TWI473339B - A reformer system, a fuel cell system and a method of operation thereof - Google Patents
A reformer system, a fuel cell system and a method of operation thereof Download PDFInfo
- Publication number
- TWI473339B TWI473339B TW97105464A TW97105464A TWI473339B TW I473339 B TWI473339 B TW I473339B TW 97105464 A TW97105464 A TW 97105464A TW 97105464 A TW97105464 A TW 97105464A TW I473339 B TWI473339 B TW I473339B
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- Prior art keywords
- temperature
- fuel cell
- fuel
- introduction
- raw fuel
- Prior art date
Links
- 239000000446 fuel Substances 0.000 title claims description 213
- 238000000034 method Methods 0.000 title claims description 22
- 239000003054 catalyst Substances 0.000 claims description 115
- 238000002407 reforming Methods 0.000 claims description 55
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000010248 power generation Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 20
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000003915 liquefied petroleum gas Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- ZZCNKSMCIZCVDR-UHFFFAOYSA-N barium(2+);dioxido(dioxo)manganese Chemical compound [Ba+2].[O-][Mn]([O-])(=O)=O ZZCNKSMCIZCVDR-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
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- 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
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
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- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
- H01M8/04022—Heating by combustion
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- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
- H01M8/04228—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during shut-down
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- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0432—Temperature; Ambient temperature
