CN1933907B - 选择性沸石催化剂改性 - Google Patents
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Abstract
一种改性沸石催化剂以增加催化剂选择性的方法通过将矾土溶解在含磷的酸溶液中，和将沸石催化剂用溶解矾土溶液处理而实现。一种制备芳族产物，如二甲苯产物的方法也通过将该改性的沸石催化剂与芳族烃，如甲苯，和烷基化剂，如甲醇，在适用于芳族烷基化的反应条件下接触而实现。对于二甲苯产物，芳族烃可以是甲苯和反应条件可适用于甲苯甲基化和烷基转移化中的至少一种。
Description
技术领域
本发明一般涉及芳族化合物的烷基化和用于这些反应的催化剂。
背景
对二甲苯是一种有价值的取代的芳族化合物，因为非常需要用于将它氧化成对苯二甲酸，一种在形成聚酯纤维和树脂时的主要组分。它可通过石脑油的加氢处理(催化重整)，石脑油或气体油的蒸汽裂解，和甲苯歧化而商业上得到。
使用甲醇的甲苯的烷基化也称作甲苯甲基化，已经用于实验室研究以生产对二甲苯。甲苯甲基化已知在酸性催化剂，尤其在沸石或沸石型催化剂上进行。尤其是，ZSM-5-型沸石，β沸石和铝磷酸盐硅石(SAPO)催化剂已用于此。一般，邻(o)-，间(m)-和对(p)-二甲苯的热动态平衡混合物可由甲苯的甲基化而形成，例如由以下反应所示。
o-，m-，和p-二甲苯的热动态平衡组合物在反应温度约500℃下可分别是约25，50和25摩尔％。但这些甲苯甲基化可在宽温度范围内进行。对二甲苯可通过吸附和异构体化的一个周期而从混合二甲苯中分离。副产物如C9+和其它芳族产物可通过二甲苯产物的二次烷基化而制成。
明显较高量的p-二甲苯可在甲苯甲基化反应中得到，如果该催化剂具有形状选择性性能。形状选择性性能可在改性的沸石催化剂中通 过窄化沸石孔开口尺寸，钝化沸石的外部表面或控制沸石酸度而得到。甲苯甲基化可在改性的ZSM-5或ZSM-5-型沸石催化剂上进行，得到得到二甲苯产物包含其量明显高于热动态浓度的p-二甲苯的二甲苯产物。
在Kaeding，等人，使用甲醇选择性烷基化甲苯生产对二甲苯，催化杂志，Vol.67，pp.159-174(1981)中，描述了一种通过引入5％磷而制造ZSM-5催化剂的步骤，其中催化剂用二苯基三价膦酸在甲苯中的溶液浸渍。如此改性的ZSM-5催化剂表现出的甲苯甲基化活性是在二甲苯产物中的84-90％对异构体。在另一步骤中，催化剂通过从含水磷酸试剂中引入8.51％磷而改性。该催化剂表现出高达97％的p-二甲苯选择性，但催化剂由于焦炭沉积而在数小时内活性下降。
遗憾的是，甲苯甲基化的商业成功存在许多技术障碍。这些包括快速催化剂减活化，低甲醇选择性，等等。用于甲苯甲基化的大多数，如果不是所有的，催化剂表现出快速催化剂减活化。通常，甲苯转化率在生产中由于在催化剂上的快速焦炭形成而随着时间下降。催化剂减活化是甲苯甲基化的商业使用所要克服的最困难的技术障碍。
具体地说，本发明公开了以下内容：
1.一种改性沸石催化剂以增加该沸石催化剂在芳族烷基化反应中的对-异构体选择性的方法，该方法包括将矾土溶解在含磷的酸溶液中，并将沸石催化剂用上述溶解了矾土的含磷的酸溶液处理。
2.上款1的方法，其中：酸包括含磷的无机酸。
3.上款1的方法，其中：酸包括浓度为至少50wt％的磷酸和亚磷酸的至少一种的水溶液。
4.上款1的方法，其中：矾土溶解包括将矾土在过量酸中溶解。
5.上款1的方法，其中：矾土以大于0.01克矾土/克沸石的量被引入沸石中。
6.上款1的方法，其中：含磷的酸溶液的用量是至少0.1g含磷的酸溶液/克沸石。
7.上款1的方法，其中：沸石催化剂是硅石/矾土比率为25至1000的 ZSM-5-型沸石催化剂。
8.上款7的方法，其中：所述处理的ZSM-5型沸石催化剂具有总孔体积0.10ml/g至0.20ml/g。
9.上款1的方法，其中：处理的沸石催化剂具有在250-350℃下显示氨温度程序化解吸峰的酸位。
10.一种制备烷基芳族产物的方法，包括：将矾土溶解在无机含磷的酸溶液中；将沸石催化剂用该酸溶液处理；和将所述处理的沸石催化剂与芳族烃和烷基化剂在适用于芳族烷基化的反应条件下接触。
