CN101180126A - 用于净化废气的催化剂 - Google Patents
用于净化废气的催化剂 Download PDFInfo
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Abstract
用于净化废气的催化剂,包括载体基体和催化剂层,所述催化剂层负载在所述载体基体上并含有贵金属、多孔氧化物和含有至少一种选自Ni、Bi、Sn、Fe、Co、Cu和Zn的元素的附加氧化物。只有位于废气流下游侧的载体基体下游段含有附加氧化物,而载体基体的上游段不含附加氧化物。使用该配置,在载体基体的上游段,贵金属和附加氧化物不共存以使贵金属不会因附加氧化物而劣化。因此,在上游段,有利地表现出作为三元催化剂的净化性能,从而在保持三元性能的同时限制了H2S的排放。
Description
技术领域
本发明涉及适用于净化来自机动车内燃机等的废气的催化剂,更特别涉及能够限制硫化氢(H2S)排放的适用于净化废气的催化剂。
背景技术
如今,三元催化剂已经广泛用作适于净化机动车废气等中的氮氧化物(NOx)、一氧化碳(CO)和烃(HC)的催化剂。三元催化剂由多孔氧化物载体或支承体构成,例如氧化铝、二氧化铈、氧化锆、二氧化铈-氧化锆固溶体等,该载体或支承体负载贵金属,例如铂(Pt)、铑(Rh)、钯(Pd)等。三元催化剂氧化HC和CO并还原NOx以将它们净化。这些反应在氧化组分和还原组分几乎等量存在的气氛中最有效进行,因此,在安装了三元催化剂的机动车中,控制空气-燃料比以使燃烧以大约理论空气-燃料比(化学计量比)(A/F=大约14.6±0.2)进行。
但是,三元催化剂存在着以下问题:当废气气氛移向还原侧时,废气中的硫氧化物被还原,并作为H2S排出。相应地,在已审日本专利申请08-15554(文献1)公报的方法中,添加Ni或Cu的氧化物作为三元催化剂的组分。Ni或Cu的氧化物由氧化气氛中的SO2形成SO3或SO4,并将硫组分以硫化物(例如Ni2S3)形式储存在还原气氛中,限制了H2S的排放。
未审日本专利申请2001-70754(文献2)公报公开了用于净化废气的装置,其中将添加了镍氧化物的三元催化剂置于NOx储存还原催化剂装置的下游侧,该下游侧含有能够减少贫化区中NOx排放的NOx储存组分。未审国际申请2004-523686(文献3)公报公开了一种催化剂复合材料,其上游段含有NOx储存组分,下游段含有铂组分和SOx吸附组分,例如镍氧化物等等。但是,在文献2和3中,添加的镍氧化物使贵金属劣化,从而降低三元催化剂依靠铂组分产生的初始净化性能等,随之CO和HC的净化变得不足。
发明内容
鉴于上述问题,本发明的目的是提供用于净化废气的催化剂,其能够限制H2S的排放,同时保持三元催化剂的净化性能。
本发明的用于净化废气的催化剂的特征在于,该催化剂包括载体基体和催化剂层,所述催化剂层负载在所述载体基体上并含有贵金属、多孔氧化物和含至少一种选自由Ni、Bi、Sn、Fe、Co、Cu和Zn组成组的元素的附加氧化物,并且只有位于废气流下游侧的载体基体下游段含有上述附加氧化物,而载体基体的上游段不含上述附加氧化物。
使用本发明用于净化废气的催化剂,在载体基体的上游段中,贵金属和附加氧化物不共存以使贵金属不会因附加氧化物而劣化。因此,在上游段,优选表现出作为三元催化剂的净化性能。相应地,本发明的用于净化废气的催化剂可以在保持三元性能的同时限制H2S的排放。
附图简述
图1是显示实施方案和对比例中用于净化废气的催化剂的THC 50%净化温度的图。
图2是显示实施方案和对比例中用于净化废气的催化剂的CO-NOx交叉净化率的图。
图3是显示在实施方案和对比例中用于净化废气的催化剂中形成的H2S的量的图。
本发明的最佳实施方式
下面,为了更详细地公开本发明,将解释本发明的最佳实施方式。
本发明用于净化废气的催化剂包括载体基体和催化剂层,该催化剂层负载在所述载体基体上并含有贵金属、多孔氧化物和含至少一种选自由镍(Ni)、铋(Bi)、锡(Sn)、铁(Fe)、钴(Co)、铜(Cu)和锌(Zn)组成的组的元素的附加氧化物。并且只有位于废气流下游侧的载体基体下游段含有上述附加氧化物,而载体基体的上游段不含上述附加氧化物。也就是说,根据本发明,用于净化废气的催化剂的上游段相当于传统三元催化剂,而其下游段含有传统三元催化剂以及附加氧化物。
氧化铝、二氧化硅、二氧化钛、二氧化铈、氧化锆、或由多种这些材料构成的复合氧化物,例如二氧化铈-氧化锆固溶体,可作为多孔氧化物获得,可以使用这些多孔氧化物中的一种或多种。在这种情况下,优选至少含有具有大的比表面积的活性氧化铝。当使用具有氧吸附和排出能力的氧化物(例如二氧化铈-氧化锆固溶体)时,可以使气氛的变化和缓,以进一步改进三元活性。
