CN101102975A - 环境友好的碳粘结的耐火产品以冷混法的制备 - Google Patents
环境友好的碳粘结的耐火产品以冷混法的制备 Download PDFInfo
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Abstract
本发明涉及由耐火颗粒和有机粘结剂制备碳粘结的耐火产品的方法,其中使用根据DIN51905具有低于500mg/kg苯并[a]芘粉含量和焦化残留物至少约80重量%的粉状可石墨化的煤焦油沥青和根据DIN51905具有焦化残留物至少约15重量%和低于500ppm苯并[a]芘粉含量的在室温下为液体的可石墨化的粘结剂作为有机粘结剂,将其与剩余组分混合,制成成型体,然后在150-约400℃温度进行热处理。
Description
本发明涉及由耐火颗粒,碳载体和有机粘结剂制备碳粘结的耐火产品的方法。
耐火产品用于冶金容器的衬里和作为耐火功能性产品,例如所谓的滑板。在设备中的磨损需要不断的产品替换,这种磨损主要归结于炉渣渗透引起的腐蚀,脱碳(焦炭粘结体(Bindung)和碳载体的氧化),磨蚀和由于热应力导致的产品碎片剥落。
用于制备这些产品的粘结剂是多功能的。它们能使耐火颗粒成型并当安装在设备中及在随后首次加热中保证产品的尺寸稳定性。在燃烧条件下,它们形成焦炭粘结体并提供减少炉渣渗透所需的碳。用作粘结相的碳由于有机起始化合物的热解而产生。为此目的,耐火颗粒或是与可焦化粘结剂进行热混合,象热塑性的沥青粘结剂,例如煤焦油沥青和芳香族石油沥青(在下文指的是粘结剂沥青),或是通常与在150-250℃硬化后形成热固性结构的可硬化合成树脂进行冷混合。
由于三维交联,由合成树脂热解或炭化制得的焦炭粘结体是各向同性的,非石墨化的,硬的和脆的,并由于大的内表面,它对氧化是敏感的。
另一方面,粘结剂沥青的热解在液相中进行,并形成有序的六方碳层。形成各向异性的,石墨化的,软的和柔韧性焦炭粘结体,由于其小的内表面,它对氧化很不敏感。由于由粘结剂沥青制得的粘结体具有各向异性的焦炭结构,因此具有更好的热冲击性能和抗氧化性能,所以粘结剂沥青的使用,不像合成树脂,通常会导致产品在设备中较少的磨损。
当粘结剂和耐火颗粒进行加工时,区分为热和冷成型(热和冷混合过程)。在冷成型中,在室温下将没有预热的耐火颗粒加入到没有加热的混合器。粘结剂通常是冷的即在室温下进行添加。在高粘性粘结剂情况下,可将预热过的粘结剂添加到混合器以更好地配料。由于在混合中颗粒的内摩擦,混合料能够升温到60℃。随后的湿物料的压实和成型同样在室温下进行。由于不需要昂贵的加热系统,冷成型和合成树脂粘结体的优点是非常少的投资成本。由于所有组分均进行冷加工,对连续操作来说可节省相当多的能量。
在热成型中,耐火颗粒和粘结剂在加入到混合器前必须加热到粘结剂的软化点以上的温度。混合器也必须进行加热。随后的压实或压制过程也在高于粘结剂软化点的温度进行。具有对应用来说足够高的焦炭产率的粘结剂沥青在室温时是固体的或高浆糊状的,只能通过热成型进行加工。粘结剂沥青特别是煤焦油沥青的主要缺点是具有对环境有污染的和对健康有危害的高达15000mg/kg的苯并[a]芘(B[a]P)含量。由于粘结剂沥青进行热加工,由于在加热中高的蒸汽压,会发生B[a]P的释放,这具有伴随的潜在的危险。当耐火产品在首次使用过程中加热时也会发生含有B[a]P的碳氢化合物馏出物的释放。立法者已经考虑到这种潜在的危险,将具有高于50mg/kgB[a]P含量的耐火产品标注作为有毒材料并必须在适当的保护措施下处理。因此在德国,只要技术上可行,在所谓的TRGS551中就要求使用苯并[a]芘含量小于50mg/kg的耐火产品。这显示了尽管具有技术上的优点,粘结剂沥青的使用在逐年减少。
使用粘结剂沥青制备冷成型的耐火产品原则上是已知的。例如GB690859描述了由耐火颗粒和粉状粘结剂沥青制备捣固料或砖,在该方法中向耐火颗粒和粉状粘结剂沥青的混合物中添加旨在提高所得产品密度的增塑剂,例如煤油,苯或杂酚油。
US 3285760描述了由耐火颗粒和粉状粘结剂沥青形成的捣固料。使用蒽油或重油作为粉状粘结剂沥青的溶剂或润滑剂。
