CN1221469C - 生产二氧化氯的方法 - Google Patents
生产二氧化氯的方法 Download PDFInfo
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Abstract
本发明涉及连续生产二氧化氯的方法和设备,所述方法包括如下步骤:向反应器中进料水溶液形式的氯酸根离子、酸和过氧化氢;在反应器中还原氯酸根离子为二氧化氯,从而在反应器中形成含二氧化氯的产物流;向包含喷嘴(26)的喷射器中进料流动水(5);使流动水流过喷嘴,并使其按至少部分盘旋或螺旋的方式进一步流过喷射器;输送来自反应器的产物流去喷射器,并使其与流动水混合,从而形成含二氧化氯的稀释水溶液,以及;从喷射器中抽出含二氧化氯的稀释水溶液。
Description
发明领域
本发明涉及由氯酸根离子、酸和过氧化氢生产二氧化氯的方法。
发明背景
二氧化氯用于各种用途中,例如用于纸浆漂白、脂肪漂白、水的净化以及从工业废物中脱除有机物质中。因为二氧化氯的贮存是不稳定的,所以其必须现场制备。
通常在含水的反应介质中通过使碱金属氯酸盐或氯酸与还原剂反应而制备二氧化氯。二氧化氯可以作为气体而从反应介质中抽出,正如在US 5091166、US 5091167和EP 612686中所描述的方法那样。通常然后将二氧化氯气体在水中吸收从而形成其水溶液。
对于在较小规模的装置中生产二氧化氯,例如水的净化用途或小型漂白装置来说,有利的是不从反应介质中分离二氧化氯气体,而直接从反应器回收含二氧化氯的溶液,并任选用水稀释后进行。这种方法在US 2833624、US 4534952、US 5895638和WO 00/76916中描述,并且在最近几年已经实现工业化。但仍需要进一步改进。具体地,已经发现对于某些应用来说很难获得所需要的具有足够高二氧化氯浓度的溶液,这些应用比如回收纸漂白、甘蔗渣漂白、或小规模的纸浆漂白。对于其中减小水的流量很重要的应用,二氧化氯浓度高也可能是有用的。
发明概述
本发明的一个目的是提供一种能够直接生产高浓度二氧化氯水溶液的方法。
本发明的另一个目的是提供一种具有高生产能力的直接生产二氧化氯水溶液的方法。
本发明的另一个目的是提供实施所述方法的设备。
发明的简要描述
已经令人惊奇地发现通过提供连续生产二氧化氯的方法有可能实现这些目的,所述方法包括如下步骤:
向反应器中进料水溶液形式的氯酸根离子、酸和过氧化氢;
在反应器中还原氯酸根离子为二氧化氯,从而在反应器中形成含二氧化氯的产物流;
向包含喷嘴的喷射器进料流动水;
使流动水流过喷嘴,并使其以至少部分、优选充分地盘旋或螺旋的方式进一步流过喷射器;
输送来自反应器的产物流去喷射器,并使其与流动水混合,从而形成含二氧化氯的稀释水溶液,以及;
从喷射器中抽出含二氧化氯的稀释水溶液。
氯酸根离子可以作为包含氯酸和/或金属氯酸盐、优选为碱金属氯酸盐的水溶液而进料至反应器中。碱金属可以为钠、钾或其混合物,并且其中钠是最优选的。如果不应用氯酸,则必须向反应器进料另一种酸,优选为无机酸,例如硫酸、盐酸或硝酸,并且其中硫酸是最优选的。进料至反应器的H2O2∶ClO3 -摩尔比适当地为约0.2∶1至约2∶1,优选为约0.5∶1至约1.5∶1,最优选为约0.5∶1至约1∶1。在金属氯酸盐和氯酸中总是含有一些氯化物杂质,但是也完全有可能向反应器进料更多的氯化物,例如金属氯化物或盐酸。但是,为了减少氯的形成,优选的是保持进料至反应器的氯离子量较低,适当地低于约1mol%ClO3 -的Cl-,优选低于约0.1mol%,更优选低于约0.05mol%,最优选低于约0.02mol%。
在一个特别优选的实施方案中,碱金属氯酸盐和过氧化氢以预先混合的水溶液形式进料至反应器,例如以WO 00/76916中所描述的组合物的形式进料至反应器,该文献在此引用作为参考。这种组合物可以为一种水溶液,所述水溶液含有约1至约6.5摩尔/升的碱金属氯酸盐,优选为约3至约6摩尔/升,还含有约1至约7摩尔/升的过氧化氢,优选为约3至约5摩尔/升,以及至少一种保护胶体、基团捕获剂或膦酸基络合剂,其中所述水溶液的pH值适当地为约0.5至约4,优选为约1至约3.5,最优选为约1.5至约3。优选存在至少一种膦酸基络合剂,其量优选为约0.1至约5毫摩尔/升,最优选为约0.5至约3毫摩尔/升。如果存在有保护胶体,其浓度优选为约0.001至约0.5摩尔/升,最优选为约0.02至约0.05摩尔/升。如果存在基团捕获剂,则其浓度优选为约0.01至约1摩尔/升,最优选为约0.02至约0.2摩尔/升。特别优选的组合物包括至少一种膦酸基络合剂,所述络合剂选自1-羟基亚乙基-1,1-二膦酸、1-氨基乙烷-1,1-二膦酸、氨基三(亚甲基膦酸)、乙二胺四(亚甲基膦酸)、己二胺四(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)、二亚乙基三胺六(亚甲基膦酸)和1-氨基烷烃-1,1-二膦酸如吗啉基甲烷二膦酸、N,N-二甲基氨基二甲基二膦酸、氨基甲基二膦酸或其盐,优选为其钠盐。有用的保护胶体包括锡化合物,例如碱金属锡酸盐,特别是锡酸钠(Na2(Sn(OH)6)。有用的基团捕获剂包括吡啶羧酸,例如2,6-吡啶二羧酸。氯离子的合适量低于约50毫摩尔/升,优选低于约5毫摩尔/升,最优选低于0.5毫摩尔/升。