可以使用包括至少一种选自由Ni、Bi、Sn、Fe、Co、Cu和Zn组成的组的元素的金属氧化物作为附加氧化物。附加氧化物可以是能够在氧化气氛中将SO2变成SO3或SO4并将硫组分作为硫化物(例如Ni2S3)储存在还原气氛中的氧化物。因此,附加氧化物可以与上述金属元素以外的金属元素形成复合氧化物,条件是可以储存硫组分并限制H2S的排放。此外,可以只使用一种上述附加氧化物,或可以一起使用两种或三种附加氧化物。通过作为复合氧化物添加两种或多种附加氧化物,所形成的H2S的量与包含相同量的一种附加氧化物的情况相比进一步降低,因此是优选的。优选在催化剂中添加每升催化剂0.05至0.5摩尔的附加氧化物。
此外,如上所述,附加氧化物使贵金属劣化。在贵金属劣化时,三元催化剂依靠贵金属产生的初始净化性能降低。因此,对于本发明的用于净化废气的催化剂,通过形成两段——一段含有附加氧化物,另一段不含附加氧化物,提供了下述配置:不含附加氧化物的区段可主要表现出作为三元催化剂的净化性能,而含有附加氧化物的区段可主要有效限制H2S的排放。
此外,由于本发明人的研究,现已清楚,含有硫的废气组分从载体基体的上游侧移向下游侧,同时重复着其排放和吸附。随着含硫组分的移动,硫组分的吸附位置也移向下游侧,因此为了限制H2S的排放,有利的是,将附加氧化物置于载体基体的下游侧,并在下游侧将硫组分充分吸附和储存。相应地,设置本发明用于净化废气的催化剂,以便只有位于废气流下游侧的载体基体下游段含有所述附加氧化物,而位于废气流上游侧的载体基体上游段不含附加氧化物,由此有效限制H2S的排放。
可以通过将其与多孔氧化物物理混合来使用附加氧化物,但也可以通过溶胶-凝胶法、共沉淀法等将附加氧化物添加到多孔氧化物中。例如,由含有至少一种上述金属元素的水溶性化合物(例如硝酸盐等)的水溶液沉积沉淀物,并将沉积的沉淀物负载在氧化铝粉末等上,并煅烧,由此可以获得附加氧化物。
优选使用以其催化作用将HC和CO氧化或将NOx还原的贵金属,例如Pt、Rh、Pd等。一起使用具有优异氧化能力的Pt和具有优异还原能力的Rh是有利的。贵金属可以部分负载在附加氧化物上,但合意地,其大部分负载在多孔氧化物上。
贵金属的载量可以与传统三元催化剂中类似,并可以根据所需性能任意选择。优选载量取决于贵金属的种类,但为每升催化剂层0.1至10克。
本发明用于净化废气的催化剂包括用于负载催化剂层的载体基体。由传统可得的陶瓷和金属构成的蜂窝状结构等可用作载体基体。为了将催化剂层负载在载体基体上,例如,可以用含有多孔氧化物和附加氧化物的浆液洗涂蜂窝结构,并煅烧以形成涂层,并用吸附负载法或水-吸收负载法使该涂层负载贵金属。或者,制备已经使贵金属预先负载在多孔载体上的催化剂粉末,并将附加氧化物混入制成的催化剂粉末以形成涂层。
对上游段和下游段的比率没有具体限制,但载体基体的上游段的体积大于其下游段。
本发明的用于净化废气的催化剂不限于上述实施方案。例如,为了使催化剂层增加另一功能,可以根据需要添加另一材料,前提是本发明用于净化废气的催化剂的效果不会受损。
根据上述实施方案制备用于净化废气的催化剂。下面,与对比例一起具体解释本发明用于净化废气的催化剂的实施方案。
在下列方法中制备实施方案和对比例的用于净化废气的催化剂(样品A~C,a~c,A’、C’和x)。
[浆液的制备]
75重量份的二氧化铈-氧化锆固溶体(摩尔比CeO2∶ZrO2∶Y2O3=65∶30∶5)、120重量份的活性氧化铝和氧化铝粘合剂(3重量份水合氧化铝、44重量份40%的硝酸氧化铝水溶液)与预定量的纯水混合,并进行研磨操作以制备浆液So。
与浆液So类似地制备浆液SB,不同的是添加氧化铋。制备2种(138重量份,414重量份)氧化铋含量不同的浆液SB。
与浆液So类似地制备浆液SS,不同的是添加氧化锡。制备2种(90重量份,180重量份)氧化锡含量不同的浆液SS。
与浆液So类似地制备浆液SN,不同的是添加氧化镍。制备2种(50重量份,150重量份)氧化镍含量不同的浆液SN。
与浆液So类似地制备浆液SF,不同的是添加氧化铁。制备2种(107重量份,321重量份)氧化铁含量不同的浆液SF。
[用于净化废气的催化剂的制备]
[对比例1(样品a)]
制备具有400cpsi孔隙密度、100微米壁厚、103毫米直径和130毫米长度的蜂窝载体(1.1升)作为载体基体。将该蜂窝载体用浆液SB(氧化铋含量:138重量份)洗涂,在120℃干燥并在650℃煅烧3小时。
