JPS62219473A - Fused carbonate fuel cell system - Google Patents
Fused carbonate fuel cell systemInfo
- Publication number
- JPS62219473A JPS62219473A JP61062441A JP6244186A JPS62219473A JP S62219473 A JPS62219473 A JP S62219473A JP 61062441 A JP61062441 A JP 61062441A JP 6244186 A JP6244186 A JP 6244186A JP S62219473 A JPS62219473 A JP S62219473A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- remover
- gas
- fuel
- electrolyte
- 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
- 239000000446 fuel Substances 0.000 title claims abstract description 32
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 21
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052815 sulfur oxide Inorganic materials 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 238000002407 reforming Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 6
- 239000008188 pellet Substances 0.000 abstract description 5
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract 2
- 230000007850 degeneration Effects 0.000 abstract 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 abstract 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 7
- 229960004424 carbon dioxide Drugs 0.000 description 6
- 239000002737 fuel gas Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 244000061354 Manilkara achras Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NCAPIWDYXGDHIK-UHFFFAOYSA-L [Li+].[K+].OC([O-])=O.OC([O-])=O Chemical compound [Li+].[K+].OC([O-])=O.OC([O-])=O NCAPIWDYXGDHIK-UHFFFAOYSA-L 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
-
- 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
Landscapes
- 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)
- Fuel Cell (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）竜業上の利用分計
本発明は溶ＦＩＩ！ｉ炭酸塩型燃料電池システムに関す
るものである。[Detailed Description of the Invention] (a) Commercial utilization meter The present invention is Molten FII! This invention relates to a carbonate fuel cell system.
（ロ）従来の技術
溶融炭酸塩燃料電池においては燃料として改質ガス中の
水素を、酸化剤として空気中の酸素を夫々用い、次の反
応を行わせる。(b) Prior Art In a molten carbonate fuel cell, hydrogen in a reformed gas is used as a fuel and oxygen in the air is used as an oxidizing agent to carry out the following reaction.
Ｈ２＋鴨０２ →Ｈ２０
す々わち燃料極側では水素が電解質の００５ との反
応により消費されて水と炭啼ガスを生じる。H2+Duck02 →H20 That is, on the fuel electrode side, hydrogen is consumed by reaction with 005 of the electrolyte to produce water and carbon gas.
一方酸素極では酸素と炭酸ガスが反応して消費されＣＯ
ニーを生じる。この電池反応においては燃料極側で生成
した炭素ガスを酸素極へ供給する必要がある。On the other hand, at the oxygen electrode, oxygen and carbon dioxide react and are consumed, resulting in CO
Causes knee. In this cell reaction, it is necessary to supply carbon gas generated on the fuel electrode side to the oxygen electrode.
しかしかから実際の電池システムにおいては燃料極側排
出ガス中に未反応の水素及び−酸化炭素が残存している
ため、一旦燃焼器で燃焼酸化させガスが酸素極へ供給さ
れる。However, in an actual battery system, unreacted hydrogen and carbon oxide remain in the exhaust gas on the fuel electrode side, so the gas is once combusted and oxidized in the combustor and then supplied to the oxygen electrode.
さて溶融炭酸塩燃料電池の燃料ガスとしては都市ガス等
の改質ガスあるいは石炭ガス化ガス等が用いられるが、
これらガスには電池てとって有害な硫黄化合物ガスが含
まれている。この丸め電池に導入する前に脱硫器を通し
ているが、硫黄化合物を完全に除去することは極めて困
帷であり、数ＰＰｍ〜数百ｐｐｍの硫黄化合物主として
硫化水素（Ｈ２８）が残存したま＼燃料ｗＬＫ導入され
る。Now, reformed gas such as city gas or coal gasification gas is used as the fuel gas for molten carbonate fuel cells.
These gases contain sulfur compound gases that are harmful to batteries. Although the battery is passed through a desulfurizer before being introduced into the rounded battery, it is extremely difficult to completely remove sulfur compounds, and several ppm to several hundred ppm of sulfur compounds, mainly hydrogen sulfide (H28), remain in the fuel. wLK is introduced.
