JPH0435722A - Co2 recovery device utilizing molten carbonate-type fuel cell and operation thereof - Google Patents

Co2 recovery device utilizing molten carbonate-type fuel cell and operation thereof

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Publication number
JPH0435722A
JPH0435722A JP2140397A JP14039790A JPH0435722A JP H0435722 A JPH0435722 A JP H0435722A JP 2140397 A JP2140397 A JP 2140397A JP 14039790 A JP14039790 A JP 14039790A JP H0435722 A JPH0435722 A JP H0435722A
Authority
JP
Japan
Prior art keywords
gas
fuel cell
molten carbonate
anode
cathode
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
JP2140397A
Other languages
Japanese (ja)
Other versions
JP2932613B2 (en
Inventor
Kenzo Nakazawa
中沢　健三
Kokichi Uematsu
宏吉 上松
Satoshi Hatori
聡 羽鳥
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.)
IHI Corp
Original Assignee
IHI 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 IHI Corp filed Critical IHI Corp
Priority to JP2140397A priority Critical patent/JP2932613B2/en
Priority to US07/584,209 priority patent/US5232793A/en
Priority to CA002025654A priority patent/CA2025654C/en
Priority to EP90118035A priority patent/EP0418864B1/en
Priority to CN90107752A priority patent/CN1037941C/en
Priority to DE69008090T priority patent/DE69008090T2/en
Publication of JPH0435722A publication Critical patent/JPH0435722A/en
Application granted granted Critical
Publication of JP2932613B2 publication Critical patent/JP2932613B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0048—Molten electrolytes used at high temperature
    • H01M2300/0051—Carbonates
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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

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

Abstract

PURPOSE:To generate electric power and to recover CO2 by supplying a gas to be treated contg. CO2 before being discharged into the atmosphere to the cathode of a molten carbonate-type fuel cell along with fresh air to cause a galvanic reaction to concentrate CO2 and generate power and then recovering the CO2. CONSTITUTION:An oxidizing gas is supplied to the cathode 3 of a molten carbonate-type fuel cell 1 from a line 8, and a reformed raw gas is supplied to the anode 4 from a line 16. A molten carbonate-type fuel cell power generating system I for generating power by the galvanic reaction on the cathode 3 side and on the anode 4 side and a CO2 separator II for separating and discharging the CO2 in the gas are provided. A gas to be treated contg. CO2 and air are supplied to the cathode 3 from the line 8, and a line 25 for introducing the CO2-enriched gas into the separator II from the anode 4 is provided. Namely, power generation and CO2 recovery are simultaneously carried out, concd. CO2 is recovered, and the power required to separate CO2 is reduced.

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明は炭酸ガス（ＣＯ２）を多く含む燃焼排ガス（処
理ガス）を大気へ放出する前に処理ガス中に含まれる炭
酸ガスを回収すると同時に発電を行わせるために用いる
溶融炭酸塩型燃料電池を利用したＣＯ２回収装置とその
運転方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention collects carbon dioxide contained in the combustion exhaust gas (processed gas) containing a large amount of carbon dioxide (CO2) before releasing it into the atmosphere. The present invention relates to a CO2 recovery device using a molten carbonate fuel cell used to generate electricity and a method of operating the same.

［従来の技術］ 天然ガス（ＮＧ）を燃料とする火力発電所等から排出さ
れる処理ガス中には、多くのＣＯ２が含まれているが、
従来は、上記処理ガス中のＣ０７を除去することなく、
そのまま大気へ放出させているのか実状である。[Conventional technology] Processed gas discharged from thermal power plants, etc. that use natural gas (NG) as fuel contains a large amount of CO2.
Conventionally, without removing C07 from the processing gas,
The reality is that it is being released directly into the atmosphere.

［発明か解決しようとする課題１ ところか、上記ＣＯ７を含む処理ガスをそのまま大気中
へ放出させると、地球表面からの長波長輻射が、大気中
に放出されて存在するＣＯ２に吸収されて大気中に透過
しにくくなるため、その分だけ地表及び下層大気か暖ま
って地球を温暖化させる結果となっている。近年、この
ＣＯ２による地球温暖化は大きな問題となってあり、地
球温暖化を緩和させることが不可欠である。[Problem to be solved by the invention 1 However, if the treated gas containing CO7 is directly released into the atmosphere, long-wavelength radiation from the earth's surface will be absorbed by the CO2 that is emitted into the atmosphere and will be absorbed into the atmosphere. Since it becomes difficult for the air to penetrate into the atmosphere, the surface of the earth and the lower atmosphere become warmer, resulting in global warming. In recent years, global warming caused by CO2 has become a major problem, and it is essential to alleviate global warming.

