JPH0613094A - Fuel exhaust gas recycle system for indirect internal reformed molten carbonate fuel cell - Google Patents
Fuel exhaust gas recycle system for indirect internal reformed molten carbonate fuel cellInfo
- Publication number
- JPH0613094A JPH0613094A JP4171101A JP17110192A JPH0613094A JP H0613094 A JPH0613094 A JP H0613094A JP 4171101 A JP4171101 A JP 4171101A JP 17110192 A JP17110192 A JP 17110192A JP H0613094 A JPH0613094 A JP H0613094A
- Authority
- JP
- Japan
- Prior art keywords
- fuel
- exhaust gas
- reforming
- electrode
- gas
- 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
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
- 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
- H01M8/0625—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 in a modular combined reactor/fuel cell structure
-
- 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
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、間接内部改質溶融炭酸
塩型燃料電池の燃料排ガスリサイクルシステムに関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel exhaust gas recycling system for indirect internal reforming molten carbonate fuel cells.
【０００２】[0002]
【従来の技術】溶融炭酸塩型燃料電池は作動温度が約６
５０℃と高温であり、通常燃料として使用される天然ガ
ス（主成分：メタン）の改質温度である８００℃に近い
ため、電池スタック内で燃料の改質を行う内部改質方式
が可能である。この内部改質方式は、燃料改質装置が不
要であるためコンパクト化が可能であると共に、電池反
応の際に生じる熱や水を、改質反応に必要な熱や水とし
て利用することができる等の優れた特長があるため外部
改質方式に比べて高い発電効率が期待できる。2. Description of the Related Art A molten carbonate fuel cell has an operating temperature of about 6
Since the temperature is as high as 50 ° C and is close to 800 ° C, which is the reforming temperature of natural gas (main component: methane) normally used as a fuel, an internal reforming method for reforming the fuel in the cell stack is possible. is there. This internal reforming system can be made compact because a fuel reforming device is unnecessary, and heat and water generated during the cell reaction can be used as heat and water necessary for the reforming reaction. Due to such excellent features, higher power generation efficiency can be expected compared to the external reforming method.
【０００３】この内部改質方式は、改質触媒の配置方法
により直接内部改質方式と，間接内部改質方式とに分類
される。前者は図７に示すように、燃料極２ａ背面の燃
料ガス通路（図示せず）に改質触媒２ｂを設置した電池
であり、水素が消費される場所に改質触媒２ｂが設けら
れているため改質効率が高くより高い発電効率が期待で
きるが、改質触媒２ｂが電解質１ａの溶融炭酸塩により
汚染されやすく特性劣化が大きいという問題がある。一
方、後者は図８に示すように、数セル（通常３〜６セ
ル）毎に改質触媒５１ａを充填した改質容器５１を設置
した電池であり、改質容器５１（即ち、改質触媒）と電
解質１ａ（即ち、溶融炭酸塩）とが隔離して配置されて
いるため、前者のような溶融炭酸塩による改質触媒の汚
染の問題がなく長寿命が期待できるという特長がある。The internal reforming system is classified into a direct internal reforming system and an indirect internal reforming system depending on the method of arranging the reforming catalyst. The former is a battery in which a reforming catalyst 2b is installed in a fuel gas passage (not shown) on the back surface of the fuel electrode 2a as shown in FIG. 7, and the reforming catalyst 2b is installed in a place where hydrogen is consumed. Therefore, the reforming efficiency is high and higher power generation efficiency can be expected, but there is a problem that the reforming catalyst 2b is easily contaminated by the molten carbonate of the electrolyte 1a and the characteristic deterioration is large. On the other hand, the latter is a battery in which a reforming container 51 filled with the reforming catalyst 51a is installed every several cells (usually 3 to 6 cells) as shown in FIG. 2) and the electrolyte 1a (that is, the molten carbonate) are separated from each other, so that there is no problem of contamination of the reforming catalyst by the molten carbonate as in the former case, and a long life can be expected.
【０００４】[0004]
【発明が解決しようとする課題】ところで、図８に示し
た従来の間接内部改質溶融炭酸塩型燃料電池は、燃料ガ
ス（天然ガスと水蒸気との混合ガス）を改質容器５１で
水素を主体とするガスに改質した後、リターンマニホー
ルド８１を介して燃料極２ｃに供給し電池反応を行って
いる。したがって、改質容器５１で生成した水素が上記
直接内部改質方式のようにその場所で消費されないた
め、直接内部改質方式に比べて改質効率が悪く（即ち、
残メタンが多い）発電効率が悪いという問題があった。By the way, in the conventional indirect internal reforming molten carbonate fuel cell shown in FIG. 8, fuel gas (mixed gas of natural gas and water vapor) is converted into hydrogen in the reforming vessel 51. After reforming into the main gas, it is supplied to the fuel electrode 2c through the return manifold 81 to cause the cell reaction. Therefore, the hydrogen generated in the reforming vessel 51 is not consumed at that place as in the direct internal reforming method, so that the reforming efficiency is lower than that of the direct internal reforming method (that is,
There was a problem that power generation efficiency was poor.
【０００５】本発明は、改質効率を向上させ（即ち、残
メタンの量を減少させ）、延いては発電効率を向上させ
ることができる間接内部改質溶融炭酸塩型燃料電池の燃
料排ガスリサイクルシステムを提供することを目的とす
る。The present invention is a fuel exhaust gas recycle of an indirect internal reforming molten carbonate fuel cell which can improve the reforming efficiency (that is, reduce the amount of residual methane) and thus the power generation efficiency. The purpose is to provide a system.
