CN1305557C - 借助于光催化剂加上磷光性固体物质进行液体处理的反应器和方法 - Google Patents

借助于光催化剂加上磷光性固体物质进行液体处理的反应器和方法 Download PDF

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CN1305557C
CN1305557C CNB038083647A CN03808364A CN1305557C CN 1305557 C CN1305557 C CN 1305557C CN B038083647 A CNB038083647 A CN B038083647A CN 03808364 A CN03808364 A CN 03808364A CN 1305557 C CN1305557 C CN 1305557C
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phosphorescent particles
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CN1646216A (zh
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维尔纳·利蒂
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Abstract

本发明涉及一种反应器(1)用于在液态或气态的反应介质中进行光催化反应，其包括带有固体的光催化剂(8)的反应容器(1)、输入和排出管道(3、4)、混合装置(2)和一用于供给电磁辐射的装置(5)，其包括微辐射体(7)，该微辐射体(7)吸收电磁辐射并且延时地辐射光，光激发光催化剂，本发明还涉及用于进行光催化反应的方法，其中固体的光催化剂悬浮于液态或气态的反应介质中并借助于微辐射体使之活化，其中微辐射体在一电磁辐射源上充电并延时地辐射该能量。

Description

借助于光催化剂加上磷光性固体物质 进行液体处理的反应器和方法
技术领域
本发明涉及一种用于工业应用光催化的新的反应器方案和方法方案。
背景技术
当使电半导体与可起反应的物质发生接触时，光催化产生一种作用。在这种情况下通过辐射处理，电子被激发进入一能量较高的导带内。留下一“空穴”。受激发的电子和空穴可以随分子或原子团，到达半导体的表面，例如氧化还原反应。这样，在存在氧的场合下实现将大多数的有机分子、细菌和病毒完全氧化。
已有关于水和气体的净化的应用(Bahnemann，Detlef：“污水的光催化解毒”，环境化学手册，O.Hutzinger(编辑)，卷2：反应和过程，部分L：环境光化学，P.Boule(发行)，Heidelberg出版社，1999年，285-351页)。最常用的光催化剂是TiO2。其具有一3.2eV的能量间距，借助于波长小于385nm的紫外光可将其活化。但也存在许多其他的具有部分较强的能量间距的光催化剂。它们可以用较长波长的光活化。在光催化剂的开发的最近时期使其以极不同的特性工作。特别是在这方面作为能量激发剂，可见光的范围的能量活化剂的这方面(Lettmann，Christian：“用于以可见光光催化的水净化的混合氧化物的传统的和组合的开发”，Saarland(萨尔)大学博士论文，2001年)和日光的应用被提及(EP 0 812619 A1)。
文献中描述了各种反应器结构形式。
广泛流行的是“多隔板反应器”，其中待处理的流体曲折形地流过涂有光催化剂层的表面(EP 0 738 686 A1)。催化剂穿过流体辐射，对此在所述的废水净化的情况中描述了日光用作为活化剂和TiO2用作催化剂。作为变型方案描述了将催化剂悬浮于流体中并且在流过装置以后再将其分离。
这样的装置需要极大的空间。
描述了涡形装置，其包含催化剂并流过待处理的流体。用灯进行照射，其横向地安装在涡形装置上(WO 96/36 565)。该装置如同“多隔板反应器”需要较大的空间。
“球形燃料反应器”包括许多玻璃球，其涂有催化剂层并且流体通过其中间空隙流动(WO 95/11751)。通过灯进行辐射，其被装入装料区内。最通常的应用是用作固定床，但也用作流化床。其缺点是，必须用微小的辐射穿透深度来获得提高的充填密度。
在悬浮液反应器中细屑的悬浮的催化剂用不同形式排列的灯进行辐射(EP 0 233 498 B1)。由于因其他的催化剂粒子或反应粒子造成强的遮蔽，如果不用大大稀释的催化剂溶液和相应微小的反应进行工作的话，现有的催化剂表面只是一很小的部分被活化。
描述了装置，其中光通过玻璃板向光催化剂传送(WO 97/37936)。空间占用和复杂的构造方式相当于上述的多隔板反应器。