- H01M8/04365—Temperature; Ambient temperature of other components of a fuel cell or fuel cell stacks
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- H01M8/0432—Temperature; Ambient temperature
- H01M8/04373—Temperature; Ambient temperature of auxiliary devices, e.g. reformers, compressors, burners
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- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
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- H01M8/04746—Pressure; Flow
- H01M8/04776—Pressure; Flow at auxiliary devices, e.g. reformer, compressor, burner
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- H—ELECTRICITY
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- H01M8/04955—Shut-off or shut-down of fuel cells
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- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/2425—High-temperature cells with solid electrolytes
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- H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
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- C01B2203/1058—Nickel catalysts
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- C01B2203/169—Controlling the feed
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- 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
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- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Health & Medical Sciences (AREA)
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- Health & Medical Sciences (AREA)
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- Hydrogen, Water And Hydrids (AREA)
Description
本發明係關於具有藉由以改質觸媒改質原燃料來生成改質氣體的改質器之改質器系統、進而具有將改質氣體作為燃料使用之固體氧化物形燃料電池之燃料電池系統、及其運轉方法。
作為習知之燃料電池系統,已知有具備在停止固體氧化物形燃料電池之發電時,將貯藏於液體氮貯藏箱之氮供給給燃料電池之燃料極的燃料極氮供給設備(譬如,參考專利文獻1)。藉由此燃料電池系統,在停止固體氧化物形燃料電池之發電時,在燃料電池中,可防止燃料極中所用之鎳等氧化膨脹,其結果,可避免包含氧化釔穩定化氧化鋯等之電解質發生破損。