接着,在涂布后,将载体基体浸在具有预定浓度的硝酸铑水溶液中以吸附和负载硝酸铑,从水溶液中取出,在120℃干燥,并在500℃煅烧以负载Rh。此外,使载体基体吸附具有预定浓度的二硝基二氨铂溶液,从该溶液中取出,在120℃干燥并在500℃煅烧1小时,由此负载Pt。由此,获得样品。每升载体基体负载的贵金属量在Rh情况下为0.2克/升,在Pt的情况下为1.0克/升。
[实施方案1(样品A)]
与对比例1(样品a)类似地制备样品A,不同的是位于废气流上游侧的蜂窝载体上游段(2/3蜂窝载体,从一个开放端面起87毫米:下文简称作“上游段”)用浆液So涂布,而蜂窝载体下游段(1/3蜂窝载体,从另一开放端面起43毫米:下文简称作“下游段”)用浆液SB(氧化铋含量:414重量份)涂布。
通过将样品A的蜂窝载体置于废气流中以使其上游侧和下游侧彼此倒置,制备样品A’(对比例1-2),并与样品A基本类似。
[对比例2(样品b)]
与对比例1(样品a)类似地制备样品b,不同的是将蜂窝载体用浆液SS(氧化锡含量:90重量份)而非浆液SB涂布。
[实施方案2(样品B)]
与对比例1(样品a)类似地制备样品B,不同的是蜂窝载体上游段用浆液So涂布,而蜂窝载体下游段用浆液SS(氧化锡含量:180重量份)而非浆液SB涂布。
[对比例3(样品c)]
与对比例1(样品a)类似地制备样品c,不同的是将蜂窝载体用浆液SN(氧化镍含量:50重量份)而非浆液SB涂布。
[实施方案3(样品C)]
与对比例1(样品a)类似地制备样品C,不同的是蜂窝载体上游段用浆液So涂布,而蜂窝载体下游段用浆液SN(氧化镍含量:150重量份)而非浆液SB涂布。
通过将样品C’的蜂窝载体置于废气流中以使其上游侧和下游侧彼此倒置,制备样品C’(对比例3-2),并与样品C基本类似。
[对比例4(样品d)]
与对比例1(样品a)类似地制备样品d,不同的是将蜂窝载体用浆液SF(氧化铁含量:107重量份)而非浆液SB涂布。
[实施方案4(样品D)]
与对比例1(样品a)类似地制备样品D,不同的是蜂窝载体上游段用浆液So涂布,而蜂窝载体下游段用浆液SF(氧化铁含量:321重量份)而非浆液SB涂布。
[对比例5(样品x)]
与对比例1(样品a)类似地制备样品x,不同的是将蜂窝载体用浆液So而非浆液SB涂布。
[实验和评测]
[净化性能试验]
将上述样品分别装在安装了V型8缸4.0升发动机的发动机试验台的废气系统中,并通过将每一样品在900℃的催化剂床温度保持100小时同时以1Hz交替A/F=15和A/F=14,进行持久性试验。
将持久性试验后的样品分别装在安装了直列式4缸2.4升发动机的汽车上,作为其地板下催化剂,以理论空气-燃料比控制发动机的燃烧,并在借助热交换器将温度以10℃/分钟的速率将温度从200℃升至450℃的同时测量HC组分的净化率。根据测量结果,计算可以净化50%的HC组分时的温度。计算出的温度作为“THC 50%净化温度”列在表1和图1中。
将持久性试验后的样品分别装在安装了直列式4缸2.4升发动机的汽车上,并在通过改变燃烧条件使空气-燃料比率从13.5变化到15.5的同时分析催化剂之前和之后的废气,并测量CO净化率和NOx净化率。进入催化剂的气体的温度为400℃。测定CO净化曲线和NOx净化曲线相互交叉点处的净化率,作为“CO-NOx交叉净化率”。NO-NOx交叉净化率显示在表1和图2中。
[H2S生成量试验]
将上述样品分别装在安装了直列式2.4升发动机的汽车上作为其地板下催化剂,且发动机以40公里/小时运行1小时,同时保持运行模式以使地板下催化剂床的温度保持至400℃。然后将节流阀完全打开,以在10秒内将速度升至110公里/小时,并在该速度保持10秒后,降低速度并在20秒内停止,在速度停止后使发动机空转10秒。
测量空转状态下废气中H2S的浓度,其峰值浓度作为“生成的H2S的量”显示在表1和图3中。
表1
样品号 | 涂布的浆液 | THC 50%净化温度[℃] | CO-NOx交叉净化率[%] | 生成的H2S的量[ppm] | ||
上游段 | 下游段 | |||||
对比例1 | a | SB | 365 | 91.2 | 7 | |
实施例1 | A | So | SB | 342 | 96.0 | 8 |
对比例1-2 | A’ | SB | So | 355 | 93.4 | 85 |
对比例2 | b | SS | 385 | 87.0 | 7 | |
实施例2 | B | So | SS | 341 | 96.1 | 9 |
对比例3 | c | SN | 358 | 94.0 | 5 | |
实施例3 | C | So | SN | 339 | 96.2 | 6 |
对比例3-2 | C’ | SN | So | 354 | 95.4 | 72 |