【０００６】[0006]
【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、以下のことを特徴とする。 燃料極と酸化剤極とを配置したセルを、セパレータ
を介して複数積層させ、且つ、前記複数のセル間の少な
くとも１部に改質容器を介挿させて成る間接内部改質溶
融炭酸塩型燃料電池の燃料排ガスリサイクルシステムに
おいて、上記燃料極から排出される燃料排ガス通路に分
岐手段が設けられ、この分岐手段で分岐された燃料排ガ
スの一方は改質容器及び／又は燃料極にリサイクルさ
れ、残余の燃料排ガスは酸化剤極にリサイクルされるこ
とを特徴とする。 上記分岐手段で分岐された燃料排ガスは燃料極にリ
サイルされると共に、この分岐手段から燃料極に至る燃
料排ガス通路には前記改質容器とは別の改質容器が設け
られていることを特徴とする。 上記分岐手段は、燃料排ガス中の炭酸ガスと炭酸ガ
ス以外の残余の燃料排ガスとに分離する第１の分離手段
を含み、この第１の分離手段によって分離された炭酸ガ
スは酸化剤極にリサイクルされ、炭酸ガス以外の燃料排
ガスは改質容器及び／又は燃料極にリサイクルされるこ
とを特徴とする。 上記第１の分離手段から改質容器及び／又は燃料極
に至る燃料排ガス通路には、燃料排ガス中の残メタンと
未反応水素とに分離する第２の分離手段が介在され、こ
の分離手段で分離された残メタンは改質容器にリサイク
ルされ、未反応水素は燃料極にリサイクルされることを
特徴とする。 上記燃料極から第１の分離手段に至る燃料排ガス通
路には改質触媒が設置され、第１の分離手段で分離され
た炭酸ガス以外の残余の燃料排ガスは直接燃料極にリサ
イクルされることを特徴とする。The present invention is characterized by the following in order to solve the above problems. An indirect internal reforming molten carbonate type in which a plurality of cells in which a fuel electrode and an oxidant electrode are arranged are laminated through a separator, and a reforming container is inserted in at least a part between the plurality of cells. In the fuel exhaust gas recycling system of a fuel cell, a branching means is provided in the fuel exhaust gas passage discharged from the fuel electrode, and one of the fuel exhaust gas branched by this branching means is recycled to the reforming container and / or the fuel electrode, The remaining fuel exhaust gas is characterized by being recycled to the oxidizer electrode. The fuel exhaust gas branched by the branching means is resold to the fuel electrode, and a reforming container different from the reforming container is provided in the fuel exhaust gas passage from the branching means to the fuel electrode. And The branching means includes a first separating means for separating carbon dioxide gas in the fuel exhaust gas and residual fuel exhaust gas other than carbon dioxide gas, and the carbon dioxide gas separated by the first separating means is recycled to the oxidizer electrode. The fuel exhaust gas other than carbon dioxide gas is recycled to the reforming container and / or the fuel electrode. A second separating means for separating residual methane and unreacted hydrogen in the fuel exhaust gas is interposed in the fuel exhaust gas passage extending from the first separating means to the reforming container and / or the fuel electrode. The separated residual methane is recycled to the reforming vessel, and the unreacted hydrogen is recycled to the fuel electrode. A reforming catalyst is installed in the fuel exhaust gas passage extending from the fuel electrode to the first separating means, and the remaining fuel exhaust gas other than carbon dioxide gas separated by the first separating means is directly recycled to the fuel electrode. Characterize.
【０００７】[0007]
【作用】上記の構成によれば、燃料排ガスを従来通り
酸化剤極にリサイクルすることができるのに加えて、新
たに改質容器及び／又は燃料極にもリサイクルすること
ができる。したがって、燃料排ガス中の残メタン等を、
改質容器等で水素を主体とするガスに改質することによ
り再利用できるので、改質効率、即ち発電効率が向上す
る。According to the above construction, the fuel exhaust gas can be recycled to the oxidizer electrode as in the conventional case, and also to the reforming container and / or the fuel electrode. Therefore, the residual methane etc. in the fuel exhaust gas
Since it can be reused by reforming it into a gas mainly containing hydrogen in a reforming container or the like, reforming efficiency, that is, power generation efficiency is improved.
【０００８】また、上記の構成によれば、第１の分離
手段によって分離された炭酸ガス以外の残余の燃料排ガ
ス（即ち、残メタン，未反応水素等）のみを、改質容器
及び／又は燃料極にリサイクルすることができるのでよ
り好ましい。更に、上記の構成によれば、第２の分離
手段によって分離された残メタンを改質容器に、未反応
水素を燃料極にそれぞれリサイクルすることができるの
で更に好ましい。Further, according to the above configuration, only the remaining fuel exhaust gas (that is, residual methane, unreacted hydrogen, etc.) other than carbon dioxide gas separated by the first separating means is reformed and / or fueled. It is more preferable because it can be extremely recycled. Further, according to the above configuration, the residual methane separated by the second separating means can be recycled to the reforming container and the unreacted hydrogen can be recycled to the fuel electrode, which is more preferable.
