JP2008163878A - 内燃機関の排気ガス浄化装置 - Google Patents
内燃機関の排気ガス浄化装置 Download PDFInfo
- Publication number
- JP2008163878A JP2008163878A JP2006355741A JP2006355741A JP2008163878A JP 2008163878 A JP2008163878 A JP 2008163878A JP 2006355741 A JP2006355741 A JP 2006355741A JP 2006355741 A JP2006355741 A JP 2006355741A JP 2008163878 A JP2008163878 A JP 2008163878A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- nox
- ozone
- exhaust gas
- adsorbent
- 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
Links
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 193
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000003463 adsorbent Substances 0.000 claims abstract description 48
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims description 72
- 239000000463 material Substances 0.000 claims description 48
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000003795 desorption Methods 0.000 abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 393
- 239000004215 Carbon black (E152) Substances 0.000 description 75
- 229930195733 hydrocarbon Natural products 0.000 description 75
- 150000002430 hydrocarbons Chemical class 0.000 description 75
- 239000007789 gas Substances 0.000 description 72
- 238000012360 testing method Methods 0.000 description 56
- 238000002474 experimental method Methods 0.000 description 26
- 238000002347 injection Methods 0.000 description 20
- 239000007924 injection Substances 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 14
- 229910000510 noble metal Inorganic materials 0.000 description 14
- 238000010586 diagram Methods 0.000 description 13
- 239000011232 storage material Substances 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- 229910052788 barium Inorganic materials 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 3
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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Abstract
【解決手段】内燃機関の排気通路に設けられた排気ガス浄化装置であって、NOx保持材と、NOx保持材の上流の排気ガスにオゾンを導入するオゾン導入手段と、排気ガスに含まれるHCを吸着するHC吸着材と、脱離したNOxとHCとが接触する部位に配置された触媒と、を備える。HC吸着材は、NOx保持材に貯蔵されたNOxが脱離するタイミングで、吸着していたHCが脱離するように調製されている。
【選択図】図1
Description
内燃機関の排気通路に設けられた排気ガス浄化装置であって、
NOx保持材と、
前記NOx保持材の上流の排気ガスにオゾンを導入するオゾン導入手段と、
排気ガスに含まれるHCを吸着するHC吸着材と、
脱離したNOxとHCとが接触する部位に配置された触媒と、を備え、
前記HC吸着材は、前記NOx保持材に貯蔵或いは吸着されたNOxが脱離するタイミングで、吸着していたHCが脱離するように調製されていることを特徴とする。
前記HC吸着材および前記NOx保持材は、前記触媒と一体化されていることを特徴とする。
前記HC吸着材と前記NOx保持材とは別体であって、