專利文獻1:日本專利公開公報特開2004-220942號
但,上述習知之燃料電池系統,由於必須設置液體氮貯藏箱及燃料極氮供給設備,而使構造複雜化。
因此,本發明係鑒於此問題而發明完成者,其目的係提供一種在停止固體氧化物形燃料電池之發電時,可以簡單之構造避免損壞燃料電池之改質器系統、燃料電池系統、及其運轉方法。
為達成上述目的,本發明之改質器系統,係具有藉由以
改質觸媒改質原燃料,而生成作為固體氧化物形燃料電池之燃料而使用之改質氣體的改質器之改質器系統,其特徵在於:包括:將原燃料導入改質觸媒之原燃料導入機構;加熱改質觸媒之加熱機構;將空氣導入改質觸媒之空氣導入機構;檢測改質觸媒溫度之溫度檢測機構;在停止燃料電池之發電時,使原燃料導入機構減少原燃料之導入量,在由溫度檢測機構所檢測之溫度下降到未改質氣體發生溫度之前,進行使加熱機構加熱改質觸媒之控制及使空氣導入機構將空氣導入於改質觸媒之控制之至少一項的控制之控制機構。
又,本發明之燃料電池系統,係包括藉由以改質觸媒改質原燃料來生成改質氣體之改質器及將改質氣體作為燃料使用之固體氧化物形燃料電池之燃料電池系統,其特徵在於:包括:將原燃料導入改質觸媒之原燃料導入機構;加熱改質觸媒之加熱機構;將空氣導入改質觸媒之空氣導入機構;檢測改質觸媒溫度之溫度檢測機構;在停止燃料電池之發電時,使原燃料導入機構減少原燃料之導入量,在由溫度檢測機構所檢測之溫度下降到未改質氣體發生溫度之前,進行使加熱機構加熱改質觸媒之控制及使空氣導入機構將空氣導入於改質觸媒之控制之至少一項的控制之控制機構。
再者,本發明之燃料電池系統之運轉方法,係包括藉由以改質觸媒改質原燃料來生成改質氣體之改質器及將改質氣體作為燃料使用之固體氧化物形燃料電池之燃料電池系
統之運轉方法,其特徵在於:在停止燃料電池之發電時,減少向改質觸媒之原燃料之導入量,在改質觸媒之溫度下降到未改質氣體發生溫度之前,進行改質觸媒之加熱及向改質觸媒之空氣之導入之任一項。
在該等改質器系統、燃料電池系統、及其運轉方法中,在停止固體氧化物形燃料電池之發電時,使導入於改質器之改質觸媒之原燃料之導入量減少,此時,在改質觸媒之溫度下降到未改質氣體發生溫度之前,進行加熱改質觸媒及向改質觸媒導入空氣之至少一項。藉此,由於改質觸媒之溫度上升,在固體氧化物形燃料電池之發電停止時,可防止未改質氣體之發生,將改質氣體供給給燃料電池。因此,在停止固體氧化物形燃料電池之發電時,即使不用如習知一樣設置液體氮貯藏箱及燃料極氮供給設備,亦可藉由簡單之構成避免對燃料電池帶來損壞。
在本發明之改質器系統中,控制機構,較佳為對應由原燃料導入機構導入之原燃料之導入量之減少,使加熱機構改變對改質觸媒之加熱量。又,在本發明之改質器系統中,控制機構,較佳為對應由原燃料導入機構導入之原燃料之導入量之減少,使空氣導入機構改變空氣之導入量。藉此,使改質觸媒之溫度上升,可確實防止未改質氣體發生。
在本發明之改質器系統中,加熱機構,以加熱器、燃燒器及燃燒廢氣者為佳。藉由加熱器、燃燒器及燃燒廢氣,可加熱改質觸媒使改質觸媒之溫度確實且容易地上升。
在本發明之改質器系統中,溫度檢測機構,以在藉由原燃料導入機構導入之原燃料之流路的中心軸線上檢測改質觸媒之溫度者為佳。藉此,可在改質觸媒中正確地檢測出原燃料之改質反應之主要發生部分之溫度。
藉由本發明,在停止固體氧化物形燃料電池之發電時,可藉由簡單之構成,避免給燃料電池帶來損壞。
以下,對本發明之較佳實施形態,參照圖式進行詳細說明。
如圖1及2所示,燃料電池系統1,包括藉由以改質觸媒2a改質原燃料來生成改質氣體之改質器2及將改質氣體作為燃料使用之固體氧化物形燃料電池3。
改質器2,以改質觸媒2a使原燃料與水蒸氣(水)發生水蒸氣改質反應,生成含有氫之改質氣體。由於水蒸氣改質反應係吸熱反應,故改質器2,將燃料電池3之排熱利用於水蒸氣改質反應。作為改質觸媒2a,可使用已知可作為水蒸氣改質觸媒之觸媒。即,作為水蒸氣改質觸媒之例,可舉例有釕系觸媒及鎳系觸媒。
作為原燃料,改質氣體之原料可從在固體氧化物型燃料電池之領域中周知之烴系燃料,即,分子中包含碳與氫之化合物(亦可包含氧等其他元素)或其混合物中適宜選取使用。譬如,烴類、醇類、醚類等分子中含有碳與氫之化合物。更具體而言,其為甲烷、乙烷、丙烷、丁烷、天然氣、LPG(液化石油氣)、市區天然氣、汽油、石腦油、燈
油、輕油等之烴類、甲醇、乙醇等之醇類、二甲醚等之醚類等。其中,燈油及LPG,由於容易取得而佳。又,燈油及LPG,由於可獨立貯藏,故在未普及市區天然氣管路之地域為有用。再者,使用燈油及LPG之固體氧化物型燃料電池,可使用作為緊急用電源。