そこで、本発明は、天然ガス火力発電所等から排出され
る処理ガス中のＣＯ２を回収すると共に発電させるよう
にしようとするものである。Therefore, the present invention aims to recover CO2 in the treated gas discharged from natural gas-fired power plants and the like, and to generate electricity at the same time.

［課題を解決するための手段］ 本発明は、上記課題を解決するために、溶融炭酸塩をし
み込ませた電解質板をカソードとアノードの画電極で挟
んでなるものを１セルとする溶融炭酸塩型燃料電池のカ
ソードに酸化ガスを供給すると共にアノードに改質原料
ガスを改質して供給するようにしてカソード側とアノー
ド側での電池反応で発電するようにしてある溶融炭酸塩
型燃料電池発電システムと、ガス中のＣＱを分離してＣ
０を回収できるようにしたＣＯ２分離装置とを設け、上
記溶融炭酸塩型燃料電池のカソードに、ＣＯ？を含む処
理ガスを空気とともに供給するようにし、且つ上記アノ
ードからＣＯ？の濃縮したガスをＣＯ２分離装置に導入
する導入ラインを設けた構成とする。又、上記カソード
へ供給する処理ガス／空気のモル比を１〜０．６５の範
囲とし、且つアノードから排出されてＣＯ２分離装置へ
導入されるＣＯ２量に対してＣＯ２分離装置で回収する
ＣＯ？量の比を０．２〜Ｏ１４の範囲のＣＯ２回収率と
する条件で運転するようにする。[Means for Solving the Problems] In order to solve the above problems, the present invention provides a molten carbonate cell in which one cell is formed by sandwiching an electrolyte plate impregnated with molten carbonate between cathode and anode picture electrodes. A molten carbonate fuel cell in which an oxidizing gas is supplied to the cathode of the fuel cell, and reformed raw material gas is supplied to the anode to generate electricity through a cell reaction between the cathode and anode sides. Power generation system and separating CQ in gas
A CO2 separator capable of recovering CO2 is installed at the cathode of the molten carbonate fuel cell. A processing gas containing CO? is supplied together with air, and CO? is supplied from the anode. The configuration includes an introduction line for introducing the concentrated gas into the CO2 separation device. Further, the molar ratio of the processing gas/air supplied to the cathode is in the range of 1 to 0.65, and the amount of CO2 recovered by the CO2 separator is adjusted to the amount of CO2 discharged from the anode and introduced into the CO2 separator. The system is operated under conditions such that the CO2 recovery rate is in the range of 0.2 to 0.14.

［作　　　用１ ＣＯ２を含む処理ガスと新鮮空気を溶融炭酸塩型燃料電
池のカソードに供給し、アノードに燃料ガスを供給する
と、カソード側とアノード側で電池反応か行われて発電
か行われると共に、カソードに供給された処理ガス中の
ＣＯ２は炭酸イオンとしてアノード側へ運ばれ、Ｃ０は
濃縮されてアノードから排出される。このＣＯ２が濃縮
されたガスは、ＣＯ２分離装置へ導かれ、ＣＯ２は分離
して回収される。ＣＯの回収はＣ０２Ｓ度を高めてから
行われることから、ＣＯ２分離に必要な動力か少なくて
すむ。[Action 1] When a process gas containing CO2 and fresh air are supplied to the cathode of a molten carbonate fuel cell, and fuel gas is supplied to the anode, a cell reaction occurs on the cathode side and the anode side, generating electricity. , CO2 in the process gas supplied to the cathode is carried to the anode side as carbonate ions, and CO2 is concentrated and discharged from the anode. This CO2-enriched gas is led to a CO2 separator, where CO2 is separated and recovered. Since CO recovery is performed after increasing the CO2S degree, less power is required for CO2 separation.

［実　施　例］ 以下、本発明の実施例を図面を参照して説明する。[Example] Embodiments of the present invention will be described below with reference to the drawings.