在WO 98/17390中描述了一种具有薄玻璃片的装置。它们在其表面上带有催化剂。通过灯进行辐射，其借助于各玻璃板中的空隙穿透玻璃板的环状设置的溜井。构造方式是很精细的并且是复杂的。
全部已知反应器构造方式相同的是，它们只达到辐射的催化剂表面的很小的充填密度。这使得装置是昂贵的。此外其常常需要占用很大的空间，这也是使应用更昂贵。
稍微紧凑的已知构造方式是很精细而复杂地构成的，因此是相应昂贵的。
在这些情况下实际上的背景在于，光催化作用至今还没有实现大规模的工业应用。
发明内容
因此提出开发一种方法和装置的目的，其将辐射的催化剂表面的尽可能高的充填密度与尽可能价廉的构造和操作方式结合起来。
该目的通过本发明的方法和反应器来实现。
按本发明的用于在液态或气态的反应介质中进行光催化反应的反应器，包括一具有固体的光催化剂、输入和排出管道、混合装置的反应容器和一用于供给电磁辐射的装置；其特征在于，包括磷光性粒子，这些磷光性粒子吸收用于供给电磁辐射的装置的电磁辐射并且在反应器内部延时地辐射光，该光激发光催化剂。
按本发明的用于进行光催化反应的方法，其特征在于，固体的光催化剂悬浮于一液态或气态的反应介质中或涂覆在一表面上并借助于磷光性粒子被活化，这些磷光性粒子在一电磁辐射源上加充能量并延时地辐射该能量。
通过磷光性物质传送能量
本发明基于新式原理，通过磷光性物质向光催化活性表面(以下称为光催化剂PK)传送必要的能量，其中磷光性粒子发射出合适的波长的光并使PK活化。
必须使磷光性粒子(以下称为微辐射体MR)借助一合适的光源“充电”。其然后被传给光催化活性层，其中它们完全或部分地发射其存储的电磁能量，以便此后重新到达UV(紫外线)光源，等等。
其优点是，在选择适合的MR时，存储的能量以几秒到几分钟的半衰期在反应室内部被继续传给PK，此时PK施加其催化剂作用，同时由于PK的活性状态的短的半衰期，其还只在能源附近反应。
作为反应器考虑各种反应器型式，其可以用于反应和/或物质传送过程，特别是：
流化床、流化床级联、流化槽，
喷流床、由喷流床构成的级联，
循环反应器、由循环反应器构成的级联，
搅拌容器、搅拌容器级联，
管式反应器，
固定床(具有PK涂层)或全部敞开的有序的结构如薄片、蜂房等。
在全部这些方法中将MR在光源上活化，物理上与反应溶液和PK相混合，在向PK发出能量以后导回光源“充电”并且重新输给催化剂。
首先可以通过在装置中的流动和粒子扩散实现混合。如果这样的传送机构是足够的，则可将光源例如UV灯直接安装在装置的壁上或装置内，借此其在流过的MR附近以高的能量密度充电，以便此后通过流动重新进入反应器的内部。
另外通过导向板、折流板、搅拌器等可以改进这样的传送机构。
可选择或附加地可以将MR经由一外部的回路在合适的灯上导过。为此优选从待处理的流体和PK中分离MR，以便提高其在灯源上的浓度和避免由于PK粒子和基片粒子的遮蔽。在这种情况下优选对流地传送MR与一微小量的待处理的流体。
最常用的光催化剂是TiO2。其具有一3.2eV的能量间距，借助于波长小于385nm的紫外光可将其活化。但也已知许多其他的光催化剂，它们可以用大于385nm的波长的光活化。作为实例其中有所谓的ZnO和其他的过渡元素的氧化物(WO 95/11751)以及CdS(EP 0 234 875 B1)和SnO2、SrTiO3、WO3、Fe2O3(WO 96/36565)。还可以继续列出一系列实例。
在最近时期开发了用于可见光范围的光催化剂(Lettmann，Christian：“用于以可见光进行光催化的水净化的混合氧化物的传统的和组合的开发”，萨尔大学博士论文，2001年)以及应用日光的光催化剂(EP 0 812619 A1)。
优选采用较硬的和耐磨的PK，其中不能被氧化的无机物质是优选的。按照应用方式PK可以具有十分不同的粒子尺寸和结构。
悬浮催化剂：粒子直径1nm至100μm
流化床反应器：粒子直径1μm至1mm
在固定床(或全部的具有有序结构如薄片、蜂房等的反应器)的应用中，光催化剂作为或多或少的薄层固定在静止的载体上。
微辐射体MR
微辐射体MR是一种磷光性固体物质，其以粒子的形式应用。其必须具有足够长的余辉时间(至少在几秒钟范围内，更好是几分钟或更长，优选5秒至30分钟)并且在波长范围内放射，光催化剂可在其中被活化。适用的磷光性固体物质的实例
已知许多具有在可见光范围内放射的磷光性固体物质，它们虽然为其他的目的开发，但满足关于这里所述的应用的全部要求。代替大量的列举，请参阅下列文献，其内容在此引入作为参考。
(US P6 287 993，DE 195 21 119 A1，DE 199 26 980 A1，DE 199 34436 A1)。
这种MR的应用例如与Lettmann，christian：“用于以可见光进行光催化的水净化的混合氧化物的传统的和组合的开发”，萨尔大学博士论文，2001年，中所述的光催化剂(PK)组合来实现。
