CN1042499C - 在流化床反应器内回收热能的方法和设备 - Google Patents
在流化床反应器内回收热能的方法和设备 Download PDFInfo
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Abstract
利用一个具有传热表面的传热室从流化床反应器内的固体颗粒中回收热能的方法和设备。热固体颗粒被连续地输送到传热室内,并将气体引入并排出该传热室,为了控制其中固体颗粒的流动,将气体引入传热室。通过在传热区内设置比固体颗粒输送区内更多的传热表面把传热室分为至少一个传热区和至少一个固体颗粒输送区。通过将独立控制的气流送入传热区和固体颗粒输送区来对热传递进行控制。
Description
本发明涉及一种从流化床反应器内的固体颗粒回收热能的方法和设备,该反应器包括一个其内具有固体颗粒流化床的处理室,并且利用了一个与该处理室相连的传热室及设在传热室内的传热表面。
热能的回收是靠如下过程进行的:连续不断地将热的固体颗粒从处理室送入传热室,引导气体进入传热室以控制传热室内固体颗粒的流动,利用传热室内设置的传热表面回收热能,同时不断将从传热室排出的固体颗粒再循环到处理室内。因此,装置包括用于引导处理室中的热固体颗粒并使它不断流入传热室的入口装置,用于使固体颗粒不断地从传热室再循环到处理室的出口装置和用于将气体引入传热室的喷嘴装置。
在各种不同的燃烧、热传递、化学或冶金过程中都要使用流化床反应器,如循环流化床反应器。从流化床燃烧过程中回收热量的典型方式是利用设置在燃烧室内和/或设在燃烧室后面的气体通道中的对流段内的传热表面进行的。传热表面也可设置在分离的外部热交换器内,该外部交换器与一个从燃烧室引出的固体物质的外部循环相连。
在循环流化床(CFB)反应器内,可以将外部热交换器或循环热交换器连接到回风管上,这样从固体物质中回收的热能在系统中处于循环状态。传热表面设在由外部热交换器内的循环物质构成的流化床内。通过控制在传热表面周围流动的流化气体可在某种程度上控制外部热交换器内的热传递。
在与一个连续提供热固体物质的系统,如CFB反应器内的回风管相连的外部交换器内,流化气体也对流经热交换器的固体物质的输送进行控制。因此,要想独立地控制外部热交换器内从固体流到热交换器之间的热传递是不可能的。比如即使由于切断流化气体的流动而也使固体物质的流动被切断时不会有热传递发生或只有很弱的热传递发生,那么在起动期间或低负荷状态下也不可能完全切断热传递。
因此在设置了外部热交换器的系统中,可以将固体物质流分成两部分,一部分流入热交换器,另一部分旁流过该热交换器。通过控制一部分流经热交换器的固体物质来控制热传递。该系统需增设用于控制这两股固体流的机械阀。这种结构相当复杂和易发生故障,而且占用空间大,系统的成本也增加。
本发明的一个目的是提供一种用于回收流化床发应器中的热能的方法和装置,并使上述的缺陷被减少到最低限度。
本发明的一个特别目的是提供一种易于控制的热交换器或传热室,该交换器或传热室与流化床反应器内的固体循环,如CFB反应器的回风管相连。
本发明的另一个目的是提供一种改进的用于控制与输送连续热固体物质流的系统相连的外部热交换器内的热传递的方法。
本发明提供了一种改进的,采用一个传热室从流化床反应器的固体颗粒中回收热能的方法,其特征在于:
连续地将热固体颗粒流从处理室导入到传热室,落到传热室中固体颗粒流化床的上表面;
允许固体颗粒在至少一个传热区和至少一个输送区之间自由流动,所述传热区和输送区不用任何隔离壁彼此隔开。
本发明进一步提供了一种改进的利用传热室从流化床反应器的固体颗粒中回收热能的设备,所述设备包括:
用于连续流动的热固体颗粒导入的入口装置设置在传热室之上,使热固体颗粒流落到其内的固体颗粒流化床的上表面;使至少一个传热区和至少一个输送区被设置成允许固体颗粒在其间自由流动,传热区和输送区不用任何隔离壁彼此隔开。
按照本发明的优选实施例的传热室被分成几个并排地水平或垂直布置的传热区,并利用固体颗粒输送区将这几个传热区互相隔开。能够控制各区内的颗粒流动的流化气体或某些其它的输送气可以通过设在传热室下面或通过设在传热室壁内的喷嘴被独立地送到传热区和固体颗粒输送区。
通过独立地控制流化或输送气流可以控制传热室内的固体颗粒的内部流动。比如可以切断或减少在一个传热区内的流化气体流,使之达到没有或几乎没有固体物质围绕表面流动的程度,这样就使传到这些表面的热传递减到最少限度。
同时,通过切断送入到传热区周围的固体颗粒输送区内的流化气流或输送气体使流过传热室的总固体流量保持在适当水平,例如恒定水平上。
传热区的流化控制在使固体颗粒在传热室内形成内部流动的范围,即控制在使来自相邻区的新物质与传热表面相接触的范围。