第１図は本発明のＣＯ，回収装置の一実施例を示すもの
で、天然ガス火力発電所５から排出されたＣＯ２を含む
処理ガスｂを新鮮空気ａとともに溶融炭酸塩型燃料電池
１のカソードに供給するようにし、且つ改質原料ガスと
しての天然ガスを改質してアノードに供給するようにし
てある溶融炭酸塩型燃料電池発電システム■と、ＣＯ２
を含むガスからＣＯ２を分離するようにしてあるＣ０分
離装置■とからなる構成としである。FIG. 1 shows an embodiment of the CO recovery device of the present invention, in which a treated gas b containing CO2 discharged from a natural gas-fired power plant 5 is sent to the cathode of a molten carbonate fuel cell 1 along with fresh air a. A molten carbonate fuel cell power generation system (■) that is configured to supply CO2 to
This is a configuration consisting of a CO separator (2) which is designed to separate CO2 from a gas containing CO2.

詳述すると、上記溶融炭酸塩型燃料電池発電システムは
、電解質として溶融炭酸塩をしみ込ませてなる電解質板
２をカソード（酸素極）３とアノード（燃料極）４で両
面から挟んでなるものを１セルとする溶融炭酸塩型燃料
電池１０カンード３に、新鮮空気ａをフィルタ６を通し
た後、圧縮＠７で圧縮して空気供給ライン８を通して供
給するようにすると共に、カソード３から排出されたカ
ソードガスは、カソードガス出ロライン９よりタービン
１０に導入した後に大気へ放出させるようにし、カソー
ドガスの一部は、分岐ライン１１を通して改質器１２の
燃焼室１２ｂへ導入させるようにし、該改質器１２の燃
焼室１２ｂから排出された排ガスはブロワ１３で昇圧し
てライン１４によりカソード３へ供給されるようにしで
ある。一方、アノード４には、天然ガスＮＧを天然ガス
予熱器１５で予熱した後、天然ガス供給うイン１６を通
して改質器１２の改質器１２ａに導入し、ここで燃料ガ
スＦＧに改質して燃料ガス供給ライン１７より燃料ガス
ＦＧを供給するようにし、アノード４がら排出されたア
ノードガスは、熱交換器１８、蒸発器１９、凝縮器２゜
を経て気液分離器２１へ導き、ここでアノードガス中の
水（Ｈ２Ｏ）を分離し、ｃＱ２を含むガスは、導入ライ
ン２５よりＣＯ？分離装置■へ導いてＣ０を分離して回
収させるようにし、上記気液分離器２１で分離されたＨ
２Ｏは、ポンプ２２て加圧して液留容器２３に入れた後
、上記蒸発器１９で蒸発させ蒸気として天然ガス供給ラ
イン１６の途中に混入されるようにしてあり、空気供給
ライン８のフィルタ６人口側に、天然ガス火力発電所５
からの処理ガスを処理ガスライン２４により供給するよ
うにしてある。To be more specific, the molten carbonate fuel cell power generation system is constructed by sandwiching an electrolyte plate 2 impregnated with molten carbonate as an electrolyte between a cathode (oxygen electrode) 3 and an anode (fuel electrode) 4. Fresh air a is passed through a filter 6 to a molten carbonate fuel cell 10 cand 3, which is made up of one cell, and then compressed by compression @ 7 and supplied through an air supply line 8, and the air is discharged from the cathode 3. The cathode gas is introduced into the turbine 10 through the cathode gas outlet line 9 and then released into the atmosphere, and a part of the cathode gas is introduced into the combustion chamber 12b of the reformer 12 through the branch line 11. Exhaust gas discharged from the combustion chamber 12b of the reformer 12 is pressurized by a blower 13 and is supplied to the cathode 3 via a line 14. On the other hand, for the anode 4, natural gas NG is preheated by a natural gas preheater 15, and then introduced into the reformer 12a of the reformer 12 through the natural gas supply inlet 16, where it is reformed into fuel gas FG. The fuel gas FG is supplied from the fuel gas supply line 17, and the anode gas discharged from the anode 4 is guided to the gas-liquid separator 21 through the heat exchanger 18, evaporator 19, and condenser 2°. The water (H2O) in the anode gas is separated, and the gas containing cQ2 is introduced from the introduction line 25 into CO? The H separated by the gas-liquid separator 21 is
After the 2O is pressurized by the pump 22 and put into the liquid distillation container 23, it is evaporated by the evaporator 19 and mixed into the natural gas supply line 16 as steam, and the filter 6 of the air supply line 8 On the population side, natural gas-fired power plant 5
A processing gas is supplied from the processing gas line 24.