11.上款10的方法，其中：芳族烃是甲苯。
12.上款11的方法，其中：烷基化剂是甲醇。
13.上款10的方法，其中：沸石催化剂是ZSM-5-型沸石催化剂。
14.上款10的方法，其中：矾土以至少0.01克矾土/克沸石的量被引入沸石中。
15.上款10的方法，其中：处理的沸石催化剂具有0.03至0.08克磷/克沸石。
16.一种制备二甲苯产物的方法，包括：将矾土溶解在磷酸溶液中；将ZSM-5-型沸石催化剂用该磷酸溶液处理；和将所述处理的沸石催化剂与甲苯在适用于甲苯甲基化和烷基转移化中的至少一种的反应条件下接触。
17.上款16的方法，其中：磷酸溶液的用量是0.2g至0.3g/克沸石。
18.上款16的方法，其中：矾土以0.01g/g沸石至0.02g/g沸石的量被引入沸石中。
19.上款16的方法，其中：矾土溶解包括将矾土在过量磷酸中溶解。
20.上款16的方法，其中：催化剂在用于甲苯甲基化时具有大于混合二甲苯的85％的对二甲苯选择性。
21.上款16的方法，其中：催化剂的甲苯转化率在大于500小时的时间内在基本上恒定的催化剂床温度下具有低于0.5％/天的转化率损失。
22.上款16的方法，其中：甲苯甲基化所用的原料包含每摩尔甲苯/ 甲醇至少0.1摩尔量的水。
23.上款16的方法，其中：甲苯甲基化所用的原料包含每摩尔甲苯/甲醇至少1.0摩尔量的氢。
24.上款16的方法，其中：反应条件包括至少10psig的反应器压力。
附图的简要描述
为了更全面地理解本发明，现结合附图进行以下描述，其中：
图1是矾土-PA改性的ZSM-5(E)，PA改性的ZSM-5(L)，和非改性的ZSM-5(P)催化剂的NH3-TPD的图。
图2是对于仅用磷酸处理的沸石催化剂和按照本发明改性的那些催化剂，对二甲苯选择性作为磷酸使用率函数的图；和
图3是对于仅用磷酸处理的催化剂和按照本发明的催化剂，总二甲苯转化率和对二甲苯转化率随着时间的图。
详细描述
与使用未改性催化剂的甲苯甲基化时的热动态平衡值相比，使用磷酸(PA)改性的ZSM-5-型沸石催化剂已经表现出明显较高量的p-二甲苯产率。但已发现，在相同的磷酸用量下，可通过将溶解或″蒸煮″矾土引入这些催化剂而实现超出仅磷酸改性的沸石时所实现的对二甲苯的 增加选择性。
本文所用的措辞″ZSM-5-型″是指结构上与ZSM-5沸石相同的那些。另外，措辞″ZSM-5″和″ZSM-5-型″也可互换地用于相互包括且不应以任何限定方式理解。ZSM-5沸石催化剂和其制备描述于U.S.专利No.3,702,886，在此作为参考并入本发明。在本发明中，ZSM-5沸石催化剂可包括在改性之前具有硅石/矾土摩尔比25至1000，更尤其在改性之前硅石/矾土摩尔比约30至约300的那些。
尽管已具体提及ZSM-5-型沸石用于本发明所特别应用的甲苯甲基化，本文所讨论的改性可应用于孔直径5.0埃至7.0埃的其它沸石，如丝光沸石，ω，等另外，具体提及该改性的催化剂在甲苯甲基化中的应用，其中所述改性的沸石非常适合于此。但对本领域熟练技术人员显而易见的是，该催化剂可用于其它种类的反应，如烷基转移化和其它芳族烷基化反应。尤其是，本发明催化剂可用于这些反应以提供对对异构体在混合二烷基化芳族产物中的增加的选择性。
本文所用的催化活性可表示为相对甲苯加料的摩尔数而言被转化成的甲苯的％摩尔，且可定义为：
摩尔％甲苯转化率＝(Ti-To/Ti)x 100 (2)
其中，Ti是加料的甲苯的摩尔数和T0是未反应的甲苯的摩尔数。本文所用的对总二甲苯的选择性可表示为：
摩尔％总二甲苯选择性＝(Xtx/Ti-To)x 100 (3)
其中，Xtx，是产物中的总(o-，m-或p-)二甲苯的摩尔数。
本文所用的p-二甲苯的选择性可表示为：
摩尔％p-二甲苯选择性＝(Xp/Xtx)x 100 (4)
其中，Xp是p-二甲苯的摩尔数。
沸石可通过将用已被预溶解在含磷(P)的无机酸，如磷酸(H3PO4，pKa＝2.12，对于步骤1)或磷酸(H3PO3，pKa＝2.00，对于步骤1)中的矾土处理而改性。尽管在以下描述中具体提及磷酸，但显然其它的含磷酸可替代使用。将起始为固体形式的矾土溶解在酸溶液中。磷酸溶液可具有足够的浓度和量以溶解所有的或基本上所有的矾土，这在容 易变透明时显然看出。任何剩余的或未溶解的矾土可根据需要被过滤或以其它方式从溶液中去除，然后用于改性沸石催化剂。