DS P6 287 993中，描述了长时间发光的磷光性物质。特别在其实例17中描述了利用锌和添加镨的玻璃，其适用于以350至450nm的放射，使TiO2作为光催化剂进行活化(参见图3)。
在DE 195 21 119 A1中还描述了“缓慢衰减”的磷光性物质，其可以用作为TiO2-活化剂，因为它也在400nm下放射。其中涉及玻璃，其添加有稀土金属。
原则上，MR颗粒大小范围如同在光催化剂PK按照应用在1nm与1mm之间，优选为1μm-0.5mm。
一个有效而经济的方案，优选对于大型装置，在于MR的粒子尺寸明显超过PK的，以便一在灯上“充电的”MR粒子辐射尽可能多的PK粒子。此外其优点是，通过过滤器或滤网易于将MR与流体和在其中包含的PK分离，并且可以回收再生。
另一有效而经济的方案，优选对于小的装置，在于MR的粒子尺寸明显小于PK的，以便达到MR和PK的简单的分离。
但原则上不能排除PK和MR的粒子尺寸的任何比例。这仅仅由于适用的装置型式的多样性就已得出。
大块粒子是适用的，其可以特别简单地制造，但也是这样的，其中磷光性物质涂覆在一载体芯部上。当采用磁芯时开启MR粒子的分离和传送的另外的可能性。
避免对MR的磨损和/或MR的腐蚀和/或溶解
为了避免磨损，当MR无论怎样不由玻璃构成时，其可以涂覆以透光的(薄)层(例如玻璃)。这还可以保护MR在待处理的流体中抗腐蚀或溶解。
光催化剂PK和微辐射体MR的分离
PK和MR(也有磨耗！)从流体中的分离可以通过经典的方法如过滤器、旋分机、离心机等但对MR也可以利用磁性分离机(见上文)来实现。
PK和MR彼此的分离可以通过粒子尺寸(过滤器、旋分机)，但也可以通过密度(旋分机、离心机)和其他的物理差异(例如MR的磁芯，见上文)来实现。
优选的方法在于，较大的MR借助于一带通过滤器从流体和PK中分离，将分离的MR借助于一富能的光源活化，并且从过滤带的末端重新送回流体中。
具有合适于激发微辐射体粒子的光谱的UV辐射器特别适合用作为光源。
在外部的回路中优选将灯安装于一专用的装置中。它通过其MR粒子的导向装置保证，实现全部MR粒子的尽可能有效的照射；例如通过：
MR粒子在一窄缝内绕灯运动；
利用良好的横向于流动方向的粒子传送的流动(例如在一具有装入的灯的流化床中或通过形成一紊流等)。
优选在外部的灯之前将光催化剂PK与微辐射体MR分离，以免在MR“充电”时被PK遮蔽。
同样在装置中直接辐射时，优选在辐射器附近将PK(至少部分地)与MR分离(例如通过导流装置或前置的过滤器或在采用MR的磁芯时的磁场)。
当然，除待处理的流体外还必须供给反应器以必要的反应物。(例如：供给O2以便氧化水中的有机污物)。
同样通常必须在反应器之后从处理过的流体中分离反应物(例如CO2)。
介质和反应的问题解决的适用性
按照本发明的方法适用于全部的化学反应，其可以在液体或气体中在光催化活性表面上实施。
本发明优选的应用是用于水和气体(同样水中的气泡)中的溶解的有机分子、散布的小滴和固体物质粒子、微生物和病毒的氧化。
用于MR的“充电”的光的波长和在通过MR辐射时的光的波长必须是不等的。通常辐射的光以长波移动。由MR辐射的光应该是足够富能的(短波的)，以便产生必需的催化剂能量(例如UV光)。
“光”的含义可以用概念“合适波长的电磁辐射”代替，因此也适用于在相应的光催化剂的应用中的其他的波长范围(特别是可见光或日光)。
通过微辐射体MR的应用使辐射的催化剂表面达到一充填密度，如其利用任何已知的方法都是不可能的。并且可以采用相当简单的可能公知的装置。它只须适配于新的方法或修改。仅仅包括外部的灯的装置可能需要新结构。
附图说明
图1为实验室悬浮液反应器；
图2为包括微辐射体MR的外部的循环的实验室悬浮液反应器；
图3为包括曲折的筋条以及光催化剂(PK)和微辐射体(MR)的分开的外部的循环的管式反应器；以及
图4为包括涂有光催化剂层的蜂房内部结构和外部分的活化作用的管式反应器。
具体实施方式
实例1：按照图1的实验室悬浮液反应器
该反应器包括具有叶片式搅拌器2的搅拌槽1、一氧(空气)的输入管道3、一废气的排出管道4和一外部的灯(UV辐射器)5，并且包括由一反应介质6、用o表示的微辐射体7和用·表示的光催化剂8组成的悬浮液。
将包括有机物质和光催化剂以及微辐射体MR的500ml的水溶液的悬浮液在一800ml反应器容积中不断地搅拌，借此产生在中心下降而在壁上上升的循环的流动，同时一UV灯(350nm辐射最大值时功率20瓦)在侧面入射(辐射面积50cm2)。由此在平均时间上全部MR粒子到达UV光源处，其在那里被活化，以小气泡的形式导过空气。
微辐射体MR的添加大大提高有机组分的分解率，其中它将辐射能量带入反应器的内部。
实例2：按照图2包括微辐射体MR的外部的循环的实验室悬浮液反应器