在应用硫酸作原料的情况下,其浓度优选为约70wt%至约96wt%,并且最优选为约75wt%至约85wt%,其优选的温度为约0℃至约80℃,最优选为约20℃至约60℃,因为这样才有可能在基本绝热的情况下操作所述过程。对于所生产的每kg ClO2来说,优选进料约2至约6kg的H2SO4,最优选为约3至约5kg的H2SO4。另外,可以应用等量的其它无机酸。
生产二氧化氯的总反应可以由下式进行描述:
其精确的机理是复杂的,并且据信其涉及氯酸根和氯化物(即使不是单独加入的,其总是在氯酸盐中作为杂质以足够量存在)之间的第一反应从而得到二氧化氯和氯,并且随后氯与过氧化氢反应形成氯化物。但是,当考虑总反应时,过氧化氢通常被视为与氯酸根离子反应的还原剂。
氯酸根离子还原为二氧化氯导致在反应器中形成产物流,所述产物流通常包括液体和泡沫,并且包含二氧化氯、氧,并且在大部分情况下还包含一些剩余的未反应原料化学物质。二氧化氯和氧可以溶解在液体中和以气泡形式存在。当金属氯酸盐和无机酸用作原料化学物质时,则产物流除了含有二氧化氯和氧外,还含有无机酸的金属盐,以及一些剩余的金属氯酸盐和无机酸。已经发现氯酸根离子转化为二氧化氯的转化程度有可能达到约75%至100%,优选为约80%至100%,最优选为约95%至100%。
在运行压力下反应器中的温度合适地保持为低于反应物和产物流的沸点,优选为约20℃至约80℃,最优选为约30℃至约60℃。反应器内所保持的压力合适地为稍低于大气压,优选为约30至约100kPa绝压,最优选为约65至约95kPa绝压。
反应器可以包括一个或几个容器,例如竖直、水平或倾斜设置的容器。反应物可以直接进料至反应器或者通过一个单独的混合设备而进料。反应器合适地优选基本为管状流通的容器或管子,最优选包括以基本均匀的方式混合反应物的设备。这种设备可以包括一个配有孔且设置在反应器内部的盘或类似物,其中金属氯酸盐和过氧化氢进料至盘的下游,而酸进料至盘的上游并且流过孔,然后与金属氯酸盐和过氧化氢混合。已经发现这种设置能达到均匀混合和稳定的操作过程,以及在保持高的化学效率的前提下改变生产速率的能力,特别是当反应器与主流动方向基本竖直向上设置时。但是,也有可能仅简单地向进料管线进料一种反应物例如酸从而代替另一种反应物或反应物的混合物,例如金属氯酸盐和过氧化氢的混合物。
所应用的反应器的长度(沿主流动方向)优选为约50至约800mm,最优选为约350至约650mm。已经发现有利的是应用内径为约25至约300mm的基本管式反应器,优选为约70至约200mm。特别有利的是应用长度与内径的比优选为约12∶1至约1∶1的基本管式反应器,最优选的长度与内径比为约8∶1至约4∶1。在大多数情况下在反应器中合适的平均停留时间为约1至约1000秒,优选为约2至约40秒。
喷射器产生一种吸力使包括任何液体、泡沫和气体的产物流流入喷射器,并与流动水混合从而形成含二氧化氯的稀释溶液。通过任何适当的设备使流动水按至少部分盘旋或螺旋的方式流入,所述设备例如螺旋叶片、内部膛线或类似物,这些设备可以与喷嘴整合或与喷嘴分离,并设置在喷嘴的内部或其上游。所述喷嘴可以为任何合适的类型并且可以包括一个或几个孔。
所述喷射器沿喷嘴的流动方向进一步合适地包括一个吸入室以及一个文丘里区,从反应器向吸入室中输送产物流,并且在这种情况下通过文丘里区抽出含二氧化氯的稀释水溶液。也可以应用带有一个以上喷嘴的喷射器。
已经发现对于给定的流动水流量来说,至少部分盘旋或螺旋流动的流动水提高了二氧化氯的生产能力,因而能够生产具有更高二氧化氯浓度的产品溶液,所述的更高是与以前的方法即仅通过从反应介质中分离二氧化氯气体,然后再在水中吸收它而可以生产的产品相比较而言,而在本发明中不必进行这些步骤。因此,有可能生产含有约1至约4克/升二氧化氯的水溶液,优选为约1.5至约3.5克/升的二氧化氯。
本发明的方法特别适合于在小规模装置中生产二氧化氯,例如在一个反应器中从约0.1至约100kg/hr,优选为约0.1至约50kg/hr。对于许多应用来说,在一个反应器中优选的二氧化氯生产速率为约0.1至约25kg/hr,更优选为约0.5至约10kg/hr。虽然有可能设置几个反应器,例如以平行方式设置约15或更多个反应器,例如作为管束而设置的反应器,但典型的小规模生产装置通常仅包括一个反应器。