对比例4 | d | SF | 400 | 82.0 | 7 | |
实施例4 | D | So | SF | 350 | 95.8 | 8 |
对比例5 | x | So | 340 | 96.2 | 300 |
[评测]
图1和图2中所示的图表明,样品A、B和C(其中只有蜂窝载体的下游段涂有含附加氧化物的浆液)表现出了三元催化剂的净化性能,其处于与不含附加氧化物的样品x类似的水平。图3表明样品A、B和C可以大大地限制H2S的生成。
因此,样品A、B和C(其中只有下游段涂有含附加氧化物的浆液)可以在保持作为三元催化剂的净化性能的同时限制H2S的生成。
在样品A’和C’(其中附加氧化物的涂布位置分别与样品A和样品C相反,即只有上游段涂有含附加氧化物的浆液)中,所形成的H2S的量明显很大。样品a、b、c和d(其蜂窝载体均匀地含有附加氧化物)实现了提高的限制H2S生成的效果,但作为三元催化剂的净化性能由于附加氧化物引起的贵金属劣化而降低。
工业适用性
本发明用于净化废气的催化剂可用作机动车的三元催化剂,但不限于机动车,条件是在接近化学计量至氧化气氛和在还原气氛中实现燃烧,而无论燃烧的控制如何。
Claims (2)
1.用于净化废气的催化剂,其包括载体基体和催化剂层,所述催化剂层负载在所述载体基体上并且含有贵金属、多孔氧化物和含至少一种选自由Ni、Bi、Sn、Fe、Co、Cu和Zn组成的组的元素的附加氧化物,其中只有位于废气流下游侧的所述载体基体下游段含有所述附加氧化物,而所述载体基体的上游段不含所述附加氧化物。
2.如权利要求1所述的用于净化废气的催化剂,其中所述附加氧化物是选自由氧化镍、氧化铋、氧化锡和氧化铁组成的组的至少一种。
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Cited By (7)
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CN102405102A (zh) * | 2009-05-19 | 2012-04-04 | 美礼联无机化工公司 | 无钒汽车催化剂的催化剂助催化剂 |
CN102513165A (zh) * | 2011-12-14 | 2012-06-27 | 刘碧兰 | 一种高效尾气净化三元催化剂涂敷方法 |
CN104801313A (zh) * | 2015-04-15 | 2015-07-29 | 永康市奥鑫科技有限公司 | 一种用于挥发性有机废气净化的催化剂及其制备方法 |
CN105772023A (zh) * | 2016-03-31 | 2016-07-20 | 湖南省吉安特技术有限公司 | 一种高效三元催化剂涂层的制作方法 |
CN107360714A (zh) * | 2015-03-27 | 2017-11-17 | 丰田自动车株式会社 | 废气净化用催化剂 |
CN107427826A (zh) * | 2015-03-27 | 2017-12-01 | 丰田自动车株式会社 | 废气净化用催化剂 |
CN111263661A (zh) * | 2017-10-27 | 2020-06-09 | 株式会社科特拉 | 使用了金属基材的排气净化装置及其制造方法 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR19980083844A (ko) * | 1997-05-19 | 1998-12-05 | 이웅열 | 새로운 아지리딘 유도체 및 그 제조방법 |
CN101674884B (zh) | 2007-05-08 | 2012-07-04 | 丰田自动车株式会社 | 废气净化用催化剂、使用该催化剂的废气净化装置和废气净化方法 |
JP5326251B2 (ja) * | 2007-10-02 | 2013-10-30 | マツダ株式会社 | 排気ガス浄化触媒装置 |
EP3448549A1 (en) | 2016-04-29 | 2019-03-06 | Johnson Matthey Public Limited Company | Exhaust system |
WO2017187412A1 (en) | 2016-04-29 | 2017-11-02 | Johnson Matthey Public Limited Company | Exhaust system |
CA3027524A1 (en) * | 2016-06-13 | 2017-12-21 | Basf Corporation | Catalytic article comprising combined pgm and osc |