该反应器包括一具有叶片搅拌器2的搅拌槽1、一氧(空气)的输入管道3、一废气的排出管道4，其中在搅拌器2的下方设有一沉积室9，其中聚集较重的MR7，以便与少量流体6一起通过泵10和管道11导入UV灯5的外部的环形间隙12，并且在活化以后通过管道13重新从上面导回到搅拌容器1中。
将包括可氧化物质、光催化剂和微辐射体的水溶液的悬浮液不断地搅拌并且通过导通的空气充满以O2。微辐射体(0至10g)在沉积室中不断地与光催化剂分离并且在经过UV灯以后导向实验室反应器。圆周速度为例如5或10ml/min。在这种情况下在外部回路中具有附加于搅拌容器中总量为10g或在两个灯时为20g的MR。微辐射体的添加大大提高有机物质的分解率。循环的流量的提高同样提高了分解率。
实例3：
按照图3的管式反应器包括曲折的筋条以及光催化剂(PK)和微辐射体(MR)的分开的外部的循环。
该反应器包括一个具有装入的曲折形设置的多个水平筋条22的管式反应器21，其从下面通过管道23由混合器24供给混合物，该混合物包括：反应溶液6，其富集有氧并通过管道25输给混合器；光催化剂8，其通过泵27和管道26/28导入回路中；以及微辐射体7，其通过管道11和13、泵10和包围UV灯5的环形外壳12导入回路中，该混合物通过分离器29离开反应器，其在该分离器中分离成各组分。反应完的反应溶液和形成的废气通过管道30排出。
实例4：
按照图4的管式反应器包括涂有光催化剂层的蜂房内部结构和外部分的活化作用。
该反应器包括具有沿管方向的蜂房内部结构32的管形反应器壳体1，其涂有光催化剂层。反应溶液6由输入管道25和已活化的微辐射体7由回路管道13通过混合器24和管道23导入反应器，通过蜂房内部结构32，并且此时在它在分离器中被从溶液中分离和通过管道11和泵10导入灯5的环形外壳12以前向PK发射其光能，其在那里用UV光活化并通过管道13重新导回反应器中。

Claims (15)

1.用于在液态或气态的反应介质中进行光催化反应的反应器，包括一具有固体的光催化剂、输入和排出管道、混合装置的反应容器和一用于供给电磁辐射的装置；其特征在于，包括磷光性粒子，这些磷光性粒子吸收用于供给电磁辐射的装置的电磁辐射并且在反应器内部延时地辐射光，该光激发光催化剂。
2.按照权利要求1所述的反应器，其特征在于，用于供给电磁辐射的装置安装在可透过辐射的壁上或反应容器的内部，并且混合装置适用于将磷光性粒子从反应容器内部输向用于供给电磁辐射的装置并返回。
3.按照权利要求1所述的反应器，其特征在于，用于供给电磁辐射的装置包括一灯和一液体通道，该通道通过磷光性粒子的传送管道和输送装置与反应容器相连通。
4.按照权利要求3所述的反应器，其特征在于，灯构成为杆状的并由液体通道外套形地包围。
5.按照权利要求3或4所述的反应器，其特征在于，反应容器设有一用于使磷光性粒子与光催化剂和/或反应介质分离的装置。
6.按照权利要求1所述的反应器，为了氧化水或废水中的有机污物，其特征在于，设有空气或氧的输入管道和废气的排出管道。
7.按照权利要求1所述的反应器，其特征在于，反应容器为一流化床反应器、一通流或管式反应器、一固定床反应器或一搅拌容器反应器。
8.按照权利要求1所述的反应器，其特征在于，反应容器为悬浮液反应器并且光催化剂具有1nm至100μm的粒子直径，或者反应容器为流化床反应器或固定床反应器并且光催化剂具有1μm至1mm的粒子直径。
9.按照权利要求1所述的反应器，其特征在于，磷光性粒子具有5秒至30分钟的磷光半衰期和大小为1nm至1mm的粒度。
10.按照权利要求9所述的反应器，其特征在于，磷光性粒子具有大小为1μm至0.5mm的粒度。
11.用于进行光催化反应的方法，其特征在于，固体的光催化剂悬浮于一液态或气态的反应介质中或涂覆在一表面上并借助于磷光性粒子被活化，这些磷光性粒子在一电磁辐射源上加充能量并延时地辐射该能量。
12.按照权利要求11所述的方法，其特征在于，磷光性粒子在通过放出能量而使光催化剂活化以后被再次导过辐射源，并被重新加充能量。
13.按照权利要求12所述的方法，其特征在于，磷光性粒子在使光催化剂活化以后与光催化剂和/或反应介质分离，接着被导向一与反应介质分开设置的辐射源并加充能量，然后被导回反应器中。
14.按照权利要求11所述的方法，其特征在于，光催化反应是在水溶液中的有机化合物的氧化。
15.按照权利要求11所述的方法，其特征在于，催化剂是TiO2细粒而磷光性粒子是玻璃粒子，磷光性粒子掺杂有稀土金属并且可用UV光或可见光激发。
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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2919811B1 (fr) * 2007-08-08 2010-10-15 Saint Gobain Quartz Sas Media pour filtre photocatalytique