US 3415667描述了制备沥青粘结的耐火材料的技术,其中使用液体有机溶剂用于液化粘结剂沥青。随后液化的粘结剂沥青首先与粗的颗粒混合,然后与细的颗粒混合并进行压制。优选三氯代碳氢化合物作为溶剂。在GB 978185中采用相似的工艺。在该方法中相互混合粘结剂沥青和有机溶剂,使得形成具有不超过80泊粘度的粘结剂。两种方法共同的特征是高的工艺技术强度和消耗,因为粘结剂沥青和有机溶剂首先必须在附加的工艺步骤中加工成可以使用的粘结剂。
在US4071593中描述的方法是联合使用粘结剂沥青和木质素磺酸盐溶液和/或热的硬化醇酸树脂在有机溶剂中的溶液。这种方法的不足在于不能处理水合敏感性的原材料例如白云石,和除各向异性的焦炭结构之外,还获得对氧化敏感的和脆的各向同性的焦炭结构。
在DE3149485A1描述的方法中,0.5-15%的粘结剂沥青和相对于粘结剂沥青含量多达5%有机液体,添加到耐火混合物中。然而,这样的混合物在压制操作时过于干燥。从典型的实施方式中推导出,额外的需要废的亚硫酸盐废液,水和粘土作为增塑剂。除焦炭粘结体之外,获得陶瓷粘结体。这种方法的一个缺点在于不能处理水合敏感性的原材料例如白云石。
上述所有方法的共同特征是粘结剂沥青高的B[a]P含量。因此根据欧洲法律,获得的产品必定被注明为有毒物质,而且不能满足TRGS551的要求。与合成树脂体系相比,就产品的性能冷抗压强度,热弯曲强度和孔隙率而言,上述粘结剂的结合已经证明效果较差,因此几乎不被使用。
最近的发展允许在合成树脂粘结的冷成型产品中加入沥青典型的可石墨化的各向异性的焦炭结构,符合TRGS551的规定。在这种情况下,一些合成树脂被研磨过的低B[a]P含量和高熔融的粘结剂沥青粉末替代。然而,与纯沥青粘结体相比的缺点是产品中存在部分各向同性并因此对氧化敏感的焦炭结构(Boenigk,W.et al.CARBORES-acarbon speciality to improve the performance of refracctoriesbonded with phenolic resins,Proceedings Burocarbon 2000,1stWorld Conference on Carbon,9 to 13 July 20O0,Berlin,pp.367-368///Anezins,C.G.et al.Studies of special binderagents for refractory MgO-C products,Proceedings,14thConference on Refractory Building Materials,20/21 May2003,Prague,pp. 118-126)。
DE4112955A1描述了具有减少致癌物质含量的煤焦油沥青的制备,和作为粘结剂和浸渍剂的使用。
本发明的主要目的是提供制备碳粘结的耐火产品的方法,允许使用的组分进行所谓的冷混合并能获得具有各向异性焦炭结构并具有高强度和低于50mg/kg苯并[a]芘含量的耐火产品。
本发明的另一个目的是提供用于上述方法的粘结剂体系。
通过由耐火颗粒和有机粘结剂制备碳粘结的耐火产品的方法实现本目的,在方法中使用的有机粘结剂是根据DIN51905具有低于500mg/kg的苯并[a]芘含量和焦化残留物至少约80重量%的粉状可石墨化的煤焦油沥青和根据DIN51905具有焦化残留物至少约15重量%和具有低于500mg/kg的苯并[a]芘含量的在室温下为液体的可石墨化的粘结剂,将其与剩余组分混合,制成成型体,然后在150-约400℃温度下进行处理。
粉状可石墨化的煤焦油沥青在高于约150℃温度下在液体粘结剂中是可溶的。优选地具有高于180℃,特别优选高于220℃的软化点。
令人惊讶的是,已经表明如果根据本发明的方法实施,能结合实现一方面使用合成树脂和另一方面使用煤焦油沥青的优点。这些优点特别是,能够以节能的冷混合方法操作和仍然能获得沥青典型的各向异性的可石墨化的焦炭结构,导致所得耐火产品的高强度和显著提高的抗氧化性能。
根据本发明使用选择的煤焦油沥青允许耐火产品中具有低于50mg/kg的低苯并[a]芘含量。根据本发明,这种煤焦油沥青用作为高温粘结剂。这种高温粘结剂优选地以粉末形式存在。平均颗粒尺寸可为10-约500μm,优选为50-约200μm。