在溶解矾土时，磷酸可过量使用，这要进一步讨论。矾土的合适量的例子可以是约0.005g至约0.10g矾土/克沸石粉末。磷酸的合适量可以是约0.05g或更多至约0.5g/克沸石粉末。酸可以是至少50％酸重量水溶液，如85％酸重量水溶液的浓缩液体形式。
为了促进溶解矾土，可首先将它加入水中并在搅拌下加热至升高的温度。磷酸可随后加入矾土中。合适的温度的一个例子是约70至约100℃。溶解矾土溶液可包含过量或残余的磷酸。
在加入含矾土的磷酸溶液之后，沸石粉末可与水相结合以制成含水淤浆或悬浮液。淤浆可被加热和搅拌以促进催化剂制备。适用于沸石淤浆的温度范围的一个例子是约70至约100℃。溶解的矾土可随后与沸石淤浆相结合。另外，可将溶解的矾土加入沸石粉末以形成沸石淤浆。
留在溶解矾土溶液中的过量或残余磷酸可促进沸石的改性以提供形状选择性性能。另外，可将其它的磷酸加入淤浆中以改性或进一步促进沸石的改性以提供形状选择性性能。在ZSM-5-型沸石的情况下，这些催化剂可通过用磷酸对沸石改性而改性增加甲苯甲基化反应中的p-二甲苯选择性。但从溶解矾土溶液中引入的矾土已经表现出进一步增加沸石的选择性，超出单独使用磷酸改性所实现的，这在以下讨论的实施例中说明。
现包含溶解矾土/酸溶液的沸石淤浆可随后被加热直至所有的液体蒸发。合适的温度范围的一个例子是70℃至100℃。淤浆也可在该步骤过程中被搅拌或搅动以确保均匀处理。
矾土-PA改性的沸石催化剂可为粘结地使用或与粘结剂粘结。合适的粘结剂的例子包括矾土，粘土，和硅石之类的材料。用于制备粘结催化剂的那些技术是本领域熟知的。粘结或未粘结的催化剂可在400℃-570℃的温度下在包含氧的环境，通常空气中煅烧。
改性的催化剂可与合适的加料在烷基化反应条件下接触以进行芳 族烷基化。本发明所应用的烷基化反应的例子包括使用烷基化剂如甲醇的甲苯烷基化。其它烷基化反应可包括烷基转移化，如在氢存在下用于得到苯和混合二甲苯的气相甲苯歧化。
用于甲苯甲基化或其它芳族烷基化的反应器压力可变化，但通常是约10至约1000psig。
反应可在常用于芳族烷基化反应的各种不同的反应器中进行。单个或串联和/或并联的多个反应器适用于进行甲苯甲基化或其它芳族烷基化反应。
尤其是，该改性的催化剂是可用于甲苯甲基化，用于由甲苯和甲醇的加料制备二甲苯产物，和增加对p-二甲苯的选择性。在这些反应中，水可按照至少0.1摩尔水/摩尔甲苯/甲醇加料的量被引入，例如描述于US.专利申请系列No.10/675,780(2003年9月30日递交，在此作为参考并入本发明)。还使用氢共加料。氢的用量可以是至少1.0摩尔/摩尔甲苯/甲醇加料。
如果按照本发明改性的ZSM-5-型沸石催化剂用于甲苯甲基化，可得到具有p-二甲苯含量80％，85％，90％或95％或更多(基于二甲苯的总摩尔数)的二甲苯产物。
以下实施例进一步说明本发明。
实施例
催化剂制备
催化剂A-H
为了形成每种催化剂，在400ml烧杯中制备将具有SiO2/Al2O3摩尔比280的NH4-ZSM-5沸石粉末在50ml去离子水中的淤浆。将烧杯放在热板上并将沸石悬浮液使用磁力搅拌棒搅拌。使沸石悬浮液(或淤浆)的温度达到约80-85℃。溶解矾土在磷酸中的溶液另外通过将一定量的矾土加入10ml去离子水中而制备。将水中的矾土随后加热和搅拌直至温度是约70至80℃，此时向淤浆中慢慢加入一定量的磷酸(H3PO4)(85wt％水溶液)。最终得到透明溶液，表明所有的矾土已经溶解。将矾土/磷酸溶液随后加入沸石淤浆。淤浆继续加热和搅拌直至基本上所有的 液体蒸发。沸石随后在约90℃下干燥过夜并随后在空气中在约510℃下煅烧10小时。将改性的和煅烧的沸石随后被粉碎和使用20和40目筛网过筛。
一系列催化剂A-H(参见表1)使用以上技术通过改变矾土磷酸的量(相对起始NH4-ZSM-5粉末的量)而制备。催化剂A-H的BET表面积和总孔体积(通过N2吸附而测定)在下表1中给出。
对比催化剂I-O