【０００９】上記の構成によれば、燃料極から第１の
分離手段に至る燃料排ガス通路に配置された改質触媒に
よって、燃料排ガス中の残メタンが略完全に改質される
ので、改質効率、即ち発電効率が向上する。According to the above construction, since the reforming catalyst arranged in the fuel exhaust gas passage extending from the fuel electrode to the first separating means reforms the residual methane in the fuel exhaust gas almost completely, Efficiency, that is, power generation efficiency is improved.
【００１０】[0010]
（第１実施例）図１は本発明の第１実施例に係る間接内
部改質溶融炭酸塩型燃料電池の配管系統の概念図であ
り、電解質１を挟んで燃料極２と酸化剤極３とを配置し
た単セル４を、セパレータ（図示せず）を介して複数積
層され、且つ、内部にニッケル系触媒５ａが充填された
改質容器５が数セル（例えば、５セル）毎に介在されて
成る電池本体６（この図では便宜上、単セル４のみを示
す）と，前記改質容器５に燃料ガス（メタンを主成分と
する天然ガスと，水蒸気との混合ガス）を供給する燃料
ガス供給管７と，前記改質容器５で水蒸気改質された水
素を主成分とする改質ガスを前記燃料極２に供給するリ
ターンマニホールド８と，前記燃料極２から排出される
燃料排ガス（残メタン，未反応水素，水蒸気，及び炭酸
ガスを主体とするガス）を燃料排ガス通路９に排出する
燃料排ガスマニホールド１０と，前記燃料排ガス通路９
から分岐して燃料排ガス燃焼器１１に燃料排ガスを供給
する燃料排ガス通路９ａと，同じく前記燃料排ガス通路
９から分岐して燃料ガス供給管７に燃料排ガスをリサイ
クルする燃料排ガス通路９ｂと，前記燃料排ガス燃焼器
１１に空気を供給する燃焼空気供給管１２と，前記燃焼
排ガス燃焼器１１から排出される空気（余剰酸素，及び
窒素）と炭酸ガスとを主成分とする酸化剤ガスを前記酸
化剤極３に供給する酸化剤ガス供給通路１３と，前記酸
化剤極３から排出される酸化剤排ガスを系外に排出する
酸化剤排ガス通路１４とから主に構成されている。(First Embodiment) FIG. 1 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a first embodiment of the present invention, in which a fuel electrode 2 and an oxidizer electrode 3 with an electrolyte 1 sandwiched therebetween. A plurality of single cells 4 in which the and are arranged are stacked via a separator (not shown), and a reforming vessel 5 having a nickel-based catalyst 5a filled therein is provided every several cells (for example, 5 cells). A fuel for supplying a fuel gas (a mixed gas of natural gas containing methane as a main component and steam) to the reforming container 5 and a battery body 6 (only a single cell 4 is shown in this figure for convenience). A gas supply pipe 7, a return manifold 8 for supplying the fuel electrode 2 with a reformed gas containing hydrogen as a main component, which has been subjected to steam reforming in the reforming container 5, and a fuel exhaust gas discharged from the fuel electrode 2 ( Gas mainly composed of residual methane, unreacted hydrogen, water vapor, and carbon dioxide ) And a fuel exhaust manifold 10 for discharging the fuel gas passage 9, the fuel gas passage 9
A fuel exhaust gas passage 9a branched from the fuel exhaust gas combustor 11 to supply the fuel exhaust gas to the fuel exhaust gas combustor 11, a fuel exhaust gas passage 9b branched from the fuel exhaust gas passage 9 to recycle the fuel exhaust gas to the fuel gas supply pipe 7, and the fuel. A combustion air supply pipe 12 for supplying air to the exhaust gas combustor 11, and an oxidant gas containing air (excess oxygen and nitrogen) and carbon dioxide gas, which are discharged from the combustion exhaust gas combustor 11, as main components. It is mainly composed of an oxidant gas supply passage 13 for supplying to the electrode 3 and an oxidant exhaust gas passage 14 for discharging the oxidant exhaust gas discharged from the oxidant electrode 3 to the outside of the system.
【００１１】上記単セル４は、炭酸リチウムと炭酸カリ
ウムとの共晶塩をγ−リチウムアルミネート（γ−Ｌｉ
ＡｌＯ2 ）を主成分とした多孔質セラミックス材中に保
持した電解質１を挟んで、ニッケルとアルミニウムとの
合金から成る燃料極２と，酸化ニッケル焼結体を主体と
する酸化剤極３とをそれぞれ配置した構造である。上記
セパレータは電子伝導性の材料で作られ、一方の面には
燃料ガスの通路となる溝が、他方の面には酸化剤の通路
となる溝がそれぞれ設けられている。各単セル４の燃料
極２は、前記セパレータによって、隣接する単セル４の
酸化剤極３と電気的に接続していて、これによって積層
した全ての単セル４が電気的に直列に接続することにな
る。In the single cell 4, the eutectic salt of lithium carbonate and potassium carbonate is γ-lithium aluminate (γ-Li).
A fuel electrode 2 made of an alloy of nickel and aluminum and an oxidizer electrode 3 mainly composed of a nickel oxide sintered body are sandwiched with an electrolyte 1 held in a porous ceramic material containing AlO 2 ) as a main component. It is a structure arranged respectively. The separator is made of an electronically conductive material, and has a groove serving as a fuel gas passage on one surface and a groove serving as an oxidant passage on the other surface. The fuel electrode 2 of each unit cell 4 is electrically connected to the oxidant electrode 3 of the adjacent unit cell 4 by the separator, and thus all the unit cells 4 stacked are electrically connected in series. It will be.