根据本发明的另一个优选的实施方式,高温粘结剂用粉尘粘结剂润湿。由此阻止了粉尘的形成,并能改善在耐火材料中的粘结。粉尘粘结剂优选为不溶解粉末的高沸点石油衍生油。具有高于300℃沸点和密度小于1的环烷烃油是特别适合的。可使用相对于高温度粘结剂全部质量的直到约5重量%、特别是0.5-3重量%的粉尘粘结剂。
根据本发明使用的液体粘结剂可以是高温粘结剂在例如从煤焦油馏出物得来的高芳烃油中的溶液。特别优选250-370℃温度的沸程。液体粘结剂作为增塑剂,因此保证了耐火混合物的可成型性并具有对于处理足够的强度。高温粘结剂在高芳烃油中的浓度依靠于要获得的液体粘结剂的粘度。例如,相对于液体粘结剂的质量,可为10-85重量%或25-65重量%。
通过在蒸发器中在常压或减压下第一蒸馏阶段的煤焦油的蒸馏和通过在优选不超过1毫巴压力下第一蒸馏阶段的残余物的蒸馏获得根据本发明用作有机粘结剂的粉状可石墨化的煤焦油沥青,其中蒸发器中温度优选在300-380℃的温度范围。在蒸发器中残余物的平均停留时间优选为2-10分钟。
根据本发明获得的耐火材料可含有相对于耐火混合物全部质量的0.5-约4重量%,优选1-约2.5重量%的高温粘结剂作为粘结剂。液体粘结剂的比例可为相对于耐火混合物全部质量的约1.3-约4重量%,优选2-3重量%。
根据本发明适合的颗粒可包括已知用于耐火物体制备的无机氧化物。优选包括氧化镁,白云石,氧化铝,氧化锆或其混合物。特别优选的是使用氧化镁,例如熔融氧化镁和/或烧结氧化镁。
为了提高耐火产品中的碳含量,可以在成型前向耐火颗粒、高温粘结剂和有机粘结剂的混合物中添加另外的含有碳的物质,特别是石墨和/或炭黑。此外,也可添加润湿剂和脱水剂,例如硫磺,有机硝基化合物或无机硝酸盐,以提高可混合性和提高焦炭产率和强度。可以加入抗氧化剂以减少当最终产品使用时碳的氧化。
可采用已知的方法通过本领域中常规使用的压制设备进行成型。例如100-300MPa的压力对成型是适合的。
然后将获得的所谓的“生”产品进行热处理。可在150-约400℃的温度进行该处理。处理时间依靠于成型产品的尺寸,可以直到约20或更多小时。这导致热抗压强度的增加。
当回火的材料在设备中第一次加热时形成粘结剂的希望的最终焦炭结构。
使用根据本发明的粘结剂体系制备的耐火砖也可没有问题的进行加工。在压制后可获得6-12MPa的冷抗压强度并因此与冷成型的合成树脂粘结的砖相似的水平。在回火后的冷抗压强度是20-30MPa,这对在设备中没有问题地进行安装和在最初加热中施加的机械负载是足够高的。在1000℃焦化后,获得20-30MPa的冷耐压强度和约11%的孔隙率。冷抗压强度和孔隙率与合成树脂粘结的产品的冷抗压强度和孔隙率是可比的。这种新的粘结剂体系形成完全各向异性的可石墨化的和软的焦炭基体(软粘结体)。这导致产品增加的热冲击性和抗氧化性。由根据本发明使用的煤焦油沥青作为高温粘结剂制备的产品具有<50ppm的苯并[a]芘含量,满足德国TRGS551的要求,根据欧洲法律不被标注作为有毒物质。
下面的实施例用于对本发明进一步说明。尽可能地应用DIN标准进行分析。
实施例
用于表征根据本发明使用的材料的技术标准在表1中给出。
表1-标准
软化点 | DIN51920 |
甲苯不溶物(TI) | DIN51906 |
喹啉不溶物(Q) | DIN51921 |
焦化残留物 | DIN51905 |
灰分 | DIN51922 |
苯并[a]芘 | HPLC |
实施例1
由煤焦油沥青制备高温粘结剂
在1毫巴的真空下蒸馏煤焦油沥青[(软化点[Mettler])EPM=113℃,TI =29℃,QI=8.5%,β树脂=20.6%,焦化残留物=59.2%,B[a]P含量=1.1%,熔融开始温度(TPA)=36℃,熔融结束温度(TMA)=86℃],在蒸发器中的蒸馏温度为355℃,平均保持时间约5分钟。根据本发明,获得的沥青用作高温粘结剂(粘结剂A),由表2的分析数据加以表征。
表2-所得高温粘结剂的性能
产品 | 焦化残留物(重量%) | 灰分(重量%) | TI(重量%) | QI(重量%) | 软化点(℃) | B[a]P含量[ppm] |
粘结剂A | 85.5 | 0.3 | 57.5 | 16.2 | 230 | 273 |
实施例2
由高温粘结剂制备液体粘结剂