为了对比，将ZSM-5沸石催化剂用磷酸，但没有溶解矾土进行处理。起始原料是具有SiO2/Al2O3摩尔比280的NH4-ZSM-5沸石粉末。对于每一催化剂，在400ml烧杯中制备包含NH4-ZSM-5沸石和100-150ml去离子水的淤浆。将烧杯放在热板上并将沸石悬浮液使用磁力搅拌棒搅拌。悬浮液的温度保持约90℃。将磷酸(85wt％水溶液)滴加到烧杯中。继续加热直至所有的液体蒸发。将仅磷酸改性的沸石在90℃至110℃下干燥至少4小时并随后在510℃下在空气下煅烧10小时。将煅烧沸石随后被粉碎和使用20和40目筛网过筛。
一系列催化剂I-O(参见表1)通过改变磷酸的量(相对起始NH4-ZSM-5粉末的量)而制备。催化剂I-O的BET表面积和总孔体积(通过N2吸附而测定)在表1中给出。
对比催化剂P
另外测试非改性的ZSM-5沸石催化剂(催化剂P)。起始原料是具有SiO2/Al2O3摩尔比280的NH4-ZSM-5沸石粉末。沸石粉末在530℃下在空气下煅烧10hr并随后压制和使用20和40目筛网过筛，用于甲苯甲基化反应的反应器。
实施例1
在表1中提及和如上所述制备的催化剂A-P用于甲苯甲基化反应。反应分别在固定床，连续流动型反应器中进行。在所有情况下，所用的催化剂通过在氢(H2)流动下慢慢升高催化剂床温度(约5℃/min)至200℃达至少1小时而干燥。将预混的甲苯和甲醇加料(摩尔比2/1)加入在200℃下的反应器并将催化剂床入口温度升至约500℃。基于甲苯/甲醇 加料的液体小时空间速度(LHSV)保持在约31hr-1并加入H2气体的共加料并保持提供H2/HC摩尔比约0.1。将水加入烃(HC)加料中和在引入到反应器中之前蒸发H2O/HC摩尔比是约0.65和反应器压力是约20psig。得到以下结果，如下表1所示。
表1
基于在制备过程中所用的PA的总量
沸石催化剂的BET表面积(SA)和总孔体积(PV)的下降源自矾土-PA改性，如表1所示。改性的沸石催化剂的总孔体积可以是0.10ml/g至0.20ml/g，更尤其0.12至0.18ml/g。例如，非改性的ZSM-5催化剂(表1中的催化剂P)相应具有SA和PV375m2/g和0.244ml/g。表1中的矾土-PA改性的催化剂A-H相应具有SA和PV223-328m2/g和0.135-0.192ml/g。
改性的和非改性的沸石催化剂的酸度通过使用氨温度程序化解吸(NH3-TPD)技术而表征。该方法是本领域熟知的。对于NH3-TPD分析，催 化剂样品(0.2g)首先在He流速10cc/min下在500℃下干燥3小时。温度随后降至100℃，这时将催化剂用氨气体保护。在使用NH3饱和之后，催化剂在100℃下在He流动下解吸，从样品中解吸出物理吸附的NH3。NH3-TPD在解吸温度温升18.4℃/min下在He流速16cc/min下进行。解吸的NH3和水(如果任何)在NH3-TPD运行过程中监控。非改性的催化剂(表1中的催化剂P)具有的NH3-TPD峰，表明该非改性的ZSM-5催化剂具有强酸位。矾土-PA改性的催化剂具有在约450℃处在约300℃处的宽NH3-TPD峰，表明该改性的催化剂具有弱至中等强度的酸位。NH3-TPD分布用于催化剂P，E和L的例子在图1中给出。
如表1和图2所示，矾土/磷酸改性的催化剂与磷酸改性的催化剂相比具有较高p-二甲苯选择性，基于所用的磷酸的总量。在用矾土-PA改性之后制备的催化剂，A-E具有随着PA增加而增加的p-二甲苯选择性(图1)。例如，通过使用0.22g H3PO4/g沸石(0.07g P/g沸石)而制备的表1中的催化剂E具有在总二甲苯中的95-97％p-二甲苯浓度。而通过仅使用磷酸而改性的催化剂表现出仅高达93％的p-二甲苯，如果与0.28g H3PO4/g沸石(0.09g P/g沸石)一起使用。
实施例2