燃料電池3,藉由稱為SOFC(Solid Oxide Fuel Cells,固體氧化物燃料單元電池)之複數個單元電池進行發電。單元電池之構成係將固體氧化物之電解質配置於燃料極與空氣極之間。電解質,譬如由氧化釔穩定化氧化鋯(YSZ)組成,在800℃~1000℃之溫度下傳導氧化物離子。燃料極,譬如由鎳與YSZ之混合物組成,使氧化物離子與改質氣體中之氫反應,使其產生電子及水。空氣極,譬如由錳酸鍶鑭組成,使空氣中之氧與電子反應,使其產生氧化物離子。
又,燃料電池系統1,包括,將原燃料及水蒸氣(水)導入改質觸媒2a之原燃料導入裝置(原燃料導入機構)4、加熱改質觸媒2a之複數個加熱器(加熱機構)5、將空氣導入改質觸媒2a之複數個空氣導入裝置(空氣導入機構)6、及將空氣導入陰極(空氣極)之陰極用空氣導入裝置(陰極用空氣導入機構)(未圖示)。原燃料導入裝置4,具有用於導入原燃料及水蒸氣之原燃料導入管、及用於調節原燃料及水蒸氣之導入量的導入量調節閥等。各空氣導入裝置6及陰極用空氣導入裝置,具有用於導入空氣之空氣導入管、及用於調節空氣之導入量的導入量調節閥等。加熱器5,譬如,為
埋設於改質觸媒2a中之陶瓷加熱器。
再者,燃料電池系統1,包括,檢測改質觸媒2a之溫度之複數個溫度檢測器(溫度檢測機構)7、檢測燃料電池3之單元電池之溫度之溫度檢測器8、及控制系統全體之控制裝置(控制機構)9。溫度檢測器7、8,譬如為熱電偶。各溫度檢測器7之測溫接點,在沿與中心軸線(由原燃料導入裝置4導入之原燃料之流路之中心軸線)L1略直交之方向對向之加熱器5與空氣導入裝置6之空氣導入管之間,其配置於中心軸線L1與中心軸線(由空氣導入裝置6導入之空氣之流路之中心軸線)L2之交點上。即,各溫度檢測器6,以與相互對向之加熱器5及空氣導入裝置6對應之方式設置而成。
又,由改質器2、原燃料導入裝置4、加熱器5、空氣導入裝置6、溫度檢測器7及控制裝置9構成改質器系統10。其次,對燃料電池系統1之運轉方法進行說明。
對於進入冷待機時之燃料電池系統1之運轉方法,參照圖3進行說明。又,冷待機係指,燃料電池系統1之運轉完全停止,燃料電池3之單元電池之溫度在室溫之狀態下,燃料電池系統1處待機狀態。冷待機,由於燃料電池系統1之啟動需要長時間,故其採用於燃料電池3中之發電之停止時間比較長之情形。
如圖3所示,首先,由控制裝置9發出冷待機命令(步驟S11),停止來自燃料電池3之電流掃引(步驟S12)。即,由控制裝置9控制燃料電池3,停止燃料電池3中之發電。接
著,由控制裝置9控制原燃料導入裝置4,減少導入改質觸媒2a之原燃料及水蒸氣之導入量(步驟S13)。在此,原燃料及水蒸氣之導入量開始漸減。藉此,燃料電池3之單元電池之溫度及改質觸媒2a之溫度開始下降。
原燃料及水蒸氣之導入量之漸減開始後,藉由控制裝置9判斷各溫度檢測器7所檢測之改質觸媒2a之溫度是否在TR
以下(步驟S14)。TR
係未改質氣體發生溫度與定格運轉時之改質觸媒2a之溫度之間之溫度,譬如原燃料為燈油之情形,為400℃~700℃之溫度。TR
於每個溫度檢測器7適宜地設定。又,未改質氣體發生溫度,指原燃料未被改質觸媒2a完全改質,產生可對燃料電池3之單元電池帶來損壞之碳數2以上之烴氣體(未改質氣體)而開始混入到改質氣體之溫度,其對應燃料之導入量而預先設定。附言之,改質氣體中之一氧化碳,在燃料極中與氧化物離子反應,成為電子及二氧化碳。
且,若各溫度檢測器7檢測之改質觸媒2a之溫度在TR
以下,則藉由控制裝置9實行以下之加熱器輸出處理及空氣導入處理之至少一項之處理(步驟S15)。又,是否只實行加熱器輸出處理、只實行空氣導入處理、或者實行加熱器輸出處理及空氣導入處理之兩項中任一項,從經濟性及改質觸媒2a之溫度上升之應答性等之觀點,每次決定為最適化。作為一例,在改質觸媒2a之溫度比較高之初期階段,實行空氣導入處理實現自熱改質反應(ATR),在改質觸媒2a之溫度成特定之溫度以下之階段時,實行加熱器輸出處
理及空氣導入處理兩項而包括由加熱器5之輔助。其後,與改質觸媒2a之溫度相均衡只實行加熱器輸出處理、或與輸出控制相均衡續行加熱器輸出處理及空氣導入處理之兩項。以上之步驟S15之處理,對於後述熱待機之步驟S25亦同樣。
在加熱器輸出處理中,對應於檢測出TR
