CN1165374C - 具有分解有机卤化物功能的吸附剂及其制造方法 - Google Patents
具有分解有机卤化物功能的吸附剂及其制造方法 Download PDFInfo
- Publication number
- CN1165374C CN1165374C CNB018012779A CN01801277A CN1165374C CN 1165374 C CN1165374 C CN 1165374C CN B018012779 A CNB018012779 A CN B018012779A CN 01801277 A CN01801277 A CN 01801277A CN 1165374 C CN1165374 C CN 1165374C
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- Prior art keywords
- active carbon
- adsorbent
- weight portion
- platinum
- tio
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Abstract
制造具有分解有机卤化物功能的吸附剂方法，其特征在于，包括使Pt和/或Pd的盐、有机钛化合物和有机结合体在溶剂中反应，由此合成在分子中含有Pt和/或Pd和Ti的有机金属化合物前体的分散液，向该分散液中加入TiO2溶胶，制造催化剂涂布溶液，用该催化剂涂布溶液浸渍活性炭并加热所得的该混合物，由此使活性炭上负载含TiO2的有机卤化物分解催化剂，并且其中分散有Pt和/或Pd的微细粒子。由该方法制得的吸附剂，可用于吸收含在排放废气中的有机卤化物，并且也可以在不再合成这些化合物的情况下将它们分解，而且还能用于吸收和除去SOx、NOx、HCl和重金属类等。
Description
技术领域
本发明主要是关于在焚化炉排放废气处理中所使用的具有分解有机卤化物(Halgoen)功能的吸附剂及其制造方法。
技术背景
在来自城市垃圾以及产业废弃物焚化炉所产生的有机卤化物的减少方法中，包括燃烧条件的改善以及排放废气处理的高度化。由于在进行一般的有机卤化物例如氯化有机物质的完全氧化分解的燃烧过程中，燃烧温度必须维持在1000℃以上的高温，因此为了避免炉壁造成损伤，通常燃烧温度只维持在800℃至900℃左右，通过改善燃烧条件不容易进行有机卤化物的完全氧化分解。
而且，对于在炉内容易产生局部低温部，即不完全燃烧部的自动供煤炉(Stocker)，为了使有机卤化物完全氧化分解必须设置再燃烧部，因而产生所谓排放废气总量的增加或再燃烧用的燃烧所造成运营成本(Running Cost)增加的问题。
此外，众所周知有机卤化物之中，二噁英(Dioxine)类以及溴化二噁英类化合物不但会在燃烧过程中生成，还会从未完全燃烧所残留下的未燃烧部分或具有苯环的前体物质在300℃至500℃左右的广泛温度范围中再合成。因此，即使在燃烧过程中，谋求减低二噁英类以及溴化二噁英类等的有机卤化物，但在后续的阶段中，二噁英类以及溴化二噁英类等的有机卤化物也会再合成，因而仍有无法减低排放废气中的二噁英类以及溴化二噁英类等有机卤化物的情况。
根据上述理由，为了使排放气中的以二噁英类以及溴化二噁英类等为主的有机卤化物稳定地维持在低浓度，因此必须在排放废气处理中进行除去处理。
作为由排放废气处理去除以二噁英类以及溴化二噁英类等为主的有机卤化物的除去处理方法，是以使用活性炭吸附的吸附法为主流。但是，吸附有机卤化物的活性炭会成为二次废弃物，其后续处理也会造成问题。