このＨ２Ｓは溶融炭酸塩電解質を汚染することば比較的
少々いが、燃料葎排ガスを燃焼酸化させた際に二酸化硫
黄（Ｓ０２）や三酸化硫黄（８０，）などの硫黄酸化物
を生成し、これが空気と共に酸素極へ供給された場合電
解質である炭酸塩と置換し硫酸塩となって電解質中に溶
は込み蓄積される。この結果電極反応速度の低下・伝導
度の低下等が起され、電池特性及び寿命が劣化するとい
う問題があった。Although this H2S contaminates the molten carbonate electrolyte, it is relatively rare to say that it produces sulfur oxides such as sulfur dioxide (S02) and sulfur trioxide (80,) when fuel seedling exhaust gas is combusted and oxidized. When it is supplied to the oxygen electrode together with air, it replaces carbonate, which is an electrolyte, and becomes sulfate, which is dissolved and accumulated in the electrolyte. As a result, a decrease in electrode reaction rate, a decrease in conductivity, etc. occur, resulting in a problem of deterioration of battery characteristics and life.
ｅう 発明が解決しようとする問題点
この発明は前記１染に起因する溶融炭酸塩電解質の変質
を防止して電池特性及び寿命を改善する ゛ものである
。Problems to be Solved by the Invention The present invention is intended to improve battery characteristics and life by preventing the deterioration of the molten carbonate electrolyte caused by the above-mentioned dyeing.
に）問題点を解決する九めの手段
この発明は燃料極排出ガスを燃焼器で酸化させた後空気
と共に酸素極に供給するものにおいて、前記燃焼器の下
流に前記酸化後のガス中に存在する硫黄酸化物（８０２
，５ｏｓ）を溶融炭酸塩により捌促せしめる除去器を設
けたものである。Ninth Means for Solving the Problem This invention provides a fuel electrode exhaust gas that is oxidized in a combustor and then supplied to an oxygen electrode together with air, in which a fuel electrode is present in the oxidized gas downstream of the combustor. sulfur oxide (802
.
（ホ）作 用
この発明によれば燃料極の排出ガス中に含まれる硫黄化
合物を燃焼酸化させた際に生じる有害な硫黄酸化物が除
去されるため、電解質を硫酸塩に変質して蓄積されるこ
とがない。従って原燃料に対する脱硫器の精覆度をあげ
ることなく使用可能となる。(E) Function According to this invention, harmful sulfur oxides generated when sulfur compounds contained in the exhaust gas of the fuel electrode are oxidized by combustion are removed. Never. Therefore, the desulfurizer can be used without increasing the degree of refinement of the raw fuel.
（へ）実施例
第１［喝は本発明による溶融炭酸塩燃料電池のシステム
フロー図である。都市ガスなどの原燃料＋１１炭素、炭
酸ガスなどを含む水素リッチガスて改質され、燃料ガス
として燃料極（ト）に導入される。尚原燃料が石炭の場
合燃料処理装置（４）で石炭ガス化されて後脱硫器（２
）を通り、燃料極（町に導入される。(f) Example 1 [Figure 1] is a system flow diagram of a molten carbonate fuel cell according to the present invention. Raw fuel such as city gas + hydrogen-rich gas containing 11 carbon and carbon dioxide gas is reformed and introduced into the fuel electrode (G) as fuel gas. If the raw fuel is coal, it is gasified in the fuel processing device (4) and then sent to the desulfurizer (2).
) through the fuel electrode (introduced into town).