前記HC吸着材は、前記NOx保持材の上流に配置され、
前記オゾン導入手段は、前記HC吸着材の下流の排気ガスにオゾンを導入することを特徴とする。
前記NOx保持材と前記触媒とは別体であって、
前記NOx保持材は、前記触媒の上流に配置されていることを特徴とする。
前記NOx保持材は、前記触媒と一体化されていることを特徴とする。
[実施の形態1の構成]
図1は、本発明の実施の形態1の構成を説明するための図を示す。図1に示すとおり、本実施の形態の排気ガス浄化装置10は、内燃機関(以下、単に「エンジン」とも称す)12に取り付けられている。
(オゾンを利用したNOx吸蔵動作)
次に、図2および図3を参照して、本実施形態の動作について説明する。排気浄化触媒20の触媒上では、NOxがHC、或いはCOと反応し、N2、H2O、CO2等に分解される。これにより、排気ガスに含まれるNOxを効果的に浄化することとしている。しかしながら、排気浄化触媒20が活性温度に達していない内燃機関12の冷間始動時においては、3元活性が低く、排気ガスに含まれるNOxを浄化できない。
NO+O3→NO2+O2 ・・・(1)
NO2+O3→NO3+O2 ・・・(2)
NO2+NO3→N2O5 ・・・(3)
(NO2+NO3←N2O5)
上述したとおり、本実施の形態においては、排気浄化触媒20に向けてオゾンが噴射される。これにより、エンジン12の冷間始動時に排出されるNOxを効果的に吸蔵して、大気への放出を抑制することができる。
[実験装置の構成]
次に、図4乃至図7を用いて、実施の形態1に示す発明の効果を確認するために行った評価試験について説明する。図4は、本評価試験の実験装置の構成を説明するための図である。図4に示すとおり、本実験装置はモデルガス発生器100を備えている。モデルガス発生器100は複数の種類のガスボンベ102から供給されるガスを混合させて、内燃機関から排出される排気ガスの模擬ガスを生成することができる。
オゾン発生器120 :岩崎電気 OP100W
オゾン分析計126 :荏原実業 EG600
オゾン分析計114 :荏原実業 EG2001B
排気ガス分析計110 :堀場製作所 MEXA9100D
(HC、CO、NOxを計測)
排気ガス分析計112 :堀場製作所 VAI−510
(CO2を計測)
先ず、γ−Al2O3をイオン交換水に分散させ、酢酸バリウム水溶液を加える。この混合物の水分を加熱除去し120℃で乾燥した後、粉砕し粉末にする。この粉末を500℃で2時間焼成する。焼成後の粉末を、炭酸水素アンモニウムを含む溶液に浸漬処理し、250℃で乾燥させ、バリウム担持触媒を得た。
先ず、γ−Al2O3をイオン交換水に分散させ、酢酸バリウム水溶液を加える。この混合物の水分を加熱除去し120℃で乾燥した後、粉砕し粉末にする。この粉末を500℃で2時間焼成する。焼成後の粉末を、炭酸水素アンモニウムを含む溶液に浸漬処理し、250℃で乾燥させ、バリウム担持触媒を得た。
この触媒のバリウム担持量は、γ−Al2O3の120g当たり0.1mol、Ptの担持量は、2gである。
本評価試験における実験条件を以下に示す。
温度 :30℃〜500℃の範囲で制御
温度上昇速度 :10℃/min.
模擬ガス組成 :ストイキ組成
C3H6(1000ppm=3000ppmC)
CO(6500ppm)
NO(1500ppm)
O2(7000ppm)
CO2(10%)
H2O(3%)
残部 N2
模擬ガス流量 :30L/min.
注入ガス組成 :O3(30000ppm)
残部 O2
注入ガス流量 :6L/min.
触媒試験体200周囲に配置された電気炉を低温側から昇温させ実験を行った。注入ガスは30℃から300℃の範囲で注入し、300℃以上の温度ではガスの注入を止め、模擬ガスのみを注入させた。実験は触媒サンプル204を使用する実験1と触媒サンプル206を使用する実験2とを行った。浄化率は、試験時間内に触媒試験体200に導入されたNOx量(以下、「導入NOx量」と称す)から、触媒試験体200の下流に排出されたNOx量(以下、「排出NOx量」と称す)を差し引いた値を、導入NOx量で除算することにより100分率で算出した。
導入NOx量=模擬ガス中のNOx濃度×模擬ガス流量×試験時間 ・・・(4)
排出NOx量=触媒200下流のNOx濃度×ガス流量(模擬ガス+注入ガス)×試験時間 ・・・(5)
浄化率=(導入NOx量−排出NOx量)/導入NOx量×100 ・・・(6)
図6は、実験1および実験2における各種成分の浄化率を示す図である。図6に示すとおり、実験1に使用された触媒試験体の方が、NOx、HC、COのいずれに関しても浄化率が優れていることが確認される。これにより、HC吸着剤をNSR触媒に加えた効果が確認できる。
[実施の形態2の特徴的構成]
次に、図7を参照して、本発明の実施の形態2について説明する。図7は、実施の形態2の構成を説明するための図を示す。尚、図7に示す排気ガス浄化装置40において、図1に示す排気ガス浄化装置10と共通する要素には、同一の符号を付して重複する説明を省略する。
上述した実施の形態1の排気ガス浄化装置10においては、HC吸着剤とNOx吸蔵剤と貴金属とが共通の担体上に担持された排気浄化触媒20を有し、エンジン12の冷間始動時に排出されるNOxを効果的に吸蔵して、大気への放出を抑制することとしている。しかしながら、かかる構成によると、排気浄化触媒20内部に配置されているHC吸着材にもオゾンが導入されてしまう。このため、導入されたオゾンは、NOxだけでなくHC吸着材に吸着していたHCとも反応してしまい、その結果NOxの酸化率が低下してしまうおそれがある。