为了解决此问题，本发明人特别以熟知的五氧化二钒-二氧化钛(V2O5-TiO2)系或五氧化二钒-三氧化钨-二氧化钛(V2O5-WO3-TiO2)系的催化剂与活性炭并用，作为以二噁英类以及溴化二噁英类等为主的有机卤化物的分解催化剂，同时延长活性炭的寿命也在研究中。但是也证明了V2O5-TiO2系或V2O5-WO3-TiO2系的催化剂在催化剂入口处的作为有机卤化物的一种的二噁英类以及溴化二噁英类浓度低的情况下，反而生成了作为有机卤化物的一种的二噁英类以及溴化二噁英类。而且，因为在考虑近年来的居民协定等大多数排放废气中的二噁英类的浓度皆没有控制在政府标准值的1/10以下，所以证明过去使用的有机卤化物的分解催化剂很可能会有相反效果。
此外，由于过去使用的有机卤化物的分解催化剂需要在200℃至500℃的高温下使用，因此必须再加热排放废气。而且因为活性炭无法承受此种高温，无法在同一位置上使用催化剂与活性炭，证明同时使用催化剂与活性炭也不容易。
发明的公开
本发明的目的就是为了解决上述以往的问题点，提供一种具有分解有机卤化物功能的吸附剂及其制造方法，该吸附剂不但能够吸附排放废气中含有的有机卤化物，还由于更有效率地进行分解而延长其使用寿命并能够抑制二次废弃物的生成量，而且此时不具有再合成二噁英类以及溴化二噁英类等有机卤化物的能力。
为了解决上述问题而开发的本发明的具有分解有机卤化物功能的吸附剂，是由活性炭以及负载在活性炭上的有机卤化物分解催化剂所组成，其特征在于该有机卤化物分解催化剂是将分子内含有铂(Pt)和/或钯(Pd)与钛(Ti)的有机金属前体分散液与二氧化钛(TiO2)溶胶混合加热而形成的，所以是使铂(Pt)和/或钯(Pd)的微粒子分散于二氧化钛(TiO2)中的。
而且，本发明的有机卤化物分解催化剂的制造方法，其特征在于，通过将铂(Pt)和/或钯(Pd)的盐、钛(Ti)的有机化合物、以及有机结合体，在溶剂中反应，合成出分子内含有铂(Pt)和/或钯(Pd)与钛(Ti)的有机金属前体分散液，将此有机金属前体分散液与二氧化钛(TiO2)溶胶混合后，将活性炭浸入其中并加热，使铂(Pt)和/或钯(Pd)的微粒子分散于二氧化钛(TiO2)中的有机卤化物分解催化剂负载在活性炭中。而且作为有机结合体是以使用L-赖氨酸(L-lysine)或L-脯氨酸(L-proline)等的氨基(Amino)酸类为佳，又作为钛(Ti)的有机化合物是以使用钛(Ti)的醇盐(Alkoxide)衍生物为佳。
本发明的具有分解有机卤化物功能的吸附剂，因为是将分子内含有铂(Pt)和/或钯(Pd)与钛(Ti)的有机金属前体分散液与二氧化钛(TiO2)溶胶混合加热而形成，所以是将铂(Pt)和/或钯(Pd)的微粒子分散于二氧化钛(TiO2)中的有机卤化物分解催化剂负载在活性炭中的，所以可使活性点极高的催化剂高活性化。因此即使减少昂贵的铂(Pt)或钯(Pd)的含量，也可以分解有机卤化物。有机金属前体分散液与二氧化钛(TiO2)溶胶的混合物的加热，是在450℃至500℃的加热温度下，空气的大气环境中，通常的大气压下进行。由于加热时间与加热温度等的关系使有机结合体完全烧掉、且铂(Pt)和/或钯(Pd)均一分散于二氧化钛(TiO2)中的充分的时间。
此外，即使是V2O5-TiO2系或V2O5-WO3-TiO2系那样的催化剂也不会使有机卤化物再合成。而且，活性炭的使用温度范围虽然是在130℃至150℃的温度范围但也可以发挥优良的机能，且使活性炭的使用寿命延长到以往的数倍，也不需要再加热排放废气。
附图的简单说明
图1是表示采用负载了铂(Pt)的活性炭去除邻氯甲苯的特性示意图。
图2是表示负载了铂(Pt)的吸附剂中的邻氯甲苯浓度的示意图。
图3是表示采用负载了铂(Pt)的活性炭除去邻溴甲苯的特性示意图。
图4是表示负载了铂(Pt)的吸附剂中的邻溴甲苯浓度的示意图。
图5是表示采用负载了钯(Pd)的活性炭除去邻氯甲苯的特性示意图。
图6是表示负载了钯(Pd)的吸附剂中的邻氯甲苯浓度的示意图。
图7是表示采用负载了钯(Pd)的活性炭除去邻溴甲苯的特性示意图。
图8是表示负载了钯(Pd)的吸附剂中的邻溴甲苯浓度的示意图。