通过独立地控制送入传热区以及固体颗粒输送区内的流化或输送气体流,可以控制固体颗粒地传热室内的流动路线以及控制固体颗粒在传热室内的一个或多个入口与一个或多个出口之间的流动路线。
固体物质可以通过溢流孔排出传热室,这些溢流孔设在传热室内的适当高度的适当位置处,固体物质也可通过传热室中的低于流化床表面高度的开孔中排出。因此,这些孔最好构成固体流动密封,以便控制固体物质的排放,利用输入的流化或输送气流来控制固体物质流经这些孔时的流量。
形成固体流动密封的排出口可以是几个竖直排列的类似通道的水平狭缝,这些狭缝设置在类似框架的结构中并上下排列。狭缝的高度应小于通道长度的一半,以防止固体物质利用重力流过该通道。
在传热室内,传热表面最好设在固体颗粒床内,但可向上延伸超过该床。也可以利用设置在传热室壁内的传热表面回收热能。
传热室可以有利地设置在循环流化床反应器回风管的下部。回风管的下部需伸长,以便给传热表面提供足够的空间,所以该伸长部分的水平横截面应比回风管上部的水平横截面大。由于CFB系统中的热能很容易对大量的循环热粒子进行蒸发和/或过热,所以CFB锅炉内蒸汽的蒸发或过热在这种回风管内进行是较为有利的。主要包含清洁气体并且非常有限的回风管传热区内的气氛为过热提供了非常有利的条件。因此在燃烧室内,尤其是烟气中含有腐蚀性成份的时候,过热器可以被加热到比通常更高的温度。
适当的流化气体流可以使颗粒贴近过热表面运动,通过将独立控制的适当的流化气体流送入至少部分传热区内的方式来控制颗粒与过热表面之间的热传递。提高表面周围的流量可以增强向表面的热传递率。可以利用几个分离开的喷嘴将作为控制热传递的流化气体的气体(例如空气或惰性气体)送入传热室。从侧壁送入的气体也可用于控制热传递。也可利用引入传热室不同部分的气体的位置和/或流量来控制热传递。
在某些情况下必须在回风管内采取气体密封措施,以防止气体向上流入与回风管上端相连接的粒子分离器。因此,气体可通过管道从回风管排入处理室。但是传热室内一定高度的固体颗粒床可在许多情况下提供气体密封,即充分减小回风管内的上升气流,因此,不需要再增设气体密封。极少量的通过流化床的气体可经过回风管向上流入粒子分离器。
本发明提供了一种非常简单的CFB锅炉结构。最好将回风管建成狭窄的垂直通道结构,该通道与燃烧室有一个共用壁,该壁可以是用在CFB锅炉内的典型膜式水冷壁。相对侧的壁也可是类似的膜式水冷壁。连接具有处理室的回风管的出口可以予制在墙内。
按照本发明的另一个优选实施例,传热室是设在处理室内并与处理室的内循环相连的。在处理室内,可以将沿壁向下流动的固体颗粒或在流化床内运动的颗粒引导到传热室内。传热室可以是连接到处理室内的一个侧壁上的壁室结构。传热室可以设置在离处理室底部有一段距离的侧壁处,或者可以将它座落在靠近底部(例如篦子)的地方或直接座落在底上。壁室可伸入到处理室内或从处理室向外延伸。
壁室可以由上述垂直回风管的类似方式构成,该壁室具有一个狭窄的入口通道和一个包括传热表面的延伸的下部。由壁室捕集的颗粒可在壁室下部内构成与上述回风管内的床相似的传热床。该床内的热传递是按在回风管内相同的方式控制的。
在高负荷状态下热的回收主要在回风管内进行,而在低负荷下主要在与处理室内的内循环相连的壁室内进行。
按照本发明的一个特定实施例,可以在传热区和固体颗粒输送区均匀地设置传热表面。因此本发明的固体颗粒区与传热区相比是非常小的,因而固体颗粒区的总传热表面面积与总传热区的总的传热表面而积相比是非常小的。从固体颗粒输送区内的总的传热表面上传递的热量最多只能达到总传热量的大约10%。大致10%的总传热表面面积可以设在固体颗粒输送区内。在正常工况下可以将基本均匀的流化气体送入所有的区内。流化气体可在整个传热室内保持向传热表面传递热量。流化气体还可在设有出口孔的小固体颗粒输送区将固体颗粒流从传热室再引入邻近的处理室内。为了在低负荷工况或起动时减少热传递量,可将除了固体颗粒输送区之外的所有传热区内的气流减至最小程度,固体物质通过该区再循环到处理室内。由于与传热室的其它部分相比较固体颗粒输送区非常小,所在只有很少量的热量在区内传递。
本发明的一个主要优点是可以独立地控制从固体流到传热室之间的热传递,即使只采用一个单个组合热传递和再循环室的情况也是如此。本发明在不扰乱流经传热室的固体流的情况下提供一种甚至可以切断热传递的方法。
在不改变通过传热室的总固体颗粒流量的情况下,改变传热室内流过不同喷嘴的气体比例可以控制热传递。总气流量可以保持恒定。增加流经位于传热表面下部或靠近传热表面的喷嘴的气流量可以增强热传递,增加流经远离传热表面的喷嘴的气流量可降低热传递。
本发明进一步提供了建造紧凑的传热室和处理室的可能性,这在加压应用中显得特别优越。