GB201004443D0 (en) * 2010-03-17 2010-05-05 Catalysystems Ltd Photocatalytic reactor and methods of use
CN102188907B (zh) * 2010-03-18 2014-01-01 清华大学 有害物质去除装置及使用其进行空气净化的空气净化装置
GB201018555D0 (en) * 2010-11-03 2010-12-15 Albagaia Ltd Fluid treatment apparatus
GB201105474D0 (en) 2011-03-31 2011-05-18 Albagaia Ltd Testing apparatus
US9593053B1 (en) 2011-11-14 2017-03-14 Hypersolar, Inc. Photoelectrosynthetically active heterostructures
GB201302035D0 (en) * 2013-02-05 2013-03-20 Ipurtech Ltd UV Apparatus
JP6165556B2 (ja) * 2013-08-27 2017-07-19 スタンレー電気株式会社 水素製造装置
JP6227355B2 (ja) * 2013-09-27 2017-11-08 スタンレー電気株式会社 水素製造装置
US10100415B2 (en) 2014-03-21 2018-10-16 Hypersolar, Inc. Multi-junction artificial photosynthetic cell with enhanced photovoltages
CN105668692A (zh) * 2016-03-30 2016-06-15 河南师范大学 一种磁性回收催化剂的光催化水处理装置及其控制方法
WO2017200336A1 (ko) * 2016-05-20 2017-11-23 김형오 필터의 세척기능을 구비하고 와류 속을 유동하는 고체 입자들의 마찰과 충돌을 이용한 수 처리용 하이드로크래셔
CN107857334A (zh) * 2017-10-24 2018-03-30 江阴市弘诺机械设备制造有限公司 一种改进的污水处理设备
DE102021132073A1 (de) 2021-12-06 2023-06-07 EKATO Rühr- und Mischtechnik GmbH Photoreaktorvorrichtung und Verfahren zum Betrieb einer Photoreaktorvorrichtung

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19521119A1 (de) * 1994-06-10 1995-12-14 Nichia Kagaku Kogyo Kk Langsam abklingende phosphoreszierende Stoffe
DE19746343A1 (de) * 1997-10-21 1999-04-22 Deutsch Zentr Luft & Raumfahrt Verfahren und Vorrichtung zur Einbringung solarer Strahlungsenergie in einen Photoreaktor
WO2000061719A1 (de) * 1999-04-13 2000-10-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Photobioreaktor mit verbessertem lichteintrag durch oberflächenvergrösserung, wellenlängenschieber oder lichttransport
DE19934436A1 (de) * 1999-07-22 2001-01-25 Riedel De Haen Gmbh Feinstkörnige anorganische Leuchtstoffe
US6214176B1 (en) * 1998-04-10 2001-04-10 Grt, Inc. Method of and apparatus for manufacturing methanol
DE19926980A1 (de) * 1999-06-14 2001-04-19 Riedel De Haen Gmbh Verstärkung der Leuchtdichte von langnachleuchtenden und/oder fluoreszierenden Oberflächen