实施发明的最佳方案
下面示出本发明的优选实施方案。
首先，作为钛的有机化合物的钛(Ti)的醇盐衍生物(例如是将钛(Ti)的醇盐的一部分以乙酰丙酮配位基(Acetylacetonato)置换的衍生物或以三乙醇胺配位基(Triethanoaminato)置换的衍生物)与铂(Pt)和/或钯(Pd)的可溶性盐，溶解于包含有机结合体的溶剂中。作为铂(Pt)的可溶性盐可以使用氯铂酸、氯铂酸六水合物、二氯化铂、四氯化铂等。作为钯(Pd)的可溶性盐可以使用氯化钯、硝酸钯等。
在本发明中作为钛与贵金属的有机结合体可以使用L-赖氨酸(L-lysine)或L-脯氨酸(L-proline)等的氨基酸类，且特别是L-脯氨酸对于作为溶剂而使用的甲醇有高溶解性所以为优选。所谓有机结合体是指使钛离子、铂(Pt)离子和/或钯(Pd)离子与有机结合体分子结合，并固定在分子内，通过加热而除去后，生成二氧化钛(TiO2)与铂(Pt)和/或钯(Pd)的微粒子结合体的物质，并且是对于所得到的有机卤化物分解催化剂的物性不会给予催化剂中毒等的不良影响的物质。通过此有机结合体使钛(Ti)离子与铂(Pt)离子和/或钯(Pd)离子结合，并固定在分子内。
上述各成分的较佳混合比例是相对于钛(Ti)的醇盐衍生物100重量份而言，铂(Pt)和/或钯(Pd)的盐为0.5重量份至5重量份，甲醇为100重量份至200重量份，氨基酸为0.1重量份至1.5重量份。在70℃至80℃的温度下使它们进行反应时可得到各成分以分子水平(level)均等地分散的有机金属前体分散液。在此有机金属前体指的是钛(Ti)离子与铂(Pt)离子和/或钯(Pd)离子在一个分子内通过化学键合而连接在一起的物质，与在溶剂中溶解的状态不同，各离子的相对的位置关系是一定的物质。在此状态下钛(Ti)与铂(Pt)和/或钯(Pd)通过氨基酸而结合在一起，但是与作为糊化作用的二氧化钛(TiO2)溶胶50重量份混合作成催化剂涂敷(Coat)溶液，将活性炭浸入其中并在450℃至500℃的温度下加热时，烧掉作为有机结合体的氨基酸、分解有机金属前体，使铂(Pt)和/或钯(Pd)超细粒子化并高度分散于二氧化钛(TiO2)中的有机卤化物催化剂本身负载入活性炭中，而可以得到相对于如此得到的具有有机卤化物分解机能的活性炭100重量份，二氧化钛(TiO2)为1重量份，铂(Pt)和/或钯(Pd)为0.01重量份的比例的吸附剂。就活性炭而言，以3mm至10mm程度的粒状活性炭，BET比表面积300m2/g以上者为佳。
二氧化钛(TiO2)溶胶是将一次粒子的粒径为10nm程度的二氧化钛(TiO2)分散于酸性溶液中而得到的物质，含二氧化钛(TiO2)本身例如是30％左右。作为溶液例如是硝酸酸性与盐酸酸性为主，在考虑对催化剂本身的活性的影响时，以使用硝酸酸性的二氧化钛(TiO2)为佳。
此有机卤化物分解催化剂由于使铂(Pt)和/或钯(Pd)超微细粒子化，则使活性点明显地增大，所以使催化剂活性提高。因此，与采用在二氧化钛(TiO2)粉末或其烧结体上涂布(Coating)或含浸铂(Pt)和/或钯(Pd)的盐的水溶液，再进行加热分解析出铂(Pt)和/或钯(Pd)的方法的情况相比较，可以大幅度的减低高价格的铂(Pt)和/或钯(Pd)的使用量。而且与以往的有机卤化物分解催化剂不同，由于在低温中也可以具有分解有机卤化物的机能，因此在作为活性炭的使用温度范围的130℃至150℃的温度范围内，也可以发挥优良的机能，并可以将活性炭的使用寿命延长到以往的数倍，而且还不需要再加热排放废气。而且，不但可以分解二噁英类以及溴化二噁英类等有机卤化物还不用担心其会再合成，也能够吸附除去排放废气中的重金属、SOX、NOX以及HCl等。