又、ＣＯ２分離装置■は、上記気液分離器２１で水と分
離された後のガス中のＣ０２を分離して、分離したｃＱ
２を回収ライン２６より取り出して回収し、ＣＯ２処理
装置２９へ送るようにすると共に、ＧＯ，を回収後、残
りのガスはライン２７より溶融炭酸塩型燃料電池発電シ
ステム■に戻し、ブロワ２８より熱交換器１８を経て改
質器１２の燃焼室１２ｂに導入するようにしてある。こ
のＣＯ７分離装置装置は、ＣＯ２をガスのまま回収する
ようにしたものと、Ｃ０を低温流体により冷却して液体
として回収するようにしたものがある。In addition, the CO2 separator (2) separates the CO2 in the gas after it has been separated from water in the gas-liquid separator 21, and converts it into separated cQ.
2 is taken out from the recovery line 26, collected, and sent to the CO2 processing device 29, and after collecting GO, the remaining gas is returned to the molten carbonate fuel cell power generation system (■) through the line 27, and is sent to the CO2 processing device 29 through the blower 28. The fuel is introduced into the combustion chamber 12b of the reformer 12 via the heat exchanger 18. There are two types of CO7 separator devices: one that recovers CO2 as a gas, and one that cools CO2 with a low-temperature fluid and recovers it as a liquid.

今、火力発電所５から排出された処理ガスｂ中のＣＯ２
を回収しようとする場合は、上記処理ガスｂを処理ガス
ライン２４より空気供給ライン８に入れ、空気ａととも
に圧縮機７で圧縮してカソード３へ供給するようにし、
一方、ＣＣｈ分離装置■でガス化された天然ガスＮＧを
天然ガス供給ライン１６に導いて改質器１２で改質した
後、燃料ガスＦＧとしてアノード４に供給して、カソー
ド３とアノード４でそれぞれ電池反応を起こさせ、ＣＯ
２を濃縮してアノード４から取り出すようにする。すな
わち、カソード３側では、ＣＯ２＋　１／２０？＋　２
８−→Ｃ０３−の反応か行われて、炭酸イオンＣＯ３−
に変えられ、この炭酸イオンは、電解質板２中を泳動し
てアノード４へ運ばれる。アノード４側では、ＣＯ３−
＋Ｈ２−）Ｈ２０＋ＣＯ２＋２　ｅ−の反応が行われる
。Now, CO2 in the treated gas b discharged from the thermal power plant 5
When attempting to recover the gas, the processing gas b is introduced from the processing gas line 24 into the air supply line 8, compressed together with air a by the compressor 7, and supplied to the cathode 3.
On the other hand, the natural gas NG gasified by the CCh separator (2) is led to the natural gas supply line 16 and reformed by the reformer 12, and then supplied to the anode 4 as fuel gas FG. Each causes a battery reaction and CO
2 is concentrated and taken out from the anode 4. In other words, on the cathode 3 side, CO2+ 1/20? +2
8-→C03- reaction is carried out, carbonate ion CO3-
The carbonate ions migrate through the electrolyte plate 2 and are transported to the anode 4. On the anode 4 side, CO3-
+H2-)H20+CO2+2 e- reaction takes place.

上記カソード３側とアノード４側での反応が進むことに
より発電が行われると共に、ＣＯ２かカソード３側から
アノード４側へ移動する。アノード４側のガス流量はカ
ソード３側のガス流量に対して数分の１と少ないため、
アノード４側のガス流量が少ない分だけ、アノード４側
へ移動したＣＯ？は濃縮され、数倍のｙＡ度になる。As the reaction progresses on the cathode 3 side and the anode 4 side, power generation is performed, and CO2 moves from the cathode 3 side to the anode 4 side. Since the gas flow rate on the anode 4 side is a fraction of the gas flow rate on the cathode 3 side,
Did CO move to the anode 4 side due to the small gas flow rate on the anode 4 side? is concentrated and becomes several times more yA degrees.

したがって、溶融炭酸塩型燃料電池１て発電とともにＣ
Ｏの濃縮が行われることになる。Therefore, the molten carbonate fuel cell 1 generates electricity as well as C.
Concentration of O will take place.