40重量份的由实施例1的煤焦油沥青溶解在60重量份的蒽油中(B[a]P含量40ppm,沸程250-370℃)。获得的粘结剂B具有表3显示的性能。
表3-获得的液体高温粘结剂的性能
产品 | 焦化残留物(重量%) | 灰分(重量%) | TI(重量%) | QI(重量%) | 动态粘度20℃(mPaS) | B[a]P含量[ppm] |
粘结剂B | 32 | 0.3 | 17.9 | 5.4 | 3.000 | 220 |
实施例3
制备三组样品和由其获得的成型体
根据本发明方法制备三组样品(3a-c)并与3组比较例(V1-3)比较。在V1中使用现在通常使用的由液体可溶性酚醛树脂和粉状酚醛清漆组成的酚醛树脂体系。在V3中使用根据US3285760的蒽油,在V2中使用常规的煤焦油沥青。
为了制备根据本发明的热解的成型体,在各颗粒中加入2重量%的由实施例2制得的液体粘结剂B,并以1.3重量%(组1),2.3重量%(组2)和3.3重量%(组3)的量加入由实施例1获得的高温粘结剂A,每种情况下相对于耐火混合物的全部质量。使用的颗粒性能在表4中给出。加入足够的石墨(9-12%),以使产品达到13-14%的剩余碳含量。使用的石墨的性能在表5中给出。在没有加热的情况下在耐火工业中常用的强制式混合机中进行混合。混合物的组分在表8中给出。
制得的湿的物料在150MPa压力下压实形成成型体。然后在300℃对成型体进行回火,然后在1000℃进行热解/焦化。在表7中归纳耐火产品的性能。
表4-耐火颗粒的性能
MgO原材料 | 颗粒体积密度,g/cm3 | MgO,重量% | Fe2O3,重量% | C/S比率 |
熔融氧化镁 | 3.52 | 97.8 | 0.5 | 3 |
烧结氧化镁 | 3.41 | 98.0 | 0.12 | 6 |
表5-使用石墨的性能
类型 | 标准片 |
碳含量 | 94-96重量% |
灰分含量(DIN 51903) | 4-6重量% |
水分含量(DIN 51904) | <0.3重量% |
颗粒尺寸分布(DIN 51938) | 至少70重量%>160μm至少95重量%>71μm |
比表面积(DIN 66131) | 1m2/g |
体积密度(DIN EN ISO 60) | 650g/l |
表6-混合物的组成
组成 | 组1(重量%) | 组2(重量%) | 组3(重量%) | 比较例V1(重量%) | 比较例V2(重量%) | 比较例V3(重量%) |
熔融氧化镁3-6mm | 19.52 | 19.50 | 19.56 | 19.61 | 19.56 | 19.59 |
熔融氧化镁1-3mm | 31.40 | 31.37 | 31.46 | 31.55 | 31.46 | 31.52 |
熔融氧化镁0s1mm | 21.22 | 21.19 | 21.26 | 21.32 | 21.26 | 21.30 |
氧化镁粉末(DIN70) | 12.73 | 12.72 | 12.75 | 12.79 | 12.75 | 12.76 |
片状石墨 | 11.57 | 11.08 | 9.86 | 11.63 | 9.86 | 11.62 |
蒽油 | 1.3 | |||||
粘结剂B | 2.0 | 2.0 | 2.0 | |||
粘结剂A | 1.3 | 2.3 | 3.3 | 2.0 | ||
酚醛清漆粉末 | 1.2 | |||||
可溶性酚醛树脂,液体 | 2.0 | |||||
煤焦油沥青 | 5.0 | |||||
剩余碳 | 13.2 | 13.5 | 13.1 | 13.1 | 13.1 | 13.2 |
表7-压制的回火的和热解的成型体的性能
实施例 | 粘结剂重量% | 压制后 | 回火后(300℃) | 焦化后(1000℃) | ||||||||||
粗密度g/cm3 | KDFN/mm3 | 粗密度g/cm3 | 长度变化% | KDFN/mm2 | OP,% | 粗密度g/cm3,% | 长度变化,% | KDFN/mm2 | OP,% | 焦炭结构 | ||||
pr.方向 | 垂直于Pr | pr*方向 | 垂直于Pr | |||||||||||