本发明的具有分解有机卤化物功能的吸附剂，可以设置在排放废气处理系统中的未满200℃的低温区域的部分而进行使用。其较佳的温度区域为排放废气温度为130℃至150℃的部分。在此并没有特别限制其使用形态，例如可以粘附在袋状过滤器(Bag Filter)的滤布上在排放废气处理中使用。因此，排放废气中的灰尘可以利用袋状过滤器过滤，同时能够通过有机卤化物分解催化剂分解排放废气中的有机卤化物，以及通过活性炭吸附SOX、NOX以及HCl等，也能够吸附除去排放废气中的重金属。因此，本发明的具有分解有机卤化物功能的吸附剂，可以同时对于排放废气中所包含的有害成分进行分解、吸附处理。而且，一度吸附于活性炭中的有害成分，可以利用有机卤化物分解催化剂慢慢分解。因此，本发明的具有分解有机卤化物功能的吸附剂，与单独使用活性炭单体的情况相比较，可以大幅延长活性炭的使用寿命，并能抑制二次废弃物的发生量。
实施例1
为了确认上述本发明的效果，在催化剂工序中使用邻氯甲苯作为二噁英类的替代物，测定其吸附除去特性。催化剂涂布溶液是以钛的醇盐衍生物100重量份中混合作为铂盐的氯铂酸六水合物的铂1重量份的比率，溶解于含有作为氨基酸的L-赖氨酸1重量份的甲醇中而合成的有机金属前体分散液，再向其中加入二氧化钛(TiO2)溶胶50重量份而制成。实验中使用的物质是，使活性炭浸入该催化剂涂布溶液中，加热而生成有机卤化物分解催化剂，相对于活性炭100重量份，二氧化钛(TiO2)量为1重量份，铂(Pt)为0.01重量份的比例。而且为了与其比较，使用未负载催化剂的活性炭。
在两种类的活性炭吸附剂中，负载了催化剂者以及未负载催化剂者，共使用四种并放置于装置中，维持200℃的温度，通入包含邻氯甲苯的模拟焚烧排放废气，测定吸附剂入口、出口处的邻氯甲苯的浓度以及吸附剂中的邻氯甲苯的浓度。
首先，根据共四种的吸附剂，其分析结果如表1所示。负载了铂/二氧化钛(Pt/TiO2)的催化剂，当然铂(Pt)、钛(Ti)的量会增加。而且在活性炭中负载了催化剂不会使比表面积减小，也不使细孔部分产生大幅的变化。
表1 吸附剂性能
| 分析项目 | 单位 | No.1 | No.2 | |||
| 空白 | 负载Pt/TiO2 | 空白 | 负载Pt/TiO2 | |||
| 比表面积 | m2/g | 292 | 319 | 637 | 575 | |
| 细孔分布 | 总吸附量 | ml/g | 0.316 | 0.325 | 0.422 | 0.474 |
| 极大细孔径 | | 7.24 | 6.28 | 7.27 | 5.57 | |
| 碘吸附性能 | mg/g | 400 | 380 | 850 | 700 | |
| 发火点 | ℃ | 700 | 700 | 687 | 700 | |
| 灰分 | wt％ | 13.7 | 17.7 | 7.2 | 12.2 | |
| 固定碳数 | wt％ | 83.4 | 76.1 | 90.8 | 81.5 | |
| 铂(Pt) | wt％ | ＜0.01 | 0.02 | ＜0.01 | 0.02 | |
| 钛(Ti) | wt％ | 0.07 | 1.2 | 0.03 | 1.1 | |
图1表示邻氯甲苯的吸附除去特性示意图。而且图2表示吸附剂中的邻氯甲苯的浓度示意图。如图所示，通过吸附使邻氯甲苯的除去率为99％以上是非常高的，而没有负载催化剂的吸附剂的内部残留有机氯化物。但是负载催化剂的吸附剂的内部不会残留大量有机氯化物，由此证明可以处理有机氯化物。
因此，使用完后的吸附剂中的相关有机氯化物可以减少残留量。而且，在活性炭的再生过程中，可以通过于500℃左右的高温下且活性炭不会燃烧的还原气氛下再生，在还原气氛下越是高温，Pt/TiO2催化剂越能发挥其效力，使负载了铂(Pt)/二氧化钛(TiO2)Pt/TiO2的活性炭更容易再生。
实施例2