本发明进一步涉及按照上述方法生产二氧化氯的设备。所述设备包括配有氯酸根离子、过氧化氢和酸进料管线的反应器,所述反应器与喷射器相连,而所述喷射器配有用于流动水的喷嘴和使流动水以至少部分盘旋或螺旋方式进一步流过喷射器的设备。
由本方法的上述描述和参考附图的下列描述,所述设备的优选实施方案将会很明显。但是,本发明并不局限于附图中所示的实施方案,而是包括在权利要求范围内的许多其它变体。
附图的简要描述
图1给出了本发明的示意性流程图。图2示意性地描述了反应器。图3a和3b示意性地描述了喷射器和引起流动水以至少部分盘旋或螺旋方式流动的设备。
附图的详细描述
参考图1,通过进料管线1向一个垂直的流通管式反应器3提供硫酸,并通过管线2向其提供预先混合的氯酸钠和过氧化氢的水溶液。在反应器3中原料物流混合并进行反应,从而形成包含二氧化氯、氧、硫酸钠和一些剩余硫酸和氯酸钠的液体、泡沫和气体产物流。通过进料管线5向喷射器6提供流动水,并产生稍微低于大气压的压力,从而驱使产物流通过管线4从反应器3流出而进入喷射器6,在喷射器6中其与流动水混合从而形成稀释的产品水溶液。这种稀释的溶液含有来自反应器3的二氧化氯和其它组分,并通过管线8作为最终产品抽出。工艺控制系统包括可程序化的逻辑控制(PLC)、二氧化氯分析仪9、压力变送器(PT)和流量变送器(FT),其控制向反应器3进料化学物质和向喷射器6进料流动水的进料泵10。
参考图2,配有孔的分配盘21设置在反应器3的下部,但是高于硫酸的进料管线1的入口。用于预先混合的氯酸钠和过氧化氢溶液的进料管线2终止于分配喷嘴20,该分配喷嘴设置在反应器横截面的中心,刚好在分配盘的上方。然后氯酸钠和过氧化氢溶液在反应器3内的横截面上喷撒,而硫酸向上流动通过分配盘上的孔,并且在分配盘21上方与氯酸钠和过氧化氢混合。混合后,开始生产二氧化氯的反应,并生产液体、泡沫和气体的产物流,这股物流在反应器3的顶部通过出口22抽出。
参考图3a和3b,喷射器6包括一个吸入室25、带有插件27的一孔喷嘴26,所述插件27(在图3b中以通过喷嘴的视图给出)包括螺旋状叶片28和文丘里区29。由进料管线5通过喷嘴26和插件27提供流动水。插件27的螺旋状叶片28造成水按至少部分盘旋或螺旋的方式进一步流过吸入室25,在其中与通过管线4来自反应器3(参见图1)的产物流混合,从而形成稀释的含二氧化氯的溶液,所述溶液通过文丘里区29而从喷射器6排出。通过喷射器的流动产生低于大气压的力,该压力足以驱使来自反应器的产物流流入喷射器。
本方法的设备,包括反应器3和喷射器6,合适地由对过氧化氢、氯酸钠、硫酸和二氧化氯具有耐受性的材料制成。这些材料包括例如玻璃、钽、钛、玻璃纤维强化的塑料、氟塑料如PVDF(聚偏二氟乙烯)、CPVC(氯代聚氯乙烯)、PTFE(聚四氟乙烯)、PFA(全氟代烷氧基聚合物)、ECTFE(乙烯氯三氟乙烯)或FEP(氟化乙烯丙烯),或应用这些材料作为结构材料如钢或不锈钢的衬里材料。适合的氟代塑料以商标Kynar®、Teflon®或Halar®销售。
通过如下实施例进一步描述本发明。
实施例:在附图所示的设备中按照本发明制备二氧化氯。向内径为75mm、长为610mm的竖直管式反应器3中连续供给78wt%硫酸和40wt%氯酸钠与10wt%过氧化氢的水溶液,所述水溶液用膦酸基络合剂稳定。将反应器保持在温度为约40-50℃、绝压为约84kPa(约低于大气压17kPa)下,通过向喷射器6提供绝压790kPa的流动水而产生低于大气压的压力。
作为比较,以相同的方式生产二氧化氯,唯一的区别在于所应用的喷射器不包含喷嘴的任何插件,从而不能使流动水按至少部分盘旋或螺旋的方式流动。
结果示于下表中:
喷射器类型 | 流动水流量(升/分钟) | ClO2生产速率(kg/h) | 最终产品中ClO2浓度(毫克/升) |
带有插件(本发明) | 48.1 | 9.1 | 3135 |
没有插件(比较例) | 45.4 | 3.9 | 1450 |
很明显,在ClO2的生产速率方面和从喷射器抽出的最终产品溶液中的ClO2浓度方面,本发明的方法都有明显提高。
Claims (18)
1.连续生产二氧化氯的方法,包括如下步骤:
向反应器中进料水溶液形式的氯酸根离子、无机酸和过氧化氢;
在反应器中还原氯酸根离子为二氧化氯,从而在反应器中形成含二氧化氯的产物流;
向包含喷嘴的喷射器中进料流动水;
使流动水流过喷嘴,并使其按至少部分盘旋或螺旋的方式进一步流过喷射器;
其中喷射器产生一种吸力使产物流从反应器流入喷射器并与流动水混合,从而形成含二氧化氯的稀释水溶液;以及