アノード４側てＣＱの濃縮されたアノードガスは、熱交
換器１８、蒸発器１９、凝縮器２ｏを経て気液分離器２
１に送られ、ここでＨ２Ｏが分離して除去された後、導
入ライン２５よりＣＯ２分離装置■に導かれ、ここで、
ガス中のｃＱ２が分離されて回収ライン２６より取り出
されて回収され、回収したｃＱ２をＣＯ２処理装置２９
へ送ること（なる。The concentrated anode gas of CQ on the anode 4 side passes through the heat exchanger 18, the evaporator 19, and the condenser 2o to the gas-liquid separator 2o.
1, where H2O is separated and removed, and then led from the introduction line 25 to the CO2 separator ■, where:
cQ2 in the gas is separated and taken out and recovered from the recovery line 26, and the recovered cQ2 is sent to the CO2 processing device 29.
to send to (become)

この場合、ＣＯ２をガスのまま回収するときは、ガス中
のＣＯ？を分離してそのまま回収すればよく、ＣＯ２を
液体の状態で回収するときは、ｃＱを低温流体で冷却し
て液化させるよう番こする。In this case, when recovering CO2 as a gas, the CO2 in the gas? It is sufficient to separate the CO2 and collect it as is. When recovering CO2 in a liquid state, cQ is cooled with a low-temperature fluid to be liquefied.

ｃｏ２分離装置■でＣｏ２を回収後、残りのガスは、ラ
イン２７より溶融炭酸塩型燃料電池発電システムにおけ
る熱交換器１８を通って改質器１２の燃焼室１２ｂへと
導かれ、カソード３にリサイクルされる。After recovering Co2 in the CO2 separator ■, the remaining gas is guided from the line 27 through the heat exchanger 18 in the molten carbonate fuel cell power generation system to the combustion chamber 12b of the reformer 12, and then to the cathode 3. Recycled.

上記ＣＯ２の回収において、たとえば、全ガス流量に対
して９％のＣＯ？を含む処理ガスを処理するとした場合
についてみると、カソード３に入ったＣＯ２流量は７％
であったものか、アノード４の出口では４２％のＣＯ２
量まで濃縮され、更に、ＣＯ２導入ライン２５からＣＯ
２分離装置装置導入されるガス中のＣＱは８２％となり
、ＧＯ２分離装置装置らライン２７へ導かれるガス中の
ＣＯ２は７４％であり、ＣＯ２分離装置装置回収される
ガスＧ、ｔＣＯ２か１００％であり、タービン１０を経
て大気中に放出されるガス中のＣＯ２は３％に低減でき
る。In the above CO2 recovery, for example, 9% CO2 with respect to the total gas flow rate? In the case of processing a processing gas containing
At the exit of anode 4, 42% of CO2
The CO2 is further concentrated to
2 CQ in the gas introduced into the CO2 separation device is 82%, CO2 in the gas led from the GO2 separation device to line 27 is 74%, and the gas G, tCO2 recovered by the CO2 separation device is 100%. Therefore, CO2 in the gas released into the atmosphere via the turbine 10 can be reduced to 3%.

かかる結果が得られるための運転には、カソード３に供
給される処理ガス／新鮮空気のモル比及びＧＯ２分離装
置装置Ｃｏ２回収率に対して範囲を設けるようにすれば
よい。その条件としては、 ■供給する処理ガスｂ／空気ａのモル比を、第２図に示
す如く、　１〜０．６５の範囲とし、■ＧＯ分離装置装
置おいて回収ライン２６より回収するＣＯ２量が、導入
ライン２５よりＧＯ２分離装置装置導入されるＣＯ２量
に対して０．２〜０．４の範囲となるＣＯ２回収率とす
るのか最適である。In order to achieve such a result, a range may be set for the molar ratio of process gas/fresh air supplied to the cathode 3 and the CO2 recovery rate of the GO2 separator. The conditions are: (1) The molar ratio of processing gas b/air a to be supplied is in the range of 1 to 0.65, as shown in Figure 2, and (2) the amount of CO2 to be recovered from the recovery line 26 in the GO separation device. However, it is optimal to set the CO2 recovery rate to be in the range of 0.2 to 0.4 with respect to the amount of CO2 introduced from the introduction line 25 into the GO2 separator.

これらの運転範囲は、 ０）溶融炭酸塩型燃料電池１のカソード３人口における
ＣＯ２量と０２蟻、及び改質器１２の燃焼室１２ｂ出口
におけるα量が適正量確保されること、 （へ）本装置より排出するガスのＣＯ２低減率、すなわ
ち、処理ガスｂ中のＣＯ２量に対してタービン１０を経
た後大気へ排出されるＣＯ２量の割り合いが１以下とな
ること、 を満足させるために定めた条件である。These operating ranges are as follows: 0) The amount of CO2 and 02 at the cathode 3 of the molten carbonate fuel cell 1 and the amount of α at the outlet of the combustion chamber 12b of the reformer 12 must be secured in appropriate amounts; In order to satisfy the CO2 reduction rate of the gas emitted from this device, that is, the ratio of the amount of CO2 emitted to the atmosphere after passing through the turbine 10 to the amount of CO2 in the processed gas b is 1 or less. This is a set condition.