在上述实施例1中是考察以二噁英类为主的有机氯化物的实施例，而实施例2是对于其他有机卤化物的溴化二噁英类为主的有机溴化物进行考察的实施例，使用邻溴甲苯，测定其吸附除去特性。催化剂涂布溶液是以钛的醇盐衍生物100重量份中混合作为铂盐的氯铂酸六水合物的铂1重量份的比率，并溶解于含有作为氨基酸的L-赖氨酸1重量份的甲醇中而合成的有机金属前体分散液，再向其中加入二氧化钛(TiO2)溶胶50重量份而制成。实验中使用的物质是，使活性炭浸入该催化剂涂布溶液中，加热而生成有机卤化物分解催化剂，对于活性炭100重量份，二氧化钛(TiO2)为1重量份，铂(Pt)为0.01重量份的比例。而且为了与其比较，使用未负载催化剂的活性炭。
在两种类的活性炭吸附剂中，负载催化剂者以及未负载催化剂者，共使用四种并放置于装置中，维持200℃的温度，通入包含邻溴甲苯的模拟焚烧排放废气，测定吸附剂入口、出口中的邻溴甲苯的浓度以及吸附剂中的邻溴甲苯的浓度。
图3表示邻溴甲苯的吸附除去特性示意图。而且图4表示吸附剂中的邻溴化甲苯的浓度示意图。如图所示，通过吸附使邻溴化甲苯的除去率为99％以上是非常高的，没有负载催化剂的吸附剂的内部残留有机溴化物。但是负载了催化剂的吸附剂的内部不会残留大量有机溴化物，由此证明可以处理有机溴化物。
实施例3
是使用钯(Pd)作为催化剂成分的情况，但是催化剂涂布溶液是由钛的醇盐衍生物100重量份中混合作为钯盐的硝酸钯的钯1重量份的比率，并溶解于含有作为氨基酸的L-赖氨酸1重量份的甲醇中而合成的有机金属前体分散液，再向其中加入二氧化钛(TiO2)溶胶50重量份而制成。实验中使用的物质是，使活性炭浸入该催化剂涂布溶液中，加热而生成有机卤化物分解催化剂，对于活性炭100重量份，二氧化钛(TiO2)量为1重量份，钯(Pd)为0.01重量份的比例。而且为了与其比较，使用未负载催化剂的活性炭。再根据实施例1的实验方法，通入包含邻氯甲苯、邻溴甲苯的模拟焚烧排放废气，测定吸附剂入口、出口处的邻氯甲苯和邻溴甲苯的浓度。图5表示邻氯甲苯的吸附除去特性示意图。且图6表示吸附剂中邻氯甲苯的浓度示意图。图7出示邻溴甲苯的吸附除去特性示意图。图8示出吸附剂中邻溴甲苯的浓度示意图。如图所示，通过吸附使邻氯甲苯和邻溴甲苯的除去率为99％以上是非常高的，没有负载催化剂的吸附剂的内部残留有机卤化物。但是负载了催化剂的吸附剂的内部不会残留大量有机卤化物，由此证明可以处理有机卤化物。
工业实用性
由以上说明的那样，按照本发明的具有分解有机卤化物功能的吸附剂，不但可以吸附分解排放废气中所包含的有机卤化物，还能够吸附除去排放废气中的重金属类、SOX、NOX以及HCl等，与单独使用活性炭单体的情况相比，可以延长活性炭的使用寿命，抑制二次废弃物的发生量。而且在催化剂入口的二噁英类以及溴化二噁英类等有机卤化物浓度低的情况下，不会使其再合成。是一种特别适合使用于焚化炉的排放废气处理的物质。而且，按照本发明的具有分解有机卤化物功能的吸附剂的制造方法，可以容易的制造上述的具有分解有机卤化物功能的吸附剂。
Claims (2)
1.一种具有分解有机卤化物功能的吸附剂，该吸附剂包括活性炭、和在该活性炭上负载的有机卤化物分解催化剂，
其特征在于，该有机卤化物分解催化剂是将分子内含有铂(Pt)和/或钯(Pd)与钛(Ti)的有机金属化合物前体分散液与二氧化钛(TiO2)溶胶混合加热而形成，并使铂(Pt)和/或钯(Pd)的微拉子分散于二氧化钛(TiO2)中，其中，上述分散液通过使0.5-5重量份的Pt盐和/或Pd盐、100重量份Ti的醇盐衍生物以及0.1-1.5重量份的氨基酸在100-200重量份的溶剂中反应合成得到。
2.一种具有分解有机卤化物功能的吸附剂的制造方法，其特征在于，使0.5-5重量份的Pt盐和/或Pd盐、100重量份Ti的醇盐衍生物以及0.1-1.5重量份的氨基酸在100-200重量份的溶剂中反应，合成得到分子内含有铂(Pt)和/或钯(Pd)和钛(Ti)的有机金属化合物前体分散液，将该有机金属化合物前体分散液与二氧化钛(TiO2)溶胶混合制成催化剂涂布溶液，使活性炭浸入其中并加热，将铂(Pt)和/或钯(Pd)的微粒子分散于二氧化钛(TiO2)中的有机卤化物分解催化剂负载在该活性炭上。