[実験装置の構成]
次に、図9乃至図11を用いて、実施の形態2に示す発明の効果を確認するために行った評価試験について説明する。図9は、本評価試験の実験装置の構成を説明するための図である。尚、図9に示す実験装置において、図4に示す実験装置と共通する要素には、同一の符号を付して重複する説明を省略する。
ZSM−5型ゼオライト(Si/Al比=40、H型)のH+イオンを、硝酸銀を用いてイオン交換し、乾燥して450℃で焼成することによりAgイオン交換ZSM−5を調製した。そして、φ30mm×L50mm、4mil/400cpsiのコージェライト製ハニカムに、先に調製した触媒をコートし、450℃で1時間焼成した。コート量は50g/Lである。
先ず、γ−Al2O3をイオン交換水に分散させ、酢酸バリウム水溶液を加える。この混合物の水分を加熱除去し120℃で乾燥した後、粉砕し粉末にする。この粉末を500℃で2時間焼成する。焼成後の粉末を、炭酸水素アンモニウムを含む溶液に浸漬処理し、250℃で乾燥させ、バリウム担持触媒を得た。
この触媒のバリウム担持量は、γ−Al2O3の120g当たり0.1mol、Ptの担持量は、2gである。
本評価試験における実験条件を以下に示す。
温度 :30℃〜500℃の範囲で制御
温度上昇速度 :10℃/min.
模擬ガス組成 :ストイキ組成
C3H6(1000ppm=3000ppmC)
CO(6500ppm)
NO(1500ppm)
O2(7000ppm)
CO2(10%)
H2O(3%)
残部 N2
模擬ガス流量 :30L/min.
注入ガス組成 :O3(30000ppm)
残部 O2
注入ガス流量 :6L/min.
触媒300および310の周囲に配置された電気炉を低温側から昇温させ実験を行った。注入ガスは30℃から300℃の範囲で注入し、300℃以上の温度ではガスの注入を止め、模擬ガスのみを注入させた。実験は、触媒サンプル304および314を使用する実験1と、触媒サンプル316を使用する実験2とを行った。浄化率は、上式(5)に基づいて算出した。
図11は、実験1および実験2における各種成分の浄化率を示す図である。図11に示すとおり、実験1に使用された触媒試験体の方が、NOx、HC、COのいずれに関しても浄化率が優れていることが確認される。これにより、HC吸着剤をオゾン導入口より上流に配置した効果が確認できる。
12 内燃機関(エンジン)
14 排気管
20 排気浄化触媒
30 オゾン供給装置
32 空気口
34 オゾン噴射口
40 排気ガス浄化システム
42 排気浄化触媒
44 NSR触媒
46 HC吸着材
50 ECU(Electronic Control Unit)
60 排気浄化触媒
62 HC吸着材
64 NOx保持材
66 3元触媒
100 モデルガス発生器
102 ガスボンベ
110、112 排気ガス分析計
114 オゾン分析計
120 オゾン発生器
122 酸素ボンベ
124、128、130 流量制御ユニット
126 オゾン分析計
200 触媒試験体
202 石英管
204、206 触媒サンプル
300、310 触媒試験体
302、312 石英管
304、314、316 触媒サンプル
Claims (5)
- 内燃機関の排気通路に設けられた排気ガス浄化装置であって、
NOx保持材と、
前記NOx保持材の上流の排気ガスにオゾンを導入するオゾン導入手段と、
排気ガスに含まれるHCを吸着するHC吸着材と、
脱離したNOxとHCとが接触する部位に配置された触媒と、を備え、
前記HC吸着材は、前記NOx保持材に貯蔵或いは吸着されたNOxが脱離するタイミングで、吸着していたHCが脱離するように調製されていることを特徴とする内燃機関の排気ガス浄化装置。 - 前記HC吸着材および前記NOx保持材は、前記触媒と一体化されていることを特徴とする請求項1記載の内燃機関の排気ガス浄化装置。
- 前記HC吸着材と前記NOx保持材とは別体であって、
前記HC吸着材は、前記NOx保持材の上流に配置され、
前記オゾン導入手段は、前記HC吸着材の下流の排気ガスにオゾンを導入することを特徴とする請求項1記載の内燃機関の排気ガス浄化装置。 - 前記NOx保持材と前記触媒とは別体であって、
前記NOx保持材は、前記触媒の上流に配置されていることを特徴とする請求項3記載の内燃機関の排気ガス浄化装置。 - 前記NOx保持材は、前記触媒と一体化されていることを特徴とする請求項3記載の内燃機関の排気ガス浄化装置。
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JP2006355741A JP4501935B2 (ja) | 2006-12-28 | 2006-12-28 | 内燃機関の排気ガス浄化装置 |
US12/520,950 US20100058742A1 (en) | 2006-12-28 | 2007-12-20 | Exhaust emission control apparatus for internal combustion engine |
PCT/JP2007/074539 WO2008081738A1 (ja) | 2006-12-28 | 2007-12-20 | 内燃機関の排気ガス浄化装置 |
CN200780045660XA CN101553649B (zh) | 2006-12-28 | 2007-12-20 | 内燃机的废气净化装置 |