以下之溫度之溫度檢測器7,由控制裝置9控制加熱器5,藉由該加熱器5加熱改質觸媒2a使改質觸媒2a之溫度上升。改質觸媒2a之加熱開始後,藉由控制裝置9判斷溫度檢測器7所檢測之改質觸媒2a之溫度是否在特定之溫度以下,若改質觸媒2a之溫度為特定之溫度以下,則藉由控制裝置9增加加熱器5之輸出。特定之溫度,對應漸減之原燃料及水蒸氣之導入量,設定複數個比可發生未改質氣體之溫度更高之溫度,每次達到各特定之溫度以下,則藉由控制裝置9使加熱器5之輸出發生變化。如此,控制裝置9,對應由原燃料導入裝置4所導入之原燃料之導入量之減少,使加熱器5改變對改質觸媒2a之加熱量。藉此,使改質觸媒2a之溫度上升,可確實防止未改質氣體之發生。
又,在空氣導入處理中,對應於檢測出TR
以下之溫度之溫度檢測器7的空氣導入裝置6由控制裝置9控制,藉由該空氣導入裝置6,開始向改質觸媒2a導入空氣。藉此,可容易地使改質觸媒2a溫度上升。即,空氣導入裝置6,藉由將空氣導入於改質觸媒2a使改質觸媒2a之溫度上升。如此,在燃料電池3之定格運轉時,由原燃料導入裝置4將原
燃料及水導入到改質觸媒2a,效率良好地實現水蒸氣改質反應,在燃料電池3中之發電停止時,由空氣導入裝置6將空氣導入到改質觸媒2a,實現ATR。
開始向改質觸媒2a導入空氣後,藉由控制裝置9判斷由溫度檢測器7檢測之改質觸媒2a溫度是否為特定之溫度以下,若改質觸媒2a之溫度為特定之溫度以下,則由控制裝置9實行O2
/C(所導入之燃料之燃燒比率)之增加處理。特定溫度,對應漸減之原燃料及水蒸氣之導入量,設定複數個比可發生未改質氣體之溫度更高之溫度,每次達到各特定溫度以下時實行O2
/C之增加處理。又,O2
/C之增加處理係指,譬如,增加空氣導入裝置6向改質觸媒2a之空氣導入量之處理。此情形,控制裝置9,對於由原燃料導入裝置4所導入之原燃料之導入量之減少,使對空氣導入裝置6之空氣導入量發生變化。藉此,使改質觸媒2a之溫度上升,可確實防止未改質氣體之發生。
在實行以上之加熱器輸出處理及空氣導入處理之至少一項之處理期間,藉由控制裝置9判斷溫度檢測器8所檢測之燃料電池3之單元電池之溫度是否在TC
1以下(步驟16)。TC
1,係燃料電池3不需要作為燃料極之還原氣體的改質氣體之溫度,其溫度,為100℃~500℃,以100℃~300℃為佳,更佳者為100℃~200℃。且,若溫度檢測器8所檢測之單元電池之溫度為TC
1以下,則原燃料導入裝置4以及加熱器5及空氣導入裝置6之中正在動作者由控制裝置9予以控制,在由原燃料導入裝置4之原燃料及水蒸氣之導入停止
之同時,停止由加熱器5之輸出及由空氣導入裝置6之空氣導入(步驟17)。
接著,藉由控制裝置9判斷溫度檢測器8所檢測之燃料電池3之單元電池之溫度是否為TC
2以下(步驟18)。TC
2,係燃料電池3不需要向陰極導入空氣之溫度,其溫度,以50℃~200℃為佳,更佳者為50℃~100℃。且,若溫度檢測器8所檢測之單元電池之溫度為TC
2以下,則藉由控制裝置9停止系統全體之運轉(步驟S19),燃料電池系統1進入冷待機。
對進入熱待機時之燃料電池系統1之運轉方法,參照圖4進行說明。又,熱待機係指,燃料電池3中發電停止,燃料電池3之單元電池之溫度在作動溫度之狀態下,燃料電池系統1處待機狀態。熱待機,由於在燃料電池系統1之啟動時不需要長時間,故可採用於燃料電池3中之發電之停止時間比較短之情形。
如圖4所示,首先,由控制裝置9發出熱待機命令(步驟S21),停止來自燃料電池3之電流掃引(步驟S22)。即,由控制裝置9控制燃料電池3,停止燃料電池3之發電。接著,由控制裝置9控制原燃料導入裝置4,減少導入改質觸媒2a之原燃料及水蒸氣之導入量(步驟S23)。在此,使原燃料及水蒸氣之導入量只減少特定之量。
而且,藉由控制裝置9判斷是否滿足各溫度檢測器7檢測之改質觸媒2a之溫度為TR
以下且溫度檢測器8檢測之燃料
電池3之單元電池之溫度為TC
3以上之條件(步驟S24)。TC
3,為單元電池之作動溫度,譬如電解質由YSZ組成之情形,其為YSZ傳導氧化物離子之800℃~1000℃之溫度。
步驟S24之判斷處理結果,當滿足該條件時,為防止改質器2中未改質氣體之發生,藉由控制裝置9實行上述加熱器輸出處理及空氣導入處理之至少一項之處理(步驟25),返回到步驟S24之判斷處理。另一方面,步驟S24之判斷結果不滿足該條件時,藉由控制裝置9判斷溫度檢測器8所檢測之燃料電池3之單元電池之溫度是否為未滿TC
3(步驟26)。
步驟S26之判斷處理結果,當燃料電池3之單元電池之溫度未滿TC