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| DE60126221T2 (de) * | 2000-04-20 | 2007-11-15 | Ngk Insulators, Ltd., Nagoya | Verfahren zur herstellung eines katalysators zur zersetzung von organischen haliden und verfahren zur herstellung eines filters zur verwendung bei der zerstetzung von organischen haliden |
| US6670300B2 (en) * | 2001-06-18 | 2003-12-30 | Battelle Memorial Institute | Textured catalysts, methods of making textured catalysts, and methods of catalyzing reactions conducted in hydrothermal conditions |
| US7552497B2 (en) | 2002-03-26 | 2009-06-30 | Colgate-Palmolive Company | Powered toothbrush with rotating sections |
| KR20050049112A (ko) * | 2003-11-21 | 2005-05-25 | 한국과학기술연구원 | 연소설비 배출가스의 미량오염물질 저감방법 |
| CN100415367C (zh) * | 2005-03-07 | 2008-09-03 | 南开大学 | 纳米金属钯/载体催化剂的制备方法 |
| CN100431705C (zh) * | 2005-03-07 | 2008-11-12 | 南开大学 | Pd络合物负载催化剂的制备方法 |
| US20100310441A1 (en) * | 2009-06-05 | 2010-12-09 | Basf Corporation | Catalytic Article for Removal of Volatile Organic Compounds in Low Temperature Applications |
| KR101278047B1 (ko) | 2010-12-20 | 2013-06-27 | 대림대학교산학협력단 | 백금이 분산된 이산화티타늄 전구체의 제조방법 |
| CN102794107A (zh) * | 2012-08-31 | 2012-11-28 | 中持依迪亚（北京）环境研究所有限公司 | 一种催化降解二恶英的方法及系统 |
| CN103100386B (zh) * | 2013-01-15 | 2014-08-06 | 汕头大学 | 一种用于降解VOCs的整体式催化剂的制备方法 |
| CN103520762A (zh) * | 2013-08-30 | 2014-01-22 | 蚌埠首创滤清器有限公司 | 一种改性活性炭吸附杀菌剂及其制备方法 |
| JP6140326B1 (ja) * | 2016-03-08 | 2017-05-31 | 株式会社流機エンジニアリング | 揮発性有機化合物の吸着剤の再生処理方法 |
| CN108283935A (zh) * | 2017-01-09 | 2018-07-17 | 青州日新特种材料有限公司 | 一种NOx脱除催化剂及其制备方法 |