EP07850974.2A EP2098699B1 (en) | 2006-12-28 | 2007-12-20 | Exhaust gas purifying apparatus for internal combustion engine |
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EP3613958A1 (en) | 2018-08-23 | 2020-02-26 | Toyota Jidosha Kabushiki Kaisha | Exhaust purification system of internal combustion engine and exhaust purification method |
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US9677448B2 (en) * | 2015-04-17 | 2017-06-13 | Ford Global Technologies, Llc | Method and system for reducing engine exhaust emissions |
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US10366594B2 (en) * | 2015-05-04 | 2019-07-30 | Mountain Optech, Inc. | Oil and gas production facility emissions sensing and alerting device, system and method |
DE102016112363B4 (de) * | 2016-07-06 | 2023-02-09 | Denso Corporation | Abgasnachbehandlungssystem |
JP2020029841A (ja) * | 2018-08-24 | 2020-02-27 | トヨタ自動車株式会社 | 内燃機関の排気浄化装置及び排気浄化方法 |
CN112930433B (zh) * | 2018-10-22 | 2023-08-15 | 上海必修福企业管理有限公司 | 一种发动机尾气臭氧净化系统和方法 |
JP7020369B2 (ja) * | 2018-10-30 | 2022-02-16 | トヨタ自動車株式会社 | 内燃機関の排気浄化システム |
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- 2007-12-20 CN CN200780045660XA patent/CN101553649B/zh not_active Expired - Fee Related
- 2007-12-20 WO PCT/JP2007/074539 patent/WO2008081738A1/ja active Search and Examination
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JP2003175318A (ja) * | 2002-10-24 | 2003-06-24 | Ngk Insulators Ltd | 排ガス浄化システム及び排ガス浄化方法 |
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JP2014235110A (ja) * | 2013-06-04 | 2014-12-15 | 株式会社堀場製作所 | 模擬ガス供給装置 |
EP3613958A1 (en) | 2018-08-23 | 2020-02-26 | Toyota Jidosha Kabushiki Kaisha | Exhaust purification system of internal combustion engine and exhaust purification method |
JP2020029829A (ja) * | 2018-08-23 | 2020-02-27 | トヨタ自動車株式会社 | 内燃機関の排気浄化装置及び排気浄化方法 |
US11002204B2 (en) | 2018-08-23 | 2021-05-11 | Toyota Jidosha Kabushiki Kaisha | Exhaust purification system of internal combustion engine and exhaust purification method |
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US20100058742A1 (en) | 2010-03-11 |
WO2008081738A1 (ja) | 2008-07-10 |
EP2098699B1 (en) | 2014-05-07 |
CN101553649B (zh) | 2012-05-02 |
CN101553649A (zh) | 2009-10-07 |
EP2098699A4 (en) | 2013-04-17 |
EP2098699A1 (en) | 2009-09-09 |
JP4501935B2 (ja) | 2010-07-14 |
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