3時,為將單元電池之溫度維持在作動溫度,由控制裝置9控制原燃料導入裝置4,由原燃料導入裝置4增加導向改質觸媒2a之原燃料及水蒸氣之導入量(步驟S27),返回到步驟S24之判斷處理。在此,原燃料及水蒸氣之導入量,僅增加比步驟S23之處理中所減少之特定量更少的特定量。另一方面,步驟S26之判斷處理結果,當燃料電池3之單元電池溫度為TC
3以上時,返回到步驟S24之判斷處理。
如此,由改質器2供給至燃料電池3之改質氣體在燃料電池3之燃燒室中燃燒,燃料電池系統1進入熱待機。
如以上所說明,改質器系統10、燃料電池系統1、及其運轉方法中,在停止燃料電池3之發電時,減少向改質器2之改質觸媒2a之原燃料導入量,而此時,在改質觸媒2a之
溫度下降到未改質氣體發生溫度之前,進行改質觸媒2a之加熱及導向改質觸媒2a之空氣導入之至少一項。藉此,由於改質觸媒2a之溫度上升,在燃料電池3中之發電停止時,可防止未改質氣體之發生,而將改質氣體供給於燃料電池3。因此,在停止燃料電池3之發電時,可以簡單之構成避免給燃料電池3帶來損壞。
又,溫度檢測器7,在中心軸線L1上檢測改質觸媒2a之溫度。藉此,可在改質觸媒2a上正確地檢測主要引起改質反應之部分之溫度。
本發明,不限定於上述實施形態。
譬如,如圖5(a)所示,加熱器5及空氣導入裝置6,可分別為1個。又,如圖5(b)所示,空氣導入裝置6,亦可使用原燃料導入裝置4之原燃料導入管作為其空氣導入管。又,亦可藉由代替加熱器5而採用燃燒及燃燒廢氣管,而加熱改質觸媒2a。藉由燃燒及燃燒廢氣,與加熱器5同樣地,亦可確實且容易地加熱改質觸媒2a使改質觸媒2a之溫度上升。
又,燃料電池系統1,在進入冷待機時,在電流掃引之停止處理(步驟S12)之前,將輸出下降到任意之部分負荷後,實施電流掃引之停止處理(步驟S12),亦可進行利用圖3所說明之冷待機停止步驟。該情形,在實行電流掃引之停止處理(步驟S12)之前,所發電之電力,譬如,可蓄於蓄電器,或在負荷器中消耗。
又,在燃料電池3之定格運轉時,可在改質器2中實現
ATR及部分氧化改質反應。該等情形,使導向改質器2之改質觸媒2a之原燃料之導入量減少,在改質觸媒2a之溫度下降到未改質氣體發生溫度之前,只要使改質觸媒2a之溫度上升,即可在燃料電池3停止發電時,以簡單之構成防止未改質氣體之發生,可避免對燃料電池3帶來損壞。又,該等情形,作為改質觸媒2a,可使用自動加熱改質(自熱改質)觸媒或週知作為部分氧化改質觸媒之觸媒。即,作為自動加熱改質觸媒之例可舉例有銠系觸媒,作為部分氧化改質觸媒之例可舉例有鉑系觸媒。
再者,燃料電池系統1,可以根據需要而適宜地設置間接內部型SOFC之周知之構成要素。若舉例具體例則係,使液體氣化之氣化器、用於加壓各種流體之泵、壓縮機、吹風機等之升壓機構,用於調節流體流量、或用於遮斷/切換流體流動之閥等的流量調節機構及流路遮斷/切換機構,用於進行熱交換.熱回收之熱交換器、凝縮氣體之凝縮器、以蒸汽等對各種機器外加熱之加熱/保溫機構,烴系燃料及可燃物之貯藏機構,計裝用之空氣及電氣系統,控制用之信號系統,控制裝置,輸出用及動力用之電氣系統等。
藉由本發明,在停止固體氧化物形燃料電池之發電時,可以簡單之構成避免對燃料電池帶來損壞。
1‧‧‧燃料電池系統
2‧‧‧改質器
2a‧‧‧改質觸媒
3‧‧‧燃料電池
4‧‧‧原燃料導入裝置(原燃料導入機構)
5‧‧‧加熱器(加熱機構)
6‧‧‧空氣導入裝置(空氣導入機構)
7‧‧‧溫度檢測器(溫度檢測機構)
8‧‧‧單元電池溫度檢測器(單元電池溫度
檢測機構)
9‧‧‧控制裝置(控制機構)
10‧‧‧改質器系統
L1‧‧‧原燃料流路之中心軸線
L2‧‧‧空氣流路之中心軸線
圖1係本發明相關之燃料電池系統一實施形態之正面
圖。
圖2係圖1所示之燃料電池系統之平面圖。
圖3係表示圖1所示之燃料電池系統進入冷待機時之運轉方法之流程圖。
圖4係表示圖1所示之燃料電池系統進入熱待機時之運轉方法之流程圖。
圖5(a)、(b)係本發明相關之燃料電池系統其他實施形態之平面圖。
1‧‧‧燃料電池系統
2‧‧‧改質器
2a‧‧‧改質觸媒
3‧‧‧燃料電池
4‧‧‧原燃料導入裝置(原燃料導入機構)
8‧‧‧加熱器(加熱機構)
9‧‧‧控制裝置(控制機構)
10‧‧‧改質器系統
Claims (7)