| JP7492743B2 (ja) * | 2018-12-27 | 2024-05-30 | 日揮ユニバーサル株式会社 | アンモニア分解用触媒及び排ガスの処理方法 |
| CN111714964B (zh) * | 2020-06-29 | 2021-08-17 | 浙江严牌过滤技术股份有限公司 | 一种除尘脱二噁英一体化滤料及其制备方法 |
| CN113731356A (zh) * | 2021-07-07 | 2021-12-03 | 生态环境部华南环境科学研究所 | 一种改性活性炭吸附剂及其制备方法和应用 |
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| US5254797A (en) * | 1989-06-07 | 1993-10-19 | Ngk Insulators, Ltd. | Method of treating exhaust gas |
| DE69012883T3 (de) * | 1989-06-07 | 1998-08-27 | Ngk Insulators Ltd | Methode für die Behandlung von Abgas. |
| JPH0714459B2 (ja) * | 1990-09-06 | 1995-02-22 | 正勝 平岡 | 排ガスの処理方法 |
| US5294419A (en) * | 1990-11-30 | 1994-03-15 | Masakatsu Hiraoka | Method for removing nitrogen oxides and organic chlorine compounds from combustion waste gas |
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| DE60126221T2 (de) | 2000-04-20 | 2007-11-15 | Ngk Insulators, Ltd., Nagoya | Verfahren zur herstellung eines katalysators zur zersetzung von organischen haliden und verfahren zur herstellung eines filters zur verwendung bei der zerstetzung von organischen haliden |
| JP4508459B2 (ja) * | 2000-04-20 | 2010-07-21 | メタウォーター株式会社 | 有機ハロゲン化合物分解触媒の製造方法および有機ハロゲン化合物分解フィルターの製造方法 |
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| KR100456600B1 (ko) | 2004-11-10 |
| CA2374957A1 (en) | 2001-11-22 |
| KR20020040751A (ko) | 2002-05-30 |
| EP1287888B1 (en) | 2009-07-22 |
| CN1380837A (zh) | 2002-11-20 |
| JP4834274B2 (ja) | 2011-12-14 |
| EP1287888A4 (en) | 2004-06-16 |
| EP1287888A1 (en) | 2003-03-05 |
| TWI286491B (en) | 2007-09-11 |
| WO2001087478A1 (fr) | 2001-11-22 |
| CA2374957C (en) | 2008-07-08 |
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