GB201721527D0 (en) * | 2017-12-21 | 2018-02-07 | Johnson Matthey Japan Godo Kaisha | Oxidation catalyst for a diesel engine exhaust |
US11745173B2 (en) * | 2020-03-31 | 2023-09-05 | Johnson Matthey Public Limited Company | Tin incorporated catalysts for gasoline engine exhaust gas treatments |
EP3978100A1 (de) * | 2020-09-30 | 2022-04-06 | UMICORE AG & Co. KG | Bismut enthaltender gezonter dieseloxidationskatalysator |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5705265A (en) * | 1986-03-24 | 1998-01-06 | Emsci Inc. | Coated substrates useful as catalysts |
FR2622126B1 (fr) * | 1987-10-21 | 1991-06-14 | Procatalyse Ste Fse Produits C | Catalyseur pour le traitement des gaz d'echappement des moteurs a combustion interne et procede de fabrication de ce catalyseur |
US4939113A (en) * | 1987-11-03 | 1990-07-03 | Engelhard Corporation | Hydrogen sulfide suppressing catalyst system using an oxide of copper, manganese, nickel or iron |
EP0664147B1 (en) * | 1994-01-20 | 1998-07-22 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gases |
JP2795182B2 (ja) | 1994-06-27 | 1998-09-10 | 日本鋼管株式会社 | 金属管被覆光ファイバーケーブルの接続方法 |
US6497851B1 (en) | 1994-12-06 | 2002-12-24 | Englehard Corporation | Engine exhaust treatment apparatus and method of use |
CN1205652A (zh) | 1995-12-21 | 1999-01-20 | 恩格尔哈德公司 | 发动机废气处理装置及应用方法 |
US6548446B1 (en) * | 1997-07-02 | 2003-04-15 | Engelhard Corporation | Catalyst for selective oxidation of carbon monoxide |
US6037307A (en) | 1998-07-10 | 2000-03-14 | Goal Line Environmental Technologies Llc | Catalyst/sorber for treating sulfur compound containing effluent |
US6375910B1 (en) | 1999-04-02 | 2002-04-23 | Engelhard Corporation | Multi-zoned catalytic trap and methods of making and using the same |
JP4221125B2 (ja) | 1999-09-01 | 2009-02-12 | 三菱自動車工業株式会社 | 希薄燃焼内燃機関の排気浄化装置 |
US20020103078A1 (en) | 2001-01-26 | 2002-08-01 | Zhicheng Hu | SOx trap for enhancing NOx trap performance and methods of making and using the same |