从喷射器中抽出含二氧化氯的稀释水溶液。
2.权利要求1的方法,其中使流动水按盘旋或螺旋的方式进一步流过喷射器。
3.权利要求1的方法,其中通过设置在喷射器的喷嘴内部或上游的螺旋状叶片使流动水按至少部分盘旋或螺旋的方式流动。
4.权利要求1的方法,其中通过喷射器的喷嘴内部或上游的内膛线使流动水按至少部分盘旋或螺旋的方式流动。
5.权利要求1-4任一项的方法,其中在喷嘴的流动方向上,喷射器进一步包括一个吸入室和一个文丘里区,其中向吸入室中输送来自反应器的产物流,而通过文丘里区抽出含二氧化氯的稀释水溶液。
6.权利要求1-4任一项的方法,其中以含有金属氯酸盐水溶液的形式向反应器进料氯酸根离子。
7.权利要求1的方法,其中无机酸为硫酸。
8.权利要求6的方法,其中以预先混合的水溶液形式向反应器进料碱金属氯酸盐和过氧化氢。
9.权利要求8的方法,其中预先混合的水溶液含有:1-6.5摩尔/升的碱金属氯酸盐,1-7摩尔/升的过氧化氢,以及碱金属锡酸盐、吡啶羧酸和膦酸基络合剂中的至少一种,并且其pH值为0.5-4。
10.权利要求1-4任一项的方法,其中进料至反应器的氯离子的量低于1摩尔%ClO3 -的Cl-。
11.权利要求1-4任一项的方法,其中在反应器中含有二氧化氯的产物流包括液体和泡沫。
12.权利要求1-4任一项的方法,其中反应器内的温度保持为30-60℃。
13.权利要求1-4任一项的方法,其中反应器内的绝压保持为30-100kPa。
14.权利要求1-4任一项的方法,其中反应器为管状流通的容器或管道。
15.权利要求14的方法,其中反应器竖直设置。
16.权利要求14的方法,其中反应器包括配有孔且设置在反应器内部的盘或类似物,金属氯酸盐和过氧化氢进料至盘的下游,而无机酸在盘的上游进料并流过孔,然后与金属氯酸盐和过氧化氢混合。
17.权利要求15的方法,其中主流动方向为向上。
18.按权利要求1-17任一项生产二氧化氯的设备,包括配有用于氯酸根离子、过氧化氢和无机酸的进料管线的反应器,所述反应器与喷射器相连,所述喷射器配有用于流动水的喷嘴以及使流动水以至少部分盘旋或螺旋方式进一步流通过喷射器的设备,从而产生一种吸力使产物流从反应器流入喷射器并与流动水混合,并且所述反应器和喷射器由对过氧化氢、氯酸钠、硫酸和二氧化氯具有耐受性的材料制成。
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---|---|---|---|---|
WO2000046153A1 (fr) * | 1999-02-04 | 2000-08-10 | Kawasaki Jukogyo Kabushiki Kaisha | Procede de production d'oxyde de titane du type anatase et d'un materiau de revetement a base de dioxyde de titane |
US20040175322A1 (en) * | 2003-03-03 | 2004-09-09 | Woodruff Thomas E. | Process for producing chlorine dioxide |
GB2415693B (en) * | 2003-07-23 | 2007-04-11 | Tristel Company Ltd | Chlorine Dioxide Generation |
GB0317155D0 (en) * | 2003-07-23 | 2003-08-27 | Tristel Company The Ltd | Chlorine dioxide generation |
US8642054B2 (en) | 2004-09-07 | 2014-02-04 | Tristel Plc | Sterilant system |
US7807118B2 (en) | 2004-09-07 | 2010-10-05 | Tristel Plc | Decontamination system |
ES2364570T5 (es) * | 2004-12-06 | 2016-01-11 | Akzo Nobel N.V. | Proceso químico y aparato |
ATE459574T1 (de) * | 2004-12-06 | 2010-03-15 | Akzo Nobel Nv | Chemisches verfahren und produktionseinheit |
EP1945566B1 (en) * | 2005-11-10 | 2019-11-20 | Akzo Nobel N.V. | Process for production of chlorine dioxide |