下面将参照附图,利用实例进一步描述本发明,其中;
图1是循环流化床反应器的垂直剖面示意图,该反应器的回风管内具有传热室;
图2沿图1的AA线截取的回风管下部的局部横剖视图;
图3是流化床反应器下部的垂直剖面示意图,该反应器的处理室内有一个传热室;
图4是沿图3的BB线截取的局部横剖视图。
图1示出了一个具有燃烧室或处理室12的循环流化床CFB燃烧器10,该燃烧室或处理室12内包含有膨胀的流化床或颗粒。颗粒分离器14连接在燃烧室12的上部,它用于分离从燃烧室排放出来的烟气和固体物质的混合物中携带的颗粒。设置一个类似回风管16这样的垂直通道,以便使分离的固体物质从分离器14中再循环到燃烧室12的下部内。对流段18连接在设在分离器14上部的气体出口20上。
燃烧室的壁22,24可以是膜式水冷壁,其中一个壁24是燃烧室12和回风管16共用的。
回风管16的下部26具有比回风管的上部更大的水平横截面。至少部分被流化的固体颗粒的床28设置在下部26内。设置在床28内的传热表面30用于回收在循环流化床(CFB)燃烧器系统内循环的固体物质中的热能。因此,回风管16的下部26构成了一个传热室26。利用对流段18内的传热表面32、34也可以回收热能。
出口孔36可形成固体流密封,能防止由于重力的作用而使固体颗粒出现不受控的流动。该出口孔36设置在传热室26的共用壁内,它用于将床28的固体颗粒再循环到燃烧室12内。出口孔低于床28的上表面38的高度并开口通向床28内。床28在出口孔36和床表面38之间的这段高度形成了气体密封,可防止气体从燃烧室12经出口孔36流入回风管16内。
为了使床至少部分流化,将流化气体从风箱40经回风管16底部内的篦条41引入床28内。为了引入输送或流化气体,还设置了喷嘴42,所以通过该喷嘴可再将输送气体经传热室26的侧壁44引入床28内。利用流化气体和/或输送气体可使输送传热室26内的固体物质至少部分流化。流化或输送气体也可以用于维持固体颗粒在床内的内部流动,例如维持在床内水平地输送固体颗粒。流化或输送气体也用于将固体颗粒输向出口孔36并使之通过该孔。
图2中所示的传热室26被分成至少两个传热区46、46’和一个设在传热区之间的固体颗粒输送区。传热区46、46’是通过在这些区内设置传热表面30、30’构成的。利用通过开孔40、40′、40″引入的独立控制的气流50、50′、50″来使传热区46、46′和固体颗粒输送区48流化。气流由阀52、52′、52″控制。固体颗粒出口孔36设置在固体颗粒输送区48内的壁24上。
传热室26内的热传递是通过控制引入到不同区域内,特别是传热区46和/或46′内的流化气体的流动来控制的(如图2所示)。有可能会出现由于气流50和/或50′的减小而使热传递减弱的情况,因此造成传热表面30和/或30′周围的固体颗粒流化程度的降低以及在区域46和/或46′内热传递的减弱。
只要将流化气体送入固体颗粒输送区48内,固体物质从传热室26进入燃烧室12的流动就不受对热传递进行控制的影响。
可以将固体物质在回风管16的整个宽度上,例如侧壁24的整个宽度上均匀或不均匀地送入传热室26内。由于固体颗粒能在室内的各个方向上自由流动,所以固体颗粒的进入地点不是很重要的。进入地点可以高于传热区46、46′或高于固体颗粒输送区48。因此,送入传热室26的固体颗粒可以从不同的位置流向出口孔36并进入燃烧室12,即使在由于传热区46、46′内的流化程度降低,从而使热传递减弱的情况下也是如此。如果需要的话,可以通过减少经开孔41″进入特定输送区48的气流的方法来防止固体流在该特定区内通过出口36。
本发明的传热室26可允许固体物质在不同的区46、46′48之间自由流动,这是因为没有使用防碍这种流动的隔离壁的缘故。流化或输送气流可以用于在不同区之间和区内引导或输送固体颗粒。固体颗粒可以在几乎没有流化或输送气体的帮助下从比相邻区的床表面高的区自由流向所述较低的相邻区。
图3显示了一个带有壁室54的流化床反应器的下部,该壁室54用于收集流化床燃烧室12内的内部循环中的固体颗粒及回收收集在壁室内的物质中的热量。
壁室54的上部有一个入口通道56,下部有一个传热室58,传热表面30设在该传热室内。壁室54可以沿燃烧室12内的部分侧壁22′或整个侧壁22′延伸。隔离壁60将壁室与燃烧室隔开。
在传热室的上部设有溢流孔62,固体颗粒可通过溢流孔流入燃烧室12。如果需要可在低于床表面38处设置一些具有固体流密封作用的辅助出口孔。
图4为沿BB线截取的传热室54的局部剖面图。传热室被分成两个传热区46、46′和一个位于这两个传热区之间的固体颗粒输送区48。在传热区46、46′内设置有传热表面30、30′。