燃料極（Ｎ）からの排出ガスは、燃焼器（５）で酸化さ
れ、ガス中ば残存している水素及び−酸化炭素が各夕水
及び炭酸ガスに変換される。このとき燃料極排出ガス中
の微量の硫黄化合物（Ｈ２Ｂ）Ｆｉ二酸化硫黄（Ｅｉ０
２）、三酸化硫黄（ＳＯＳ＞のような硫黄酸化物とｈる
。これらθ０！やｅｏｓけ、常温下では水と反応してＨ
２日０４になり易いが、燃焼器（５）の温度は７００℃
以上であるのでＨ２ＢＯ３となるとと々く、８０ｚや８
０ｇのガス状で存在し、これらが空気及び炭酸ガスと共
に酸素極（ト）に供給されると電解質に）の＠融炭酸塩
を序々に硫酸塩に変質して蓄積されることになる。The exhaust gas from the fuel electrode (N) is oxidized in the combustor (5), and the remaining hydrogen and carbon oxides in the gas are converted into water and carbon dioxide. At this time, trace amounts of sulfur compounds (H2B), Fi, sulfur dioxide (Ei0
2) and sulfur oxides such as sulfur trioxide (SOS).
It tends to be 04 on the 2nd, but the temperature of the combustor (5) is 700℃
Because of the above, when it comes to H2BO3, 80z and 8
It exists in a gaseous state of 0 g, and when these are supplied to the oxygen electrode (g) together with air and carbon dioxide gas, the molten carbonate (in the electrolyte) gradually transforms into sulfate and accumulates.
本発明はこの特性を利用し燃焼器（６）の下流側に設置
した硫黄酸化物除去器（６）を通過する間にＢｏ２や８
０３が器内の溶嘔炭Ｑ［Ｋより捕捉される。The present invention makes use of this characteristic to make Bo2 and 8
03 is captured from the dissolved charcoal Q[K in the vessel.
この除去器１６＋内の溶融炭酸塩は電池性解質と同様に
炭酸リチウム−炭酸カリウム混合塩Ｃモル比６２：３Ｂ
）を６０を量慢及び炭酸塩保持材としてγ−アルミン費
リチウム（γ−Ｌｉ ＡｚＯｚ）を４０重４！ｆ％混合
した粉末をホットプレスしたペレット（））として用い
る。これらペレット（７）は第２図及び筆３［４に示す
ように流通ガスとの接触面積が大きくなるよう配置され
る。The molten carbonate in this remover 16+ has a lithium carbonate-potassium carbonate mixed salt C molar ratio of 62:3B, similar to the battery electrolyte.
) to 60% and carbonate retaining material, γ-aluminous lithium (γ-Li AzOz) to 40% weight 4! The powder mixed with f% is used as hot-pressed pellets ()). These pellets (7) are arranged so that the contact area with the circulating gas is large, as shown in FIG. 2 and the brush 3 [4].
溶虫炭酸４、篭と三酸化硫黄あるいは三酸化硫黄との平
衡は、下式に表わされるように非常に右にかたよってお
り、二酸化硫黄あるいは三酸化硫黄を置換により完全に
除去することができる。The equilibrium between soluble carbonic acid 4 and sulfur trioxide or sulfur trioxide is extremely shifted to the right as shown in the equation below, and sulfur dioxide or sulfur trioxide can be completely removed by substitution. .
９ｏｘ 十Ｍ２Ｃ０ｇ ＝ Ｍｚ８０ｓ ＋ ＣＯ２
８０ｓ ＋ Ｍ２Ｃ０Ｓ ＝Ｍ２８０４ ＋Ｃ０２（
ここでＭはリチウム・カリウム等の金属である）
このようにして硫黄酸化物が除去さねぇ排ガス（ＣＯ２
）は、新岬空気（８）と混合して嘴素＠（ト）に供給さ
れる。9ox 10M2C0g = Mz80s + CO2
80s + M2C0S = M2804 +C02(
Here, M is a metal such as lithium or potassium) In this way, sulfur oxides are not removed from the exhaust gas (CO2
) is mixed with the new cape air (8) and supplied to the beak element@(g).