1 | 1.3%A+2.0%B | 2.99 | 10 | 2.97 | 0.40 | 0.24 | 30 | 7.9 | 2.92 | 0.37 | 0.36 | 27 | 11.2 | 各向异性 |
2 | 2.3%A+2.0%B | 2.99 | 10 | 2.94 | 0.58 | 0.28 | 26 | n.b. | 2.88 | 0.45 | 0.36 | 26 | 11.5 | 各向异性 |
3 | 3.3%A+2.0%B | 2.96 | 10 | 2.88 | n.b. | nb. | 21 | n.b. | 2.81 | 0.54 | 0.39 | 21 | n.b. | 各向异性 |
V1 | 2.0%可溶性酚醛树脂+1.2%酚醛清漆粉末 | 3.05 | 10 | 3.03 | 0.08 | 0.04 | 69 | 3.3 | 2.98 | 0.10 | 0.24 | 28 | 9.5 | 各向同性 |
V2 | 煤焦油 | 2.95 | 24 | 2.84 | 0.94 | 0.74 | 22.9 | 10. 6 | 2.82 | 2.86 | 0.89 | 24.4 | 12.5 | 各向异性 |
V3 | 1.3%蒽油+2%B | 2.99 | 7 | 2.91 | n.b. | n.b. | 18 | n.b. | 1.03 | 0.35 | 0.31 | 16 | 13.5 | 各向异性 |
A=粉状可石墨化高温粘结剂,
B =液体可石墨化高温粘结剂
*=pr=加压方向
在本发明的组1到3中,液体粘结剂沥青的浓度保持不变,而粉状高温粘结剂的浓度变化。表明随着粉状高温粘结剂含量的增加,成型体的孔隙度增加和强度降低。能通过根据本发明的方法成功地制备具有与酚醛树酯粘结的成型体相当强度的成型体。然而,根据本发明制备的成型体的主要优点是它们的各向异性的焦炭结构。各向异性焦炭结构的优点在于通常更高的柔韧性,更高的抗氧化性和更高的抗热冲击性。
能从实施例3和比较例中看出根据本发明制备的碳粘结的耐火产品与通过常规煤焦油或合成树脂粘结剂体系获得的产品相比具有相当的优点。它们结合了两种上述体系的优点。能以节能和环境友好的方式通过冷混合方法制备成型体,它们只具有低的苯并[a]芘含量,形成各向异性的焦炭结构并具有它们已知的有利性能。
Claims (9)
1.由耐火颗粒和有机粘结剂制备碳粘结的耐火产品的方法,特征在于使用根据DIN51905具有低于500mg/kg苯并[a]芘含量和焦化残留物至少约80重量%的粉状可石墨化的煤焦油沥青和根据DIN51905具有焦化残留物至少约15重量%和低于500ppm苯并[a]芘含量的在室温下为液体的可石墨化的粘结剂作为有机粘结剂,将其与剩余组分混合,制成成型体,然后在150-约400℃温度下进行热处理。
2.根据权利要求1的方法,特征在于相对于耐火材料混合物的全部质量,使用0.5-约4重量%,特别1-2.5重量%的高温粘结剂,和1.3-约4重量%,特别2-3重量%的液体粘结剂作为有机粘结剂。
3.根据权利要求1或2的方法,特征在于煤焦油沥青通过在蒸发器中在正常压力或减压下第一蒸馏阶段的煤焦油的蒸馏,和在不超过1毫巴压力下第一蒸馏阶段的残余物的蒸馏获得,其中蒸发器中温度在300-380℃的范围,和残余物的平均停留时间为2-10分钟。
4.根据权利要求1-3中任一项的方法,特征在于使用根据权利要求3的煤焦油沥青在蒽油中的溶液作为液体粘结剂。
5.根据权利要求1-4中任一项的方法,特征在于使用平均粒径为10-约500μm的粉末形式的粉状煤焦油沥青。
6.根据权利要求1-5中任一项的方法,特征在于粉状煤焦油沥青具有超过约180℃的软化点。
7.根据权利要求1-6任一项的方法,特征在向在与液体粘结剂混合前在粉状煤焦油沥青中添加不溶解沥青的粉尘油。
8.根据权利要求1的方法,特征在于在成型前向耐火颗粒和有机粘结剂的混合物中添加碳载体,特别是石墨和/或炭黑。
9.根据权利要求1-7中任一项的方法获得的具有石墨型碳结构的耐火产品,具有低于50mg/kg的苯并[a]芘含量。
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- 2005-01-11 WO PCT/EP2005/000147 patent/WO2005068391A1/de active Application Filing