上記運転条件により処理ガス／空気のモル比を第２図の
に）の如く設定し、且つＣＯ２分離装置装置おけるＣＯ
２回収率をＳ）の如＜　０．２８〜０．３５程度に設定
すると、改質器１２の燃焼室出口の０２量と、ＧＯ−２
低減率は、第３図の（Ｃ）と０）に示す如くなり、上、
Ｊした（イ）（へ）の条件を満足している。Based on the above operating conditions, the molar ratio of processing gas/air is set as shown in Figure 2), and the CO2 separation equipment is
When the 2 recovery rate is set to about < 0.28 to 0.35 as shown in S), the 02 amount at the combustion chamber outlet of the reformer 12 and the GO-2
The reduction rate is as shown in (C) and 0) in Figure 3.
It satisfies the conditions of (a) and (f).

上記において、ＣＯ２回収率を、第２図に示す如く、０
．２８〜０，３５程度に設定すると、ＧＯ７分離装置装
置おいて、ＣＱを液化分離する際の００分圧か高くなり
、必要な動力か少なくてすむ利点がある。In the above, the CO2 recovery rate is 0 as shown in Figure 2.
．． When the pressure is set to about 28 to 0.35, the partial pressure when liquefying and separating CQ in the GO7 separation device becomes higher, which has the advantage of requiring less power.

なお、本発明は上記実施例に限定されるものではなく、
天然ガス火力発電所５から排出される処理ガス中のＣＱ
を発電に利用して回収する場合を示したか、火力発電所
以外のものから排出される処理ガスでも同様に扱えるこ
と、又、溶融炭酸塩型燃料電池発電システムは一例を示
すもので、これに限定されるものではないこと、タービ
ン１０を経て排出される先に別の溶融炭酸塩型燃料電池
を置くようにしてもよい。Note that the present invention is not limited to the above embodiments,
CQ in treated gas discharged from natural gas-fired power plant 5
We have shown that it can be used in the same manner as treated gas discharged from sources other than thermal power plants, and that a molten carbonate fuel cell power generation system is an example of this. Without limitation, another molten carbonate fuel cell may be placed before exhausting through the turbine 10.

［発明の効果］ 以上述へた如く、本発明の溶融炭酸塩型燃料電池を利用
したｃｏ２回収装′置装よれば、大気へ放出される前の
ＣＯを含む処理ガスを新鮮空気とともに溶融炭酸塩型燃
料電池のカソードに供給して電池反応を起こさせ、発電
と共にＣＯ２を濃縮させるようにし、濃度の高いＣＯ２
をｃｏ２分離装置へ導入してＣＯ２回収を行わせるよう
にするので、発電とＣＯ２回収が同時にできると共に、
Ｃ０２ａ度を高めてから回収することから、ｃｏ２分離
に必要な動力か少なくてすむ、等の優れた効果を奏し得
られ、更に、カソード（供給する上記処理ガス／新鮮空
気のモル比を１〜０，６５の範囲、ＣＯ分離装置のＣＯ
２回収率を、ＣＣｈ分離装置で回収するｃｏ２ｔｉかｃ
ｏ２分離装置に導入されるｃｏ２ｍに対して０．２〜０
．４の範囲となるように特定して運転することにより、
ＣＯ２回収量の増大と効率の高い溶融炭酸塩型燃料電池
発電を確保することができる、という効果も奏し得られ
る。[Effects of the Invention] As described above, according to the CO2 recovery device using the molten carbonate fuel cell of the present invention, the process gas containing CO before being released into the atmosphere is converted into molten carbon dioxide together with fresh air. It is supplied to the cathode of a salt-type fuel cell to cause a cell reaction, and the CO2 is concentrated while generating electricity.
Since CO2 is introduced into the CO2 separator and CO2 is recovered, power generation and CO2 recovery can be performed at the same time.
Since the CO2a degree is increased before recovery, excellent effects such as less power required for CO2 separation can be achieved. CO in the range 0,65, CO separator
2 recovery rate, co2ti or c recovered by CCh separator
0.2 to 0 for the CO2m introduced into the O2 separator
．． By specifying and driving within the range of 4,
It is also possible to achieve the effects of increasing the amount of CO2 recovered and ensuring highly efficient molten carbonate fuel cell power generation.