为了对比，将使用基本上相同的量的磷酸(分别为0.22g PA和0.28g PA，每克沸石)制备的催化剂E(矾土/PA改性的)和L(PA改性的)用于甲苯甲基化反应。反应分别在固定床，连续流动型反应器中进行。在所有情况下，催化剂通过在氢(H2)流动下慢慢升高催化剂床温度(约5℃/min)至200℃达至少1小时而干燥。将预混的甲苯和甲醇加料(摩尔比2/1)加入在200℃下的反应器中并将H2气体的共加料加入和保持提供H2/HC摩尔比约7。将水加入烃(HC)加料中和在引入到反应器中之前蒸发。催化剂床温度随后升至500℃。保持液体小时空间速度(LHSV)(仅基于甲苯/甲醇加料计算)约2hr-1。H2O/HC摩尔比是约0.7和反应器压力是约20psig。得到以下结果并在下表2和图3中给出。
表2
在455-500小时运行时间内出现的停电导致完全停止运行，并重新启动反应器。
从表2和图3可以看出，矾土/PA改性的沸石具有高于仅PA改性的沸石的p-二甲苯选择性。催化剂E和L都具有几乎相同的减活化分布。催化剂E(矾土/PA改性的)在恒定催化剂床入口温度约500℃下最高约450小时运行期内表现出小的甲苯转化率下降(甲苯转化率下降0.19％，每24小时)，此时发生停电，导致反应器完全停止工作。如果重新启动反应，该催化剂在500-630运行小时内具有较低但稳定的甲苯转化率。而催化剂L(PA改性的)也具有小的甲苯转化率下降(甲苯转化率下降0.33％， 每24小时)。在催化剂L的情况下，催化剂床入口温度在头194小时内是约500℃，然后升至约525℃和继续运行约340小时。
尽管本发明仅根据其某些形式进行显示，但对本领域熟练技术人员显而易见的是，它不受如此据信，而是可在不背离本发明范围的情况下进行各种改变和改进。因此，所附权利要求书要被宽泛地和按照与本发明范围一致的方式进行合理理解。
Claims (24)
1.一种改性沸石催化剂以增加该沸石催化剂在芳族烷基化反应中的对-异构体选择性的方法，该方法包括将矾土溶解在含磷的酸溶液中，并将沸石催化剂用上述溶解了矾土的含磷的酸溶液处理。
2.权利要求1的方法，其中：酸包括含磷的无机酸。
3.权利要求1的方法，其中：酸包括浓度为至少50wt％的磷酸和亚磷酸的至少一种的水溶液。
4.权利要求1的方法，其中：矾土溶解包括将矾土在过量酸中溶解。
5.权利要求1的方法，其中：矾土以大于0.01克矾土/克沸石的量被引入沸石中。
6.权利要求1的方法，其中：含磷的酸溶液的用量是至少0.1g含磷的酸溶液/克沸石。
7.权利要求1的方法，其中：沸石催化剂是硅石/矾土比率为25至1000的ZSM-5-型沸石催化剂。
8.权利要求7的方法，其中：所述处理的ZSM-5型沸石催化剂具有总孔体积0.10ml/g至0.20ml/g。
9.权利要求1的方法，其中：处理的沸石催化剂具有在250-350℃下显示氨温度程序化解吸峰的酸位。
10.一种制备烷基芳族产物的方法，包括：将矾土溶解在无机含磷的酸溶液中；将沸石催化剂用该酸溶液处理；和将所述处理的沸石催化剂与芳族烃和烷基化剂在适用于芳族烷基化的反应条件下接触。
11.权利要求10的方法，其中：芳族烃是甲苯。
12.权利要求11的方法，其中：烷基化剂是甲醇。
13.权利要求10的方法，其中：沸石催化剂是ZSM-5-型沸石催化剂。
14.权利要求10的方法，其中：矾土以至少0.01克矾土/克沸石的量被引入沸石中。
15.权利要求10的方法，其中：处理的沸石催化剂具有0.03至0.08克磷/克沸石。
16.一种制备二甲苯产物的方法，包括：将矾土溶解在磷酸溶液中；将ZSM-5-型沸石催化剂用该磷酸溶液处理；和将所述处理的沸石催化剂与甲苯在适用于甲苯甲基化和烷基转移化中的至少一种的反应条件下接触。
17.权利要求16的方法，其中：磷酸溶液的用量是0.2g至0.3g/克沸石。
18.权利要求16的方法，其中：矾土以0.01g/g沸石至0.02g/g沸石的量被引入沸石中。
19.权利要求16的方法，其中：矾土溶解包括将矾土在过量磷酸中溶解。
20.权利要求16的方法，其中：催化剂在用于甲苯甲基化时具有大于混合二甲苯的85％的对二甲苯选择性。
21.权利要求16的方法，其中：催化剂的甲苯转化率在大于500小时的时间内在基本上恒定的催化剂床温度下具有低于0.5％/天的转化率损失。
22.权利要求16的方法，其中：甲苯甲基化所用的原料包含每摩尔甲苯和甲醇至少0.1摩尔量的水。
23.权利要求16的方法，其中：甲苯甲基化所用的原料包含每摩尔甲苯和甲醇至少1.0摩尔量的氢。
