯｚ（ｃ）　・ＰＯｙ：（ｃ
）　・ｐＨｚ（ａ）　・ＰＣＯｚ（ａ）　−は電極にお
ける各成分の分圧を表す。This can be understood from the main cell reactions of molten carbonate fuel cells and the Nernst equation. That is, the main cell reaction of a molten carbonate fuel cell is at the cathode (rule (c)
! 40t+COz+2e -COx"-...Song ■
(a) H! +CO, T -* Co, +H, O+
2e −・−−−■, and the electromotive force E (V) corresponding to the reactions of ■ and ■ is given by the Nernst equation. In addition, PIIzO(a) ・PCOz(c) ・POy:(c
) ・pHz(a) ・PCOz(a) − represents the partial pressure of each component at the electrode.

したがって、カソードの炭酸ガス分圧を高めることによ
って、電池起電力は高くなり、かつ電池の発電効率ら向
上する。Therefore, by increasing the partial pressure of carbon dioxide gas at the cathode, the battery electromotive force increases and the power generation efficiency of the battery also improves.

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

図面は本発明の燃料電池の一実施例を示す原理図である
。 １・・・溶融炭酸塩型燃料電池本体、 １ａ・・・アノード、 ■ｂ・・・電解質、 ＩＣ・・・カソード、 ３．４・・・ガス分離装置、 ６・・・カソード排ガス系、 ■・・・回収されるＣ０２、 ■・・・回収ＣＯ２と酸化剤カスとの混合カス、■・・
・カソード排ガス。The drawing is a principle diagram showing an embodiment of the fuel cell of the present invention. 1... Molten carbonate fuel cell main body, 1a... Anode, ■b... Electrolyte, IC... Cathode, 3.4... Gas separation device, 6... Cathode exhaust gas system, ■ ...Recovered CO2, ■...Mixed residue of recovered CO2 and oxidizer residue, ■...
・Cathode exhaust gas.

Claims (1)

【特許請求の範囲】[Claims] 溶融炭酸塩型燃料電池のカソード排ガス系統にガス分離
装置を設け、カソード排ガス中の炭酸ガスを分離してカ
ソードに再循環させることを特徴とする溶融炭酸塩型燃
料電池。A molten carbonate fuel cell characterized in that a gas separation device is provided in the cathode exhaust gas system of the molten carbonate fuel cell, and carbon dioxide gas in the cathode exhaust gas is separated and recirculated to the cathode.
JP63010745A 1988-01-22 1988-01-22 Fuel battery with fusion carbonate Pending JPH01187775A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63010745A JPH01187775A (en) 1988-01-22 1988-01-22 Fuel battery with fusion carbonate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63010745A JPH01187775A (en) 1988-01-22 1988-01-22 Fuel battery with fusion carbonate

Publications (1)

Publication Number Publication Date
JPH01187775A true JPH01187775A (en) 1989-07-27

Family

ID=11758846

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63010745A Pending JPH01187775A (en) 1988-01-22 1988-01-22 Fuel battery with fusion carbonate

Country Status (1)

Country Link
JP (1) JPH01187775A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03238765A (en) * 1990-02-15 1991-10-24 Ishikawajima Harima Heavy Ind Co Ltd How to operate a molten carbonate fuel cell
WO2006043494A1 (en) * 2004-10-19 2006-04-27 Central Research Institute Of Electric Power Industry Combined power generation equipment
GB2498246A (en) * 2011-11-30 2013-07-10 Bosch Gmbh Robert Fuel cell system with afterburner for anode waste gas

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5719974A (en) * 1980-07-09 1982-02-02 Toshiba Corp Molten salt fuel cell system
JPS60165063A (en) * 1984-02-07 1985-08-28 Ishikawajima Harima Heavy Ind Co Ltd Fuel cell power generation system
JPS60230365A (en) * 1984-04-27 1985-11-15 Mitsubishi Electric Corp Composite type fuel cell power generating system
JPS62274561A (en) * 1986-05-22 1987-11-28 Mitsubishi Heavy Ind Ltd Molten carbonate fuel cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5719974A (en) * 1980-07-09 1982-02-02 Toshiba Corp Molten salt fuel cell system
JPS60165063A (en) * 1984-02-07 1985-08-28 Ishikawajima Harima Heavy Ind Co Ltd Fuel cell power generation system
JPS60230365A (en) * 1984-04-27 1985-11-15 Mitsubishi Electric Corp Composite type fuel cell power generating system
JPS62274561A (en) * 1986-05-22 1987-11-28 Mitsubishi Heavy Ind Ltd Molten carbonate fuel cell

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03238765A (en) * 1990-02-15 1991-10-24 Ishikawajima Harima Heavy Ind Co Ltd How to operate a molten carbonate fuel cell
WO2006043494A1 (en) * 2004-10-19 2006-04-27 Central Research Institute Of Electric Power Industry Combined power generation equipment
JPWO2006043494A1 (en) * 2004-10-19 2008-05-22 財団法人電力中央研究所 Combined power generation facility
US8329345B2 (en) 2004-10-19 2012-12-11 Central Research Institute Of Electric Power Industry Combined power generation equipment
GB2498246A (en) * 2011-11-30 2013-07-10 Bosch Gmbh Robert Fuel cell system with afterburner for anode waste gas
GB2498246B (en) * 2011-11-30 2016-09-28 Bosch Gmbh Robert Fuel cell system

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