- 一種改質器系統,其特徵為具有藉由以改質觸媒改質原燃料,生成作為固體氧化物形燃料電池之燃料而使用之改質氣體的改質器,該改質器系統包括:將前述原燃料導入前述改質觸媒之原燃料導入機構;加熱前述改質觸媒之加熱機構;將空氣導入前述改質觸媒之空氣導入機構;檢測前述改質觸媒之溫度之溫度檢測機構;及控制機構,在停止前述燃料電池發電之際,使前述原燃料導入機構減少前述原燃料之導入量,在由前述溫度檢測機構所檢測之溫度下降到未改質氣體發生溫度之前,進行使前述加熱機構加熱前述改質觸媒之控制及進行使前述空氣導入機構將空氣導入於前述改質觸媒之控制之至少一項的控制。
- 如請求項1之改質器系統,其中前述控制機構,對應於前述原燃料導入機構所導入之前述原燃料之導入量之減少,使前述加熱機構改變對前述改質觸媒之加熱量。
- 如請求項1之改質器系統,其中前述控制機構,對應於前述原燃料導入機構所導入之前述原燃料之導入量之減少,對於前述空氣導入機構改變前述空氣之導入量。
- 如請求項1之改質器系統,其中前述加熱機構為加熱器、燃燒器或燃燒廢氣。
- 如請求項1之改質器系統,其中前述溫度檢測機構,在前述原燃料導入機構所導入之前述原燃料之流路之中心 軸線上,檢測前述改質觸媒之溫度。
- 一種燃料電池系統,其特徵為包括藉由以改質觸媒改質原燃料而生成改質氣體之改質器以及將前述改質氣體作為燃料使用之固體氧化物形燃料電池,該燃料電池系統包括:將前述原燃料導入前述改質觸媒之原燃料導入機構;加熱前述改質觸媒之加熱機構;將空氣導入前述改質觸媒之空氣導入機構;檢測前述改質觸媒之溫度之溫度檢測機構;控制機構,在停止前述燃料電池發電之際,使前述原燃料導入機構減少前述原燃料之導入量,在由前述溫度檢測機構所檢測之溫度下降到未改質氣體發生溫度之前,進行使前述加熱機構加熱前述改質觸媒之控制及使前述空氣導入機構將空氣導入於前述改質觸媒之控制之至少一項的控制。
- 一種燃料電池系統之運轉方法,該燃料電池系統包括藉由以改質觸媒改質原燃料而生成改質氣體之改質器以及將前述改質氣體作為燃料使用之固體氧化物形燃料電池,該運轉方法之特徵在於:在停止前述燃料電池發電之際,使導向前述改質觸媒之前述原燃料之導入量減少,在前述改質觸媒之溫度下降到未改質氣體發生溫度之前,進行加熱前述改質觸媒及對於前述改質觸媒導入空氣之至少一項。
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- 2008-02-14 US US12/527,097 patent/US20100119894A1/en not_active Abandoned
- 2008-02-14 CN CN2008800050910A patent/CN101611513B/zh active Active
- 2008-02-14 WO PCT/JP2008/052456 patent/WO2008099893A1/ja active Application Filing
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Also Published As
Publication number | Publication date |
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US20100119894A1 (en) | 2010-05-13 |
EP2124282B1 (en) | 2013-05-22 |
TW200847517A (en) | 2008-12-01 |
CA2678397C (en) | 2015-01-06 |
CN101611513B (zh) | 2012-07-04 |
EP2124282A4 (en) | 2012-05-09 |
KR20090109572A (ko) | 2009-10-20 |
CN102701150A (zh) | 2012-10-03 |
CN101611513A (zh) | 2009-12-23 |
CA2678397A1 (en) | 2008-08-21 |
WO2008099893A1 (ja) | 2008-08-21 |
CN102701150B (zh) | 2014-10-01 |
JP5064830B2 (ja) | 2012-10-31 |
KR101361597B1 (ko) | 2014-02-12 |
JP2008204655A (ja) | 2008-09-04 |
EP2124282A1 (en) | 2009-11-25 |
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