【００１２】ここで、上記の如く構成された間接内部改
質溶融炭酸塩型燃料電池のガスの流れについて説明す
る。先ず、燃料ガス供給管７を介して改質容器５に供給
された燃料ガス（メタンを主成分とする天然ガスと，水
蒸気との混合ガス）は、水素を主体とする改質ガスに水
蒸気改質される。尚、この改質ガス中には、改質容器５
で改質されなかった３〜４％程度の残メタンが含まれて
いる。この改質ガスは、リターンマニホールド８を介し
て燃料極２に供給され、改質ガス中の水素は電池反応に
利用される。一方、改質ガス中の残メタンはそのまま燃
料排ガスとして燃料排ガスマニホールド１０を介して、
燃料排ガス通路９に排出される。尚、燃料排ガスには、
前記残メタンと，燃料極２での電池反応に寄与しなかっ
た未反応水素と，電池反応で生成した水蒸気及び炭酸ガ
スが含まれている。前記燃料排ガス通路９から分岐して
設けられた燃料排ガス通路９ａを流れる燃料排ガス中の
残メタン，及び未反応水素は、前記燃料排ガス燃焼器１
１によって酸化される。その後、酸化剤ガス供給通路１
３を介して、空気（余剰酸素，及び窒素）と炭酸ガスと
を主成分とする酸化剤ガスが前記酸化剤極３に供給さ
れ、電池反応に使用された後、酸化剤排ガス通路１４を
介して系外に排出される。The gas flow of the indirect internal reforming molten carbonate fuel cell constructed as described above will now be described. First, the fuel gas (mixed gas of natural gas containing methane as a main component and steam) supplied to the reforming container 5 through the fuel gas supply pipe 7 is converted into steam containing a reforming gas containing hydrogen as a main component. Be quality. The reforming container 5 is contained in this reformed gas.
It contains about 3-4% residual methane that was not reformed. This reformed gas is supplied to the fuel electrode 2 via the return manifold 8, and hydrogen in the reformed gas is used for the cell reaction. On the other hand, the residual methane in the reformed gas is directly used as fuel exhaust gas via the fuel exhaust gas manifold 10,
The fuel is discharged into the fuel exhaust gas passage 9. In addition, in the fuel exhaust gas,
The residual methane, unreacted hydrogen that did not contribute to the cell reaction at the fuel electrode 2, and water vapor and carbon dioxide gas generated in the cell reaction are included. Residual methane and unreacted hydrogen in the fuel exhaust gas flowing through the fuel exhaust gas passage 9a branched from the fuel exhaust gas passage 9 are removed by the fuel exhaust gas combustor 1
It is oxidized by 1. Then, the oxidant gas supply passage 1
The oxidant gas containing air (excess oxygen and nitrogen) and carbon dioxide gas as main components is supplied to the oxidant electrode 3 via 3 and used for the battery reaction, and then via the oxidant exhaust gas passage 14. Is discharged outside the system.
【００１３】一方、燃料排ガス通路９から分離した設け
られた燃料排ガス通路９ｂを流れる燃料排ガスは、燃料
ガス供給管７にリサイクルされる。したがって、燃料排
ガス中の残メタン等を改質容器５で再び改質した後、燃
料極２に供給することができるので、改質効率，即ち発
電効率が向上する。 （第２実施例）図２は本発明の第２実施例に係る間接内
部改質溶融炭酸塩型燃料電池の配管系統の概念図であ
る。尚、上記第１実施例と同様の機能を有する構成部分
については、上記第１実施例と同様の番号を付して説明
を省略する。On the other hand, the fuel exhaust gas flowing through the fuel exhaust gas passage 9b provided separately from the fuel exhaust gas passage 9 is recycled to the fuel gas supply pipe 7. Therefore, the residual methane and the like in the fuel exhaust gas can be reformed in the reforming vessel 5 and then supplied to the fuel electrode 2, so that the reforming efficiency, that is, the power generation efficiency is improved. (Second Embodiment) FIG. 2 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a second embodiment of the present invention. The components having the same functions as those in the first embodiment are designated by the same reference numerals as those in the first embodiment and the description thereof is omitted.
【００１４】この間接内部改質溶融炭酸塩型燃料電池
は、燃料排ガス通路９ｂを介してリサイクルされた燃料
排ガス中の残メタン等を改質容器５０で改質した後、リ
ターンマニホールド８ａを介して、再び燃料極２に供給
する他は、上記第１実施例と同様の構成である。上記改
質容器５０は前記改質容器５と同様の構成であるが、燃
料排ガス中の残メタンのみを改質するだけで、燃料ガス
を改質する必要がないので、改質容器５の約１／１０の
量の改質触媒が設置されている。In this indirect internal reforming molten carbonate fuel cell, the residual methane and the like in the fuel exhaust gas recycled through the fuel exhaust gas passage 9b is reformed in the reforming container 50 and then through the return manifold 8a. The configuration is the same as that of the first embodiment except that the fuel is again supplied to the fuel electrode 2. The reforming container 50 has the same structure as the reforming container 5, but only the residual methane in the fuel exhaust gas is reformed, and it is not necessary to reform the fuel gas. 1/10 amount of reforming catalyst is installed.