图中示出了位于各分开的区46、46′上方的三个溢孔62、62′62″,其中一个孔62″高于另外两个孔。通过独立的风箱66、66′66″引入独立控制的流化气流50、50′50″。靠减少气流50和50′可减弱传热室内的热传递,从而使传热表面周围的固体颗粒的流化程度降低,热传递也减弱。然而,送入到传热室的固体颗粒可以继续流过溢流孔62、62′。如果传热室内床的高度增加,那么固体颗粒也可通过溢流孔62″排出传热室。
在某些特殊情况下也可以使传热室的底部完全停止流化,这时固体颗粒仍可在通过设在高于固体颗粒输送和传热表面处的喷嘴51(参见图3)引入的流化或输送气体的作用下,利用溢流作用再循环到燃烧室内。因此,固体颗粒输送区应设在传热区46、46′垂直的上方。
虽然这里结合目前最实用的本发明优选实施例描述了本发明,但应理解到,本发明不受所公开的实施例的限制,相反它包括了权利要求表述的精神实质和范围内的各种变型和等效结构。
Claims (20)
1.从流化床反应器内的固体颗粒中回收热能的方法,该流化床反应器包括一个其内具有固体颗粒流化床的处理室,并利用一个与该具有固体颗粒流化床的处理室相连的传热室,传热室内设有传热表面,该方法包括:
连续地将热固体颗粒从处理室导入到传热室内的固体颗粒流化床;
为了控制传热室内固体颗粒的流动而将气体送入传热室;
利用设在传热室内的传热表面回收热能;
在传热室的固体颗粒流化床,在基本相同的水平高度设置至少一个传热区和至少一个固体颗粒输送区;
通过将独立控制的气流引入传热区来控制传热区的热传递,将独立控制的气流引入固体颗粒输送区来控制固体颗粒的再循环;
连续地将从传热室的所述固体颗粒输送区排出的固体颗粒通过出口装置再循环到处理室内;
其特征在于:连续地将热固体颗粒流从处理室导入到传热室,落到传热室中固体颗粒流化床的上表面;
允许固体颗粒在至少一个传热区和至少一个输送区之间自由流动,所述传热区和输送区不用任何隔离壁彼此隔开。
2.按照权利要求1的方法,其特征在于将独立控制的流化气体送入传热区和固体颗粒输送区,以便控制所述区之间的固体颗粒内部流动。
3.按照权利要求1的方法,其特征在于在设置在循环流化床反应器的回风管内的传热室内,将独立控制的气流送入传热区和固体颗粒输送区,以便控制所述传热室内一个或多个入口与一个或多个出口之间的固体颗粒的流动路线。
4.按照权利要求1的方法,其特征在于在设置在处理室内的传热室内将独立控制的气流送入传热区和固体颗粒输送区,以便控制所述传热室内一个或多个入口与一个或多个出口之间的固体颗粒的流动路线。
5.按照权利要求1的方法,其特征在于将独立控制的流化气体送入传热区和固体颗粒输送区,以便控制固体颗粒通过传热区和固体颗粒输送区的内部的水平流动,所述传热区由固体颗粒输送区将它们互相分离,该传热区设置在与固体颗粒输送区大致相同的水平高度上。
6.按照权利要求1的方法,其特征在于将流化气体送入传热室的传热区并通过控制流化气体的流动来控制热传递。
7.按照权利要求1的方法,其特征在于将输送气体流送入传热室的固体输送区内,并通过控制所述输送气体流来控制热传递。
8.按照权利要求1的方法,其特征在于通过溢流的方式使固体从传热室排出。
9.按照权利要求1的方法,其特征在于利用在低于流化床表面高度处设置的开孔来将固体排出传热室,所述的开孔成为固体流的密封。
10.按照权利要求1的方法,其特征在于使从处理室引出的热固体颗粒基本上通过传热室的整个水平横截面。
11.从流化床反应器内的固体颗粒中回收热能的设备,它具有一个其内有固体颗粒流化床的处理室(12),所述设备包括:
与处理室(12)相连并具有固体颗粒流化床(28)的传热室(26,58),
设置在传热室(26,58)内的传热表面(30,30′),
用于将连续流动的热固体颗粒从处理室(12)送入传热室(26,58)的入口装置(16,56),
用于将固体颗粒从传热室(26,58)连续地再循环到处理室(12)的出口装置(36,62,62′,62″),
用于将气体送入传热室(26,58)的喷嘴装置(40,40′,40″;41,41′,41″;42;50,50′,50″,51,66,66′,66″),
在所述传热室(26,58)内的固体颗粒流化床(28)内,在基本相同的水平高度的至少一个传热区(46,46′)和至少一个固体颗粒输送区(48),
用于在传热室内控制热传递的装置,所述装置包括用来将气流引入所述固体颗粒流化床的传热区(46,46′)和固体颗粒输送区(48)内的独立控制装置(52,52′,52″),
其特征在于,用于连续流动的热固体颗粒导入的入口装置(16,56)设置在传热室(26,58)之上,使热固体颗粒流落到其内的固体颗粒流化床(28)的上表面(38);使至少一个传热区(46,46)和至少一个输送区(48)被设置成允许固体颗粒在其间自由流动,传热区和输送区(46,46′,48)不用任何隔离壁彼此隔开。