US6287993B1 (en) * 1998-09-22 2001-09-11 Kabushiki Kaisha Ohara Long-lasting phosphorescent glasses and glass-ceramics

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3459672A (en) * 1966-05-18 1969-08-05 Sybron Corp Composite spheroidal phosphorescent organic polymer article and process
US4210953A (en) * 1973-12-13 1980-07-01 Stone Wilfred S Self-illuminated case
DE19514372A1 (de) * 1995-04-18 1996-10-24 Roehm Gmbh Reaktoren für die photokatalytische Abwasserreinigung mit Stegmehrfachplatten als Solarelementen
JP3690864B2 (ja) * 1996-03-29 2005-08-31 株式会社ティオテクノ 光触媒体の製造法
FR2749777B1 (fr) * 1996-06-12 1998-07-31 Kodak Pathe Composition photocatalytique transparente inorganique
SE514449C2 (sv) * 1998-10-23 2001-02-26 Cleanosol Ab Ytbeläggning avsedd att användas på markeringsbeläggningar för vägar, parkeringsplatser och liknande
JP2000288560A (ja) * 1999-04-02 2000-10-17 Hitachi Ltd 水の浄化処理装置及びその方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19521119A1 (de) * 1994-06-10 1995-12-14 Nichia Kagaku Kogyo Kk Langsam abklingende phosphoreszierende Stoffe
DE19746343A1 (de) * 1997-10-21 1999-04-22 Deutsch Zentr Luft & Raumfahrt Verfahren und Vorrichtung zur Einbringung solarer Strahlungsenergie in einen Photoreaktor
US6214176B1 (en) * 1998-04-10 2001-04-10 Grt, Inc. Method of and apparatus for manufacturing methanol
US6287993B1 (en) * 1998-09-22 2001-09-11 Kabushiki Kaisha Ohara Long-lasting phosphorescent glasses and glass-ceramics
WO2000061719A1 (de) * 1999-04-13 2000-10-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Photobioreaktor mit verbessertem lichteintrag durch oberflächenvergrösserung, wellenlängenschieber oder lichttransport
DE19926980A1 (de) * 1999-06-14 2001-04-19 Riedel De Haen Gmbh Verstärkung der Leuchtdichte von langnachleuchtenden und/oder fluoreszierenden Oberflächen
DE19934436A1 (de) * 1999-07-22 2001-01-25 Riedel De Haen Gmbh Feinstkörnige anorganische Leuchtstoffe

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