【００１５】（第３実施例）図３は本発明の第３実施例
に係る間接内部改質溶融炭酸塩型燃料電池の配管系統の
概念図である。尚、上記第１実施例と同様の機能を有す
る構成部分については、上記第１実施例と同様の番号を
付して説明を省略する。燃料極２より排出された燃料排
ガスは、燃料排ガスマニホールド１０を介して、燃料排
ガス通路９に排出される。前記燃料排ガス中の水蒸気
は、前記燃料排ガス通路９を流れる間に冷却除去され、
その他の燃料排ガスは炭酸ガス分離器１５によって、炭
酸ガスと，その他の燃料排ガス（即ち、残メタンと未反
応水素）とに分離される。前記炭酸ガス分離器１５によ
って分離された燃料排ガス中の炭酸ガスは、燃料排ガス
通路９ａを流れる間に、燃焼空気供給管１２から供給さ
れる空気と共に、酸化剤ガスとして酸化剤極３に供給さ
れる。一方、前記炭酸ガス分離器１５によって分離され
た燃料排ガス中の残メタン，及び未反応水素は燃料排ガ
ス通路９ｂを通って燃料ガス供給管７にリサイクルされ
る。(Third Embodiment) FIG. 3 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a third embodiment of the present invention. The components having the same functions as those in the first embodiment are designated by the same reference numerals as those in the first embodiment and the description thereof is omitted. The fuel exhaust gas discharged from the fuel electrode 2 is discharged into the fuel exhaust gas passage 9 via the fuel exhaust gas manifold 10. Water vapor in the fuel exhaust gas is cooled and removed while flowing through the fuel exhaust gas passage 9,
The other fuel exhaust gas is separated by the carbon dioxide separator 15 into carbon dioxide gas and other fuel exhaust gas (that is, residual methane and unreacted hydrogen). The carbon dioxide gas in the fuel exhaust gas separated by the carbon dioxide separator 15 is supplied to the oxidizer electrode 3 as an oxidizer gas together with the air supplied from the combustion air supply pipe 12 while flowing through the fuel exhaust gas passage 9a. It On the other hand, the residual methane and unreacted hydrogen in the fuel exhaust gas separated by the carbon dioxide separator 15 are recycled to the fuel gas supply pipe 7 through the fuel exhaust gas passage 9b.
【００１６】上記炭酸ガス分離器１５は、ガスの圧力を
変化させて吸着と脱着とを繰り返すことにより、目的の
ガスを分離精製することができるＰＳＡ（Pressure Swi
ng Adsorption)方式を採用している。上記第３実施例に
よれば、燃料排ガス中の燃料成分（残メタン，及び未反
応水素）のみを改質容器５にリサイクルすることができ
るので、燃料ガス中の水素分圧を高く保つことができ
る。したがって、高い電池特性を得ることができる。The carbon dioxide gas separator 15 is a PSA (Pressure Swi) that can separate and purify a target gas by changing the gas pressure and repeating adsorption and desorption.
ng Adsorption) method is adopted. According to the third embodiment described above, since only the fuel components (residual methane and unreacted hydrogen) in the fuel exhaust gas can be recycled to the reforming vessel 5, the hydrogen partial pressure in the fuel gas can be kept high. it can. Therefore, high battery characteristics can be obtained.
【００１７】また、酸化剤極３には燃料排ガス中の未反
応水素が供給されないため、この未反応水素を燃焼する
ための燃料排ガス燃焼器１１が不要である。したがっ
て、燃焼空気供給管１２から供給された空気を、未反応
水素の燃焼に利用する必要がないので、酸素濃度の高い
酸化剤ガスを供給することができる。 （第４実施例）図４は本発明の第４実施例に係る間接内
部改質溶融炭酸塩型燃料電池の配管系統の概念図であ
る。尚、上記第３実施例と同様の機能を有する構成部分
については、上記第３実施例と同様の番号を付して説明
を省略する。Further, since the unreacted hydrogen in the fuel exhaust gas is not supplied to the oxidizer electrode 3, the fuel exhaust gas combustor 11 for burning the unreacted hydrogen is unnecessary. Therefore, it is not necessary to use the air supplied from the combustion air supply pipe 12 for the combustion of unreacted hydrogen, so that the oxidant gas having a high oxygen concentration can be supplied. (Fourth Embodiment) FIG. 4 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a fourth embodiment of the present invention. The constituent parts having the same functions as those in the third embodiment are designated by the same reference numerals as those in the third embodiment, and the description thereof will be omitted.
【００１８】この間接内部改質溶融炭酸塩型燃料電池
は、燃料排ガス通路９ｃを流れる燃料排ガス中の残メタ
ン，及び未反応水素が、メタン水素分離器１６によって
残メタンと未反応水素とに分離され、残メタンは燃料排
ガス通路９ｂを介して燃料ガス供給管７に、未反応水素
は燃料排ガス通路９ｄ，リターンマニホールド８を介し
て燃料極２にそれぞれリサイクルされる他は、上記第３
実施例と同様の構成である。In this indirect internal reforming molten carbonate fuel cell, the residual methane and unreacted hydrogen in the fuel exhaust gas flowing through the fuel exhaust gas passage 9c are separated by the methane hydrogen separator 16 into residual methane and unreacted hydrogen. The remaining methane is recycled to the fuel gas supply pipe 7 via the fuel exhaust gas passage 9b, and the unreacted hydrogen is recycled to the fuel electrode 2 via the fuel exhaust gas passage 9d and the return manifold 8, respectively.
The configuration is similar to that of the embodiment.