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

第１図は本発明の一実施例を示す概要図、第２図は処理
ガスと空気のモル比及びＣＯ２回収率の運転範囲を示す
図、第３図は第２図の運転範囲にあける改質器燃焼全出
口のＯ？量及びＣＯ：！低減率を示す図である。 ■・・・溶融炭酸塩型燃料電池発電システム、■・・・
ＣＯ２分離装置、１・・・溶融炭酸塩型燃料電池、２・
・・電解質板、３・・・カソード、４・・・アノード、
８・・・空気供給ライン、１２・・・改質器、１６・・
・天然ガス供給ライン、２１・・・気液分離器、２５・
・・導入ライン、２６・・・回収ライン、ａ・・・空気
、ｂ・・・処理ガス、ＮＧ・・・天然ガス。 第１図Figure 1 is a schematic diagram showing an embodiment of the present invention, Figure 2 is a diagram showing the operating range of the molar ratio of process gas to air and CO2 recovery rate, and Figure 3 is a diagram showing changes made to the operating range of Figure 2. O at all outlets of the combustion chamber? Amount and CO:! It is a figure showing a reduction rate. ■... Molten carbonate fuel cell power generation system, ■...
CO2 separation device, 1... molten carbonate fuel cell, 2.
... Electrolyte plate, 3... Cathode, 4... Anode,
8... Air supply line, 12... Reformer, 16...
・Natural gas supply line, 21... Gas-liquid separator, 25.
...Introduction line, 26...Recovery line, a...Air, b...Processing gas, NG...Natural gas. Figure 1

Claims (4)