（ト）発明の効果
本発明によれば原燃料を改質処理した燃料ガスには、原
燃料もしくは燃料ガスを脱硫しても微量のジ日が残存し
ており、これが燃料極へ送られて後排ガスを燃焼酸化し
た際に生成する８０２や８０３々どの有害々ガスは、除
去器内の溶融炭酸塩により捕捉されて酸素極に供給され
るので、電極の腐食や電解質の変質が防止され、従って
原燃料は精製間の良好々脱硫器を使用することなくシス
テムを構築することができる。(g) Effects of the Invention According to the present invention, the fuel gas obtained by reforming the raw fuel contains a trace amount of residual gas even after the raw fuel or fuel gas is desulfurized, and this is sent to the fuel electrode. Harmful gases such as 802 and 803 generated when exhaust gas is combusted and oxidized are captured by molten carbonate in the eliminator and supplied to the oxygen electrode, preventing corrosion of the electrode and deterioration of the electrolyte. Therefore, it is possible to construct a system for raw fuel without using a desulfurizer during refining.
第１図は本発明溶融炭酸塩燃料電池のシステム黄酸化物
フロー図、第２図は本発明による硫学鴫除去器の断面図
、筑３Ｍ（イ）０口）は同上の他実施例による除去器の
断面図及びペレットの正面図を夫々示す。
４・・・燃料処理装置、２・・・脱硫器、５・・・燃焼
器、６・・・硫黄酸化物除去器、７・・・ペレット。Fig. 1 is a system yellow oxide flow diagram of the molten carbonate fuel cell according to the present invention, Fig. 2 is a sectional view of the sulfuric acid remover according to the present invention, and Chiku 3M (A) 0) is according to another embodiment of the same. A cross-sectional view of the remover and a front view of the pellet are shown, respectively. 4...Fuel processing device, 2...Desulfurizer, 5...Combustor, 6...Sulfur oxide remover, 7...Pellet.
Claims (1)
極に供給し、前記燃料極の排出ガスを燃焼器で酸化させ
て生成する炭酸ガスが空気と共に酸素極に供給されるシ
ステムにおいて、前記燃焼器の下流に前記酸化後のガス
中に存在する硫黄酸化物を溶融炭酸塩で捕促する除去器
を設けたことを特徴とする溶融炭酸塩燃料電池システム
。(1) In a system in which hydrogen-rich gas produced by reforming raw fuel is supplied to the fuel electrode, and carbon dioxide produced by oxidizing the exhaust gas of the fuel electrode in a combustor is supplied to the oxygen electrode together with air, A molten carbonate fuel cell system, characterized in that a remover is provided downstream of the combustor to trap sulfur oxides present in the oxidized gas with molten carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61062441A JPS62219473A (en) | 1986-03-19 | 1986-03-19 | Fused carbonate fuel cell system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61062441A JPS62219473A (en) | 1986-03-19 | 1986-03-19 | Fused carbonate fuel cell system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62219473A true JPS62219473A (en) | 1987-09-26 |
Family
ID=13200291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61062441A Pending JPS62219473A (en) | 1986-03-19 | 1986-03-19 | Fused carbonate fuel cell system |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62219473A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002093452A (en) * | 2000-09-11 | 2002-03-29 | Ishikawajima Harima Heavy Ind Co Ltd | Impurity gas removing method for fuel cell power generation facility and impurity gas removing device thereof |
| JP2006261007A (en) * | 2005-03-18 | 2006-09-28 | Matsushita Electric Ind Co Ltd | Hydrogen generator and fuel cell system |
-
1986
- 1986-03-19 JP JP61062441A patent/JPS62219473A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002093452A (en) * | 2000-09-11 | 2002-03-29 | Ishikawajima Harima Heavy Ind Co Ltd | Impurity gas removing method for fuel cell power generation facility and impurity gas removing device thereof |
| JP2006261007A (en) * | 2005-03-18 | 2006-09-28 | Matsushita Electric Ind Co Ltd | Hydrogen generator and fuel cell system |
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