【００１９】上記メタン水素分離装置１６は、膜分離器
を使用しているため、透過速度の速い未反応水素と，透
過速度の遅い残メタンとに分離することができる。上記
第４実施例によれば、改質反応の反応生成物である未反
応水素は、燃料極２にのみリサイクルされ、改質容器９
にリサイクルされることがない。したがって、改質反応
がスムーズに行われる。Since the methane-hydrogen separator 16 uses a membrane separator, it can separate unreacted hydrogen having a high permeation rate and residual methane having a low permeation rate. According to the fourth embodiment, unreacted hydrogen, which is a reaction product of the reforming reaction, is recycled only to the fuel electrode 2, and the reforming container 9
Never recycled. Therefore, the reforming reaction is smoothly performed.
【００２０】（第５実施例）図５は本発明の第５実施例
に係る間接内部改質溶融炭酸塩型燃料電池の配管系統の
概念図である。尚、上記第１実施例と同様の機能を有す
る構成部分については、上記第１実施例と同様の番号を
付して説明を省略する。この間接内部改質溶融炭酸塩型
燃料電池は、電池本体６のリターンマニホールド８が取
り付けられている反対側の側面に取り付けられている燃
料排ガスマニホールド１０に改質触媒１０ａが設置され
ているので、燃料極２から排出された燃料排ガス中の残
メタンは略完全に改質される。したがって、燃料排ガス
通路９ｄを流れる燃料排ガス中には未反応水素のみが燃
料極２にリサイクルされる他は、上記第４実施例と同様
の構成である。(Fifth Embodiment) FIG. 5 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a fifth embodiment of the present invention. The components having the same functions as those in the first embodiment are designated by the same reference numerals as those in the first embodiment and the description thereof is omitted. In this indirect internal reforming molten carbonate fuel cell, the reforming catalyst 10a is installed in the fuel exhaust gas manifold 10 attached to the side surface of the cell body 6 opposite to the side where the return manifold 8 is attached. The residual methane in the fuel exhaust gas discharged from the fuel electrode 2 is almost completely reformed. Therefore, the structure is the same as that of the fourth embodiment except that only unreacted hydrogen is recycled to the fuel electrode 2 in the fuel exhaust gas flowing through the fuel exhaust gas passage 9d.
【００２１】（第６実施例）図６は本発明の第６実施例
に係る間接内部改質溶融炭酸塩型燃料電池の配管系統の
概念図である。尚、上記第５実施例と同様の機能を有す
る構成部分については、上記第５実施例と同様の番号を
付して説明を省略する。酸化剤極３から排出された酸化
剤排ガスは、酸化剤排ガス通路１４ａに設けられた熱交
換器（図示せず）により冷却された後、ガス分離器１７
に供給される。このガス分離器１７は、中空糸タイプの
透過膜を使用しているため、透過速度の遅い窒素は、酸
化剤排ガス通路１４ｂを介して系外に排出される。一
方、透過速度の速い酸素，及び炭酸ガスは、酸化剤排ガ
スリサイクル通路１８ａを通って、酸化剤排ガス循環ブ
ロア１９に入り、酸化剤排ガスリサイクル通路１８ｂを
介して酸化剤ガス供給通路１３を通って、酸化剤極３に
リサイクルされる。(Sixth Embodiment) FIG. 6 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a sixth embodiment of the present invention. The components having the same functions as those in the fifth embodiment are designated by the same reference numerals as those in the fifth embodiment and the description thereof will be omitted. The oxidant exhaust gas discharged from the oxidant electrode 3 is cooled by a heat exchanger (not shown) provided in the oxidant exhaust gas passage 14a, and then the gas separator 17
Is supplied to. Since this gas separator 17 uses a hollow fiber type permeable membrane, nitrogen having a slow permeation rate is discharged to the outside of the system through the oxidant exhaust gas passage 14b. On the other hand, oxygen and carbon dioxide having a high permeation rate enter the oxidant exhaust gas circulation blower 19 through the oxidant exhaust gas recycle passage 18a, pass through the oxidant exhaust gas recycle passage 18b, and pass through the oxidant gas supply passage 13. , The oxidizer electrode 3 is recycled.
【００２２】上記第６実施例によれば、酸化剤反応に必
要な酸素，及び炭酸ガスのみをリサイクルすることがで
きるので、酸化剤ガス中の酸素分圧および炭酸ガス分圧
を高くすることができる。したがって、溶融炭酸塩型燃
料電池の特性向上、発電効率の向上を図ることができ
る。 〔その他の事項〕 上記第３〜６実施例においては、炭酸ガス分離器１
５として分離機能の優れたＰＳＡ方式を用いたが、本発
明は何らこれに限定されるものではなく、例えば、膜分
離方式を用いることも勿論可能である。 上記第５実施例においては、燃料排ガスマニホール
ド１０に改質触媒１０ａを設置したが、例えば、燃料排
ガス通路９に設けることも可能である。 上記第６実施例では、ガス分離器１７として中空糸
タイプ透過膜を使用したが、本発明は何らこれに限定さ
れるものではなく、例えば、ＰＳＡ等を使用することも
可能である。 本発明は、上記第１実施例〜第６実施例に何ら限定
されるものではなく、これらの実施例を組み合わせて構
成することも勿論可能である。According to the sixth embodiment, since only oxygen and carbon dioxide gas necessary for the oxidant reaction can be recycled, the oxygen partial pressure and carbon dioxide gas partial pressure in the oxidant gas can be increased. it can. Therefore, the characteristics of the molten carbonate fuel cell and the power generation efficiency can be improved. [Other Matters] In the above third to sixth embodiments, the carbon dioxide gas separator 1 is used.