WO2007117205A1 (en) * | 2006-04-10 | 2007-10-18 | Akzo Nobel N.V. | Process for the production of chlorine dioxide |
HUP0600735A2 (en) | 2006-09-21 | 2009-04-28 | Zoltan Dr Noszticzius | Permeation method and apparatus for preparing fluids containing high-purity chlorine dioxide |
TWI447065B (zh) * | 2007-07-13 | 2014-08-01 | Akzo Nobel Nv | 二氧化氯之製造方法 |
ITMI20072388A1 (it) | 2007-12-19 | 2009-06-20 | Caffaro Chimica S R L | Apparecchiatura e metodo per la disinfezione di acque |
KR101034747B1 (ko) | 2009-05-29 | 2011-05-17 | 삼성에스디아이 주식회사 | 믹싱 장치 |
KR101162536B1 (ko) | 2009-10-23 | 2012-07-05 | 주식회사 에코시아 | THMs등이 생성되지 않는 녹색 친환경 살균소독제인 이산화염소 수용액 제조장치 및 그 제조방법 |
DE202010017479U1 (de) * | 2010-04-16 | 2012-02-16 | Infracor Gmbh | Tauchreaktor |
RU2562997C2 (ru) * | 2010-07-08 | 2015-09-10 | Акцо Нобель Кемикалз Интернэшнл Б.В. | Способ получения диоксида хлора |
GB2495309B (en) | 2011-10-05 | 2014-02-19 | Paradigm Flow Services Ltd | Fire main cleaning apparatus and method |
GB201612077D0 (en) * | 2016-07-12 | 2016-08-24 | Gaffey Technical Services Ltd | A chlorine dioxide solution generating apparatus |
US11535541B2 (en) | 2017-02-27 | 2022-12-27 | Ecolab Usa Inc. | Method for onsite production of chlorine dioxide |
US11130677B2 (en) | 2017-03-24 | 2021-09-28 | Ecolab Usa Inc. | Low risk chlorine dioxide onsite generation system |
TWI750356B (zh) | 2017-08-17 | 2021-12-21 | 美商藝康美國公司 | 低風險二氧化氯現場產生系統 |
CN108328578B (zh) * | 2018-01-29 | 2020-03-10 | 荣成海奥斯生物科技有限公司 | 气态有效氯水溶液的灌装装置 |
US11970393B2 (en) | 2018-07-05 | 2024-04-30 | Ecolab Usa Inc. | Decomposition mediation in chlorine dioxide generation systems through sound detection and control |
CN109133008B (zh) * | 2018-08-23 | 2020-05-19 | 四川齐力绿源水处理科技有限公司 | 一种高纯二氧化氯的制备设备 |
US10881111B1 (en) | 2019-11-26 | 2021-01-05 | NEOCL Co., Ltd. | Composition for providing room temperature long-term constant-concentration chlorine dioxide solution in aqueous medium and preparation method thereof |