12.按照权利要求11的设备,其特征在于传热室(26,58)内的相同水平高度上设置二个或更多的传热区(46,46′),所述传热区(46,46′)由固体颗粒输送区(48)将安们互相隔开。
13.按照权利要求11的设备,其特征在于出口装置(36,62,62′,62″)包括利用溢流的方式使固体颗粒排出的开孔。
14.按照权利要求11的设备,其特征在于出口装置(36,62,62′,62″)包括设置在传热室(26,58)流化床的表面(38)高度这下几个狭窄的水平缝状的开孔,所述开孔形成了传热室(26,58)内的固体流动密封。
15.按照权利要求11的设备,其特征在于循环流化床反应器内的传热室(26,58)设置在回风管(16)的底部(26)。
16.按照权利要求15的设备,其特征在于其中回风管(16,56)位于与处理室(12)壁平行的两个实质上是平面的管壁之间,回内管(16,56)上具有基本上为长方形的狭缝状出口孔,所述回风管(16,56)内的出口孔也构成了传热室(26,58)内的入口孔。
17.按照权利要求11的设备,其特征在于其中传热室(58)设在处理室(12)内。
18.按照权利要求11的设备,其特征在于其中传热表面(30,30′,30″)均匀地设在传热区(46,46′)和固体颗粒输送区(48)内,固体颗粒输送(48)小于传热区(46,46′),这样,总传热区(46,46′)内的总的传热表面面积大于总固体颗粒输送区(48)内的总的传热表面面积。
19.按照权利要求18的设备,其特征在于其中固体颗粒输送区(48)内的总的传热表面面积与传热区(46,46′)内的总传热表面面积相比要小得多。
20.按照权利要求11的设备,其特征在于传热室(26,58)包括均匀设置在传热区(46,46′)和固体颗粒输送区(48)内的传热表面(30,30′,30″)总热区(46,46′)大于总的固体颗粒输送区(48),这样,在固定颗粒输送区(48)的内总热传递量小于传热区(46,46′)总热传递量的10%。
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/973,396 US5341766A (en) | 1992-11-10 | 1992-11-10 | Method and apparatus for operating a circulating fluidized bed system |
US041,571 | 1993-04-05 | ||
US08/041,571 US5332553A (en) | 1993-04-05 | 1993-04-05 | Method for circulating solid material in a fluidized bed reactor |
US973,396 | 1993-05-26 | ||
US066,277 | 1993-05-26 | ||
US08/066,277 US5540894A (en) | 1993-05-26 | 1993-05-26 | Method and apparatus for processing bed material in fluidized bed reactors |
US08/131,852 US5406914A (en) | 1992-11-10 | 1993-10-05 | Method and apparatus for operating a circulating fluidized bed reactor system |
US131,852 | 1993-10-05 |
Publications (2)
Publication Number | Publication Date |
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CN1088477A CN1088477A (zh) | 1994-06-29 |
CN1042499C true CN1042499C (zh) | 1999-03-17 |
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Application Number | Title | Priority Date | Filing Date |
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CN93112936A Expired - Fee Related CN1042499C (zh) | 1992-11-10 | 1993-11-10 | 在流化床反应器内回收热能的方法和设备 |