24.权利要求16的方法，其中：反应条件包括至少10psig的反应器压力。
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| US10/790,948 US6943131B1 (en) | 2004-03-02 | 2004-03-02 | Selective zeolite catalyst modification |
| US10/790,948 | 2004-03-02 | ||
| PCT/US2005/006757 WO2005084798A1 (en) | 2004-03-02 | 2005-03-02 | Selective zeolite catalyst modification |
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| US6187982B1 (en) * | 1999-10-15 | 2001-02-13 | Mobil Oil Corporation | Process for converting dienes and oxygenates to para-xylene and light olefins |
| US6726834B2 (en) * | 1999-10-22 | 2004-04-27 | Intevep, S.A. | Process for catalytic cracking of a hydrocarbon feed with a MFI aluminisilcate composition |
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| JP3489048B2 (ja) * | 2000-02-01 | 2004-01-19 | 日産自動車株式会社 | 排気ガス浄化用触媒 |
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- 2005-03-02 KR KR1020067018459A patent/KR101117860B1/ko active IP Right Grant
- 2005-03-02 WO PCT/US2005/006757 patent/WO2005084798A1/en active Application Filing
- 2005-03-02 CN CN2005800096107A patent/CN1933907B/zh not_active Expired - Fee Related
- 2005-03-02 EP EP05724327.1A patent/EP1725329B1/en active Active
- 2005-05-20 US US11/134,567 patent/US7196237B2/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| US20050197245A1 (en) | 2005-09-08 |
| US20050209494A1 (en) | 2005-09-22 |
| WO2005084798A1 (en) | 2005-09-15 |
| EP1725329B1 (en) | 2020-01-08 |
| EP1725329A1 (en) | 2006-11-29 |
| US6943131B1 (en) | 2005-09-13 |
| KR101117860B1 (ko) | 2012-03-15 |
| KR20070004700A (ko) | 2007-01-09 |
| CN1933907A (zh) | 2007-03-21 |
| EP1725329A4 (en) | 2012-04-11 |
| US7196237B2 (en) | 2007-03-27 |
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