Although the PSA method having an excellent separation function was used as 5, the present invention is not limited to this, and it is of course possible to use a membrane separation method, for example. Although the reforming catalyst 10a is installed in the fuel exhaust gas manifold 10 in the fifth embodiment, it may be installed in the fuel exhaust gas passage 9, for example. Although the hollow fiber type permeable membrane is used as the gas separator 17 in the sixth embodiment, the present invention is not limited to this, and PSA or the like may be used, for example. The present invention is not limited to the first to sixth embodiments described above, and it is of course possible to combine these embodiments.
【００２３】[0023]
【発明の効果】上記の構成によれば、燃料排ガスを従
来通り酸化剤極にリサイクルすることができるのに加え
て、新たに改質容器及び／又は燃料極にもリサイクルす
ることができる。したがって、燃料排ガス中の残メタン
等を、改質容器等で水素を主体とするガスに改質するこ
とにより再利用できるので、改質効率、即ち発電効率が
向上する。According to the above construction, the fuel exhaust gas can be recycled to the oxidizer electrode as in the conventional manner, and can also be newly recycled to the reforming container and / or the fuel electrode. Therefore, the residual methane or the like in the fuel exhaust gas can be reused by reforming it into a gas mainly containing hydrogen in a reforming container or the like, so that the reforming efficiency, that is, the power generation efficiency is improved.
【００２４】また、上記の構成によれば、第１の分離
手段によって分離された炭酸ガス以外の残余の燃料排ガ
ス（即ち、残メタン，未反応水素等）のみを、改質容器
及び／又は燃料極にリサイクルすることができるのでよ
り好ましい。更に、上記の構成によれば、第２の分離
手段によって分離された残メタンを改質容器に、未反応
水素を燃料極にそれぞれリサイクルすることができるの
で更に好ましい。Further, according to the above construction, only the remaining fuel exhaust gas other than carbon dioxide gas separated by the first separating means (ie, residual methane, unreacted hydrogen, etc.) is reformed and / or fueled. It is more preferable because it can be extremely recycled. Further, according to the above configuration, the residual methane separated by the second separating means can be recycled to the reforming container and the unreacted hydrogen can be recycled to the fuel electrode, which is more preferable.
【００２５】上記の構成によれば、燃料極から第１の
分離手段に至る燃料排ガス通路に配置された改質触媒に
よって、燃料排ガス中の残メタンが略完全に改質される
ので、改質効率、即ち発電効率が向上する。According to the above construction, the reforming catalyst arranged in the fuel exhaust gas passage extending from the fuel electrode to the first separating means reforms the residual methane in the fuel exhaust gas almost completely, so that the reforming is performed. Efficiency, that is, power generation efficiency is improved.
【図１】本発明の第１実施例に係る間接内部改質溶融炭
酸塩型燃料電池の配管系統の概念図である。FIG. 1 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a first embodiment of the present invention.
【図２】本発明の第２実施例に係る間接内部改質溶融炭
酸塩型燃料電池の配管系統の概念図である。FIG. 2 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a second embodiment of the present invention.
【図３】本発明の第３実施例に係る間接内部改質溶融炭
酸塩型燃料電池の配管系統の概念図である。FIG. 3 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a third embodiment of the present invention.
【図４】本発明の第４実施例に係る間接内部改質溶融炭
酸塩型燃料電池の配管系統の概念図である。FIG. 4 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a fourth embodiment of the present invention.
【図５】本発明の第５実施例に係る間接内部改質溶融炭
酸塩型燃料電池の配管系統の概念図である。FIG. 5 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a fifth embodiment of the present invention.
【図６】本発明の第６実施例に係る間接内部改質溶融炭
酸塩型燃料電池の配管系統の概念図である。FIG. 6 is a conceptual diagram of a piping system of an indirect internal reforming molten carbonate fuel cell according to a sixth embodiment of the present invention.
【図７】従来の直接内部改質溶融炭酸塩型燃料電池の配
管系統配管系統の概念図である。FIG. 7 is a conceptual diagram of a piping system of a conventional direct internal reforming molten carbonate fuel cell.
【図８】従来の間接内部改質溶融炭酸塩型燃料電池の配
管系統配管系統の概念図である。FIG. 8 is a conceptual diagram of a piping system of a conventional indirect internal reforming molten carbonate fuel cell.
１ 電解質 ２ 燃料極 ３ 酸化剤極 ４ セル ５ 改質容器 1 Electrolyte 2 Fuel electrode 3 Oxidizer electrode 4 Cell 5 Reforming container
Claims (5)
を、セパレータを介して複数積層させ、且つ、前記複数
のセル間の少なくとも１部に改質容器を介挿させて成る
間接内部改質溶融炭酸塩型燃料電池の燃料排ガスリサイ
クルシステムにおいて、 上記燃料極から排出される燃料排ガス通路に分岐手段が
設けられ、この分岐手段で分岐された燃料排ガスの一方
は改質容器及び／又は燃料極にリサイクルされ、残余の
燃料排ガスは酸化剤極にリサイクルされることを特徴と
する間接内部改質溶融炭酸塩型燃料電池の燃料排ガスリ
サイクルシステム。1. An indirect internal reforming comprising a plurality of cells in which a fuel electrode and an oxidant electrode are arranged, with a separator interposed between the cells, and a reforming container inserted in at least a part of the plurality of cells. In a fuel exhaust gas recycling system for a high-melting carbonate fuel cell, a branch means is provided in a fuel exhaust path discharged from the fuel electrode, and one of the fuel exhaust branches by the branch means is a reforming container and / or a fuel. A fuel exhaust gas recycle system for an indirect internal reforming molten carbonate fuel cell, which is characterized in that it is recycled to the pole and the remaining fuel exhaust gas is recycled to the oxidizer electrode.