CN112999993B (zh) * | 2021-02-08 | 2023-04-07 | 乌兰浩特市圣益商砼有限公司 | 一种制备聚羧酸减水剂的涡喷双级强化反应器及制备方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1015665B (it) * | 1974-07-04 | 1977-05-20 | Snam Progetti | Metodo per la preparazione in con tinuo di emulsioni acqua olio ed apparecchiatura adatta allo scopo |
US4247531A (en) * | 1979-08-13 | 1981-01-27 | Rio Linda Chemical | Chlorine dioxide generation apparatus and process |
CA1163420A (en) * | 1982-09-09 | 1984-03-13 | Gerald Cowley | Production of chlorine dioxide on a small scale |
US5204081A (en) * | 1991-05-03 | 1993-04-20 | Rio Linda Chemical Co., Ltd. | Process for the generation of chlorine dioxide |
GB2294646B (en) * | 1994-10-29 | 1999-03-17 | Transvac Systems Ltd | Material treatment |
US5968454A (en) * | 1998-04-02 | 1999-10-19 | Vulcan Chemical Technologies, Inc. | Chlorine dioxide generator |
US7070710B1 (en) * | 1999-06-11 | 2006-07-04 | Eka Chemicals Inc. | Chemical composition and method |
-
2002
- 2002-06-03 WO PCT/SE2002/001068 patent/WO2003000586A1/en active Application Filing
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- 2002-06-03 CN CNB028126734A patent/CN1221469C/zh not_active Expired - Lifetime
- 2002-06-03 RU RU2004101962/15A patent/RU2268241C2/ru active
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EP1399383B1 (en) | 2010-04-28 |
PL200136B1 (pl) | 2008-12-31 |
EP1399383A1 (en) | 2004-03-24 |
PL364357A1 (en) | 2004-12-13 |
BR0210340B1 (pt) | 2010-12-14 |
DE60236154D1 (de) | 2010-06-10 |
MY130748A (en) | 2007-07-31 |
WO2003000586A1 (en) | 2003-01-03 |
RU2004101962A (ru) | 2005-04-10 |
KR20040012889A (ko) | 2004-02-11 |
BR0210340A (pt) | 2004-07-13 |
KR100590345B1 (ko) | 2006-06-15 |
PT1399383E (pt) | 2010-07-19 |
MXPA03010884A (es) | 2004-02-17 |
CN1520378A (zh) | 2004-08-11 |
RU2268241C2 (ru) | 2006-01-20 |
JP4006019B2 (ja) | 2007-11-14 |
ATE465972T1 (de) | 2010-05-15 |
ES2345185T3 (es) | 2010-09-17 |
JP2004530626A (ja) | 2004-10-07 |
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