Country Status (13)
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---|---|
US (1) | US5406914A (zh) |
EP (1) | EP0682761B1 (zh) |
JP (1) | JP3084064B2 (zh) |
KR (1) | KR100338694B1 (zh) |
CN (1) | CN1042499C (zh) |
AT (1) | ATE163218T1 (zh) |
CA (1) | CA2149047C (zh) |
DE (1) | DE69317002T2 (zh) |
DK (1) | DK0682761T3 (zh) |
ES (1) | ES2114074T3 (zh) |
FI (1) | FI104215B1 (zh) |
PL (1) | PL176693B1 (zh) |
WO (1) | WO1994011672A1 (zh) |
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- 1993-11-09 ES ES93924632T patent/ES2114074T3/es not_active Expired - Lifetime
- 1993-11-09 DE DE69317002T patent/DE69317002T2/de not_active Expired - Lifetime
- 1993-11-09 CA CA002149047A patent/CA2149047C/en not_active Expired - Fee Related
- 1993-11-09 JP JP06511754A patent/JP3084064B2/ja not_active Expired - Lifetime
- 1993-11-09 AT AT93924632T patent/ATE163218T1/de not_active IP Right Cessation
- 1993-11-09 WO PCT/FI1993/000467 patent/WO1994011672A1/en active IP Right Grant
- 1993-11-09 KR KR1019950701859A patent/KR100338694B1/ko not_active IP Right Cessation
- 1993-11-09 DK DK93924632T patent/DK0682761T3/da active
- 1993-11-09 EP EP93924632A patent/EP0682761B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
FI104215B (fi) | 1999-11-30 |
CA2149047C (en) | 2000-01-11 |
ES2114074T3 (es) | 1998-05-16 |
DE69317002D1 (de) | 1998-03-19 |
FI952156A0 (fi) | 1995-05-05 |
DK0682761T3 (da) | 1998-09-23 |
EP0682761A1 (en) | 1995-11-22 |
EP0682761B1 (en) | 1998-02-11 |
JPH08503291A (ja) | 1996-04-09 |
JP3084064B2 (ja) | 2000-09-04 |
CN1088477A (zh) | 1994-06-29 |
KR100338694B1 (ko) | 2002-10-18 |
FI104215B1 (fi) | 1999-11-30 |
FI952156A (fi) | 1995-07-06 |
PL308954A1 (en) | 1995-09-04 |
KR950704644A (ko) | 1995-11-20 |
CA2149047A1 (en) | 1994-05-26 |
ATE163218T1 (de) | 1998-02-15 |
WO1994011672A1 (en) | 1994-05-26 |
PL176693B1 (pl) | 1999-07-30 |
US5406914A (en) | 1995-04-18 |
DE69317002T2 (de) | 1998-08-13 |
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