US7118717B2 (en) * | 2002-09-06 | 2006-10-10 | Engelhard Corporation | Simplified article for carbon monoxide removal |
-
2005
- 2005-05-26 JP JP2005153781A patent/JP2006326495A/ja not_active Withdrawn
-
2006
- 2006-05-25 KR KR1020077027483A patent/KR100921994B1/ko not_active IP Right Cessation
- 2006-05-25 US US11/921,026 patent/US7795174B2/en not_active Expired - Fee Related
- 2006-05-25 CN CNA2006800176040A patent/CN101180126A/zh active Pending
- 2006-05-25 EP EP06747061A patent/EP1883472A2/en not_active Withdrawn
- 2006-05-25 WO PCT/JP2006/310956 patent/WO2006126734A2/en active Application Filing
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CN102405102A (zh) * | 2009-05-19 | 2012-04-04 | 美礼联无机化工公司 | 无钒汽车催化剂的催化剂助催化剂 |
CN102513165A (zh) * | 2011-12-14 | 2012-06-27 | 刘碧兰 | 一种高效尾气净化三元催化剂涂敷方法 |
CN107360714A (zh) * | 2015-03-27 | 2017-11-17 | 丰田自动车株式会社 | 废气净化用催化剂 |
CN107427826A (zh) * | 2015-03-27 | 2017-12-01 | 丰田自动车株式会社 | 废气净化用催化剂 |
US10539056B2 (en) | 2015-03-27 | 2020-01-21 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purification catalyst |
US11224840B2 (en) | 2015-03-27 | 2022-01-18 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purification catalyst |
CN104801313A (zh) * | 2015-04-15 | 2015-07-29 | 永康市奥鑫科技有限公司 | 一种用于挥发性有机废气净化的催化剂及其制备方法 |
CN104801313B (zh) * | 2015-04-15 | 2017-08-29 | 永康市奥鑫科技有限公司 | 一种用于挥发性有机废气净化的催化剂及其制备方法 |
CN105772023A (zh) * | 2016-03-31 | 2016-07-20 | 湖南省吉安特技术有限公司 | 一种高效三元催化剂涂层的制作方法 |
CN111263661A (zh) * | 2017-10-27 | 2020-06-09 | 株式会社科特拉 | 使用了金属基材的排气净化装置及其制造方法 |
CN111263661B (zh) * | 2017-10-27 | 2023-05-30 | 株式会社科特拉 | 使用了金属基材的排气净化装置及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2006126734A2 (en) | 2006-11-30 |
WO2006126734A3 (en) | 2007-02-08 |
EP1883472A2 (en) | 2008-02-06 |
US20090082199A1 (en) | 2009-03-26 |
KR100921994B1 (ko) | 2009-10-14 |
JP2006326495A (ja) | 2006-12-07 |
US7795174B2 (en) | 2010-09-14 |
KR20080007633A (ko) | 2008-01-22 |
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