【特許請求の範囲】[Claims] （１）溶融炭酸塩型燃料電池のカソードに酸化ガスを供
給すると共にアノードに改質原料ガスを改質して供給す
るようにして、カソード側とアノード側での電池反応で
発電するようにしてある溶融炭酸塩型燃料電池発電シス
テムと、ガス中のＣＯ＿２を分離して取出せるようにし
たＣＯ＿２分離装置とを設け、上記溶融炭酸塩型燃料電
池のカソードに、ＣＯ＿２を含む処理ガスを空気ととも
に供給するようにし、且つ上記アノードからＣＯ＿２の
濃縮したガスをＣＯ＿２分離装置に導入する導入ライン
を設けてなることを特徴とする溶融炭酸塩型燃料電池を
利用したＣＯ＿２回収装置。(1) Oxidizing gas is supplied to the cathode of the molten carbonate fuel cell, and reformed raw material gas is supplied to the anode, so that power is generated through cell reactions between the cathode and anode sides. A molten carbonate fuel cell power generation system and a CO_2 separation device capable of separating and extracting CO_2 from the gas are installed, and a process gas containing CO_2 is delivered to the cathode of the molten carbonate fuel cell together with air. A CO_2 recovery device using a molten carbonate fuel cell, characterized in that it is provided with an introduction line for supplying CO_2 and introducing concentrated CO_2 gas from the anode to the CO_2 separation device. （２）溶融炭酸塩型燃料電池のカソードに供給するＣＯ
＿２を含む処理ガス／空気のモル比を１〜０．６５の範
囲として運転し、溶融炭酸塩型燃料電池のアノードから
排出されたアノードガスを水を分離した後、ＣＯ＿２分
離装置に導入し、該ＣＯ＿２分離装置でＣＯ＿２を分離
して回収するように運転することを特徴とする溶融炭酸
塩型燃料電池を利用したＣＯ＿２回収装置の運転方法。(2) CO supplied to the cathode of a molten carbonate fuel cell
operating with a molar ratio of process gas/air containing _2 in the range of 1 to 0.65, and introducing the anode gas discharged from the anode of the molten carbonate fuel cell into a CO_2 separator after separating water; A method of operating a CO_2 recovery device using a molten carbonate fuel cell, characterized in that the CO_2 separation device is operated to separate and recover CO_2. （３）溶融炭酸塩型燃料電池のカソードに、ＣＯ＿２を
含む処理ガスを空気とともに供給し、溶融炭酸塩型燃料
電池のアノードから排出されたアノードガスを水を分離
した後にＣＯ＿２分離装置に導入し、該ＣＯ＿２分離装
置でＣＯ＿２を分離して回収するとき、ＣＯ＿２分離装
置で回収するＣＯ＿２量がアノードから出てＣＯ＿２分
離装置へ導入されるＣＯ＿２量に対して０．２〜０．４
の範囲の回収率となるように運転することを特徴とする
溶融炭酸塩型燃料電池を利用したＣＯ＿２回収装置の運
転方法。(3) A process gas containing CO_2 is supplied together with air to the cathode of the molten carbonate fuel cell, and the anode gas discharged from the anode of the molten carbonate fuel cell is introduced into the CO_2 separation device after separating water. When CO_2 is separated and recovered by the CO_2 separator, the amount of CO_2 recovered by the CO_2 separator is 0.2 to 0.4 with respect to the amount of CO_2 released from the anode and introduced into the CO_2 separator.
A method for operating a CO_2 recovery device using a molten carbonate fuel cell, characterized by operating the CO_2 recovery device so that the recovery rate is in the range of . （４）溶融炭酸塩型燃料電池のカソードに供給するＣＯ
＿２を含む処理ガス／空気のモル比を１〜０．６５の範
囲とし、且つＣＯ＿２を分離するＣＯ＿２分離装置で回
収するＣＯ＿２量がアノードから出てＣＯ＿２分離装置
へ導入されるＣＯ＿２量に対して０．２〜０．４の範囲
のＣＯ＿２回収率となるように運転することを特徴とす
る溶融炭酸塩型燃料電池を利用したＣＯ＿２回収装置の
運転方法。(4) CO supplied to the cathode of a molten carbonate fuel cell
The molar ratio of process gas/air containing _2 is in the range of 1 to 0.65, and the amount of CO_2 recovered by the CO_2 separator that separates CO_2 is relative to the amount of CO_2 that comes out from the anode and is introduced into the CO_2 separator. 1. A method of operating a CO_2 recovery device using a molten carbonate fuel cell, characterized by operating the CO_2 recovery rate in a range of 0.2 to 0.4.
JP2140397A 1989-09-19 1990-05-30 Operating method of CO 2 recovery device using molten carbonate fuel cell Expired - Lifetime JP2932613B2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2140397A JP2932613B2 (en) 1990-05-30 1990-05-30 Operating method of CO 2 recovery device using molten carbonate fuel cell
US07/584,209 US5232793A (en) 1989-09-19 1990-09-18 Method of and apparatus for utilizing and recovering co2 in combustion exhaust gas
CA002025654A CA2025654C (en) 1989-09-19 1990-09-18 Method of and apparatus for utilizing and recovering co2 combustion exhaust gas
EP90118035A EP0418864B1 (en) 1989-09-19 1990-09-19 Method of and apparatus for utilizing and recovering carbondioxide in combustion exhaust gas
CN90107752A CN1037941C (en) 1989-09-19 1990-09-19 Method of and apparatus for utilizing and recovering CO2 in combustion exhaust gas
DE69008090T DE69008090T2 (en) 1989-09-19 1990-09-19 Method and device for using and recovering carbon dioxide in a combustion exhaust gas.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2140397A JP2932613B2 (en) 1990-05-30 1990-05-30 Operating method of CO 2 recovery device using molten carbonate fuel cell

Publications (2)

Publication Number Publication Date
JPH0435722A true JPH0435722A (en) 1992-02-06
JP2932613B2 JP2932613B2 (en) 1999-08-09

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006196268A (en) * 2005-01-12 2006-07-27 Chugoku Electric Power Co Inc:The Power generation facility and power generation method
JP2009240881A (en) * 2008-03-31 2009-10-22 Chugoku Electric Power Co Inc:The Method of desulfurizing exhaust gas, exhaust gas desulfurizer, and carbon dioxide-recovering fuel cell power generation system equipped with the exhaust gas desulfurizer
JP5282103B2 (en) * 2008-11-18 2013-09-04 東京瓦斯株式会社 Hydrogen recycling type MCFC power generation system

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006196268A (en) * 2005-01-12 2006-07-27 Chugoku Electric Power Co Inc:The Power generation facility and power generation method
JP2009240881A (en) * 2008-03-31 2009-10-22 Chugoku Electric Power Co Inc:The Method of desulfurizing exhaust gas, exhaust gas desulfurizer, and carbon dioxide-recovering fuel cell power generation system equipped with the exhaust gas desulfurizer
JP5282103B2 (en) * 2008-11-18 2013-09-04 東京瓦斯株式会社 Hydrogen recycling type MCFC power generation system

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