は燃料極にリサイルされると共に、この分岐手段から燃
料極に至る燃料排ガス通路には前記改質容器とは別の改
質容器が設けられていることを特徴とする請求項１記載
の間接内部改質溶融炭酸塩型燃料電池の燃料排ガスリサ
イクルシステム。2. The fuel exhaust gas branched by the branching means is re-sold to the fuel electrode, and a reforming vessel different from the reforming vessel is provided in the fuel exhaust gas passage extending from the branching means to the fuel electrode. The fuel exhaust gas recycle system of the indirect internal reforming molten carbonate fuel cell according to claim 1, wherein
ガスと炭酸ガス以外の残余の燃料排ガスとに分離する第
１の分離手段を含み、この第１の分離手段によって分離
された炭酸ガスは酸化剤極にリサイクルされ、炭酸ガス
以外の燃料排ガスは改質容器及び／又は燃料極にリサイ
クルされることを特徴とする請求項１記載の間接内部改
質溶融炭酸塩型燃料電池の燃料排ガスリサイクルシステ
ム。3. The branching means includes a first separating means for separating carbon dioxide gas in the fuel exhaust gas and residual fuel exhaust gas other than carbon dioxide gas, and the carbon dioxide gas separated by the first separating means is The fuel exhaust gas recycling of the indirect internal reforming molten carbonate fuel cell according to claim 1, wherein the fuel exhaust gas other than carbon dioxide gas is recycled to the oxidizing agent electrode and is recycled to the reforming container and / or the fuel electrode. system.
／又は燃料極に至る燃料排ガス通路には、燃料排ガス中
の残メタンと未反応水素とに分離する第２の分離手段が
介在され、この分離手段で分離された残メタンは改質容
器にリサイクルされ、未反応水素は燃料極にリサイクル
されることを特徴とする請求項３記載の間接内部改質溶
融炭酸塩型燃料電池の燃料排ガスリサイクルシステム。4. A second separating means for separating residual methane and unreacted hydrogen in the fuel exhaust gas is provided in the fuel exhaust gas passage extending from the first separation means to the reforming container and / or the fuel electrode. The fuel of the indirect internal reforming molten carbonate fuel cell according to claim 3, wherein the residual methane separated by the separating means is recycled to the reforming container, and unreacted hydrogen is recycled to the fuel electrode. Exhaust gas recycling system.
燃料排ガス通路には改質触媒が設置され、第１の分離手
段で分離された炭酸ガス以外の残余の燃料排ガスは直接
燃料極にリサイクルされることを特徴とする請求項３記
載の間接内部改質溶融炭酸塩型燃料電池の燃料排ガスリ
サイクルシステム。5. A reforming catalyst is installed in a fuel exhaust gas passage extending from the fuel electrode to the first separating means, and the remaining fuel exhaust gas other than carbon dioxide gas separated by the first separating means is directly delivered to the fuel electrode. The fuel exhaust gas recycling system of the indirect internal reforming molten carbonate fuel cell according to claim 3, which is recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4171101A JPH0613094A (en) | 1992-06-29 | 1992-06-29 | Fuel exhaust gas recycle system for indirect internal reformed molten carbonate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4171101A JPH0613094A (en) | 1992-06-29 | 1992-06-29 | Fuel exhaust gas recycle system for indirect internal reformed molten carbonate fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0613094A true JPH0613094A (en) | 1994-01-21 |
Family
ID=15917002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4171101A Pending JPH0613094A (en) | 1992-06-29 | 1992-06-29 | Fuel exhaust gas recycle system for indirect internal reformed molten carbonate fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0613094A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2344109A (en) * | 1998-11-30 | 2000-05-31 | Masco Corp | Multi-layer coated article |
| JP2006500758A (en) * | 2002-09-27 | 2006-01-05 | クエストエアー テクノロジーズ インコーポレイテッド | Improved solid oxide fuel cell system |
| ITMI20091246A1 (en) * | 2009-07-14 | 2011-01-15 | Ansaldo Fuel Cells Spa | APPARATUS AND METHOD FOR THERMAL MANAGEMENT OF MCFC PILE |
| KR101324112B1 (en) * | 2011-05-31 | 2013-10-31 | 삼성중공업 주식회사 | Fuel cell system |
-
1992
- 1992-06-29 JP JP4171101A patent/JPH0613094A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2344109A (en) * | 1998-11-30 | 2000-05-31 | Masco Corp | Multi-layer coated article |
| GB2344109B (en) * | 1998-11-30 | 2003-06-04 | Masco Corp | Coated article |
| JP2006500758A (en) * | 2002-09-27 | 2006-01-05 | クエストエアー テクノロジーズ インコーポレイテッド | Improved solid oxide fuel cell system |
| ITMI20091246A1 (en) * | 2009-07-14 | 2011-01-15 | Ansaldo Fuel Cells Spa | APPARATUS AND METHOD FOR THERMAL MANAGEMENT OF MCFC PILE |
| KR101324112B1 (en) * | 2011-05-31 | 2013-10-31 | 삼성중공업 주식회사 | Fuel cell system |
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