- 2005-01-11 AT AT05700787T patent/ATE444268T1/de active
- 2005-01-11 CN CN2005800025332A patent/CN101102975B/zh active Active
- 2005-01-11 DE DE502005008234T patent/DE502005008234D1/de active Active
- 2005-01-11 EP EP05700787A patent/EP1704128B1/de active Active
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Cited By (9)
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CN104342082A (zh) * | 2013-07-24 | 2015-02-11 | 中冶建筑研究总院有限公司 | 用于耐火材料的环保型碳质结合剂的制备方法 |
CN104944968A (zh) * | 2014-03-31 | 2015-09-30 | 中冶建筑研究总院有限公司 | 不定形耐火材料及其制备方法 |
CN104944966A (zh) * | 2014-03-31 | 2015-09-30 | 中冶建筑研究总院有限公司 | 耐火材料及其制备方法 |
CN104944969A (zh) * | 2014-03-31 | 2015-09-30 | 中冶建筑研究总院有限公司 | 耐火材料及其制备方法 |
CN104944967A (zh) * | 2014-03-31 | 2015-09-30 | 中冶建筑研究总院有限公司 | 不定形耐火材料及其制备方法 |
CN104944966B (zh) * | 2014-03-31 | 2018-05-01 | 中冶建筑研究总院有限公司 | 耐火材料及其制备方法 |
CN107364866A (zh) * | 2017-06-28 | 2017-11-21 | 大连华锐重工集团股份有限公司 | 一种低阶煤制备电石炉料的方法及复合粘结剂 |
CN110016358A (zh) * | 2019-03-18 | 2019-07-16 | 中国铝业股份有限公司 | 一种铝用阴极炭块焙烧烟气净化焦油的处理和使用方法 |
CN110016358B (zh) * | 2019-03-18 | 2021-05-07 | 中国铝业股份有限公司 | 一种铝用阴极炭块焙烧烟气净化焦油的处理和使用方法 |
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EP1704128B1 (de) | 2009-09-30 |
DE502005008234D1 (de) | 2009-11-12 |
JP2007517757A (ja) | 2007-07-05 |
DE102004002561A1 (de) | 2005-08-11 |
WO2005068391A1 (de) | 2005-07-28 |
ATE444268T1 (de) | 2009-10-15 |
EP1704128A1 (de) | 2006-09-27 |
KR20070015119A (ko) | 2007-02-01 |
KR101157880B1 (ko) | 2012-07-06 |
DE102004002561B4 (de) | 2009-09-17 |
JP5536299B2 (ja) | 2014-07-02 |
US20070161496A1 (en) | 2007-07-12 |
PL1704128T3 (pl) | 2010-03-31 |
CN101102975B (zh) | 2010-04-14 |
US7772145B2 (en) | 2010-08-10 |
ES2334148T3 (es) | 2010-03-05 |
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