CN100371566C - 污染控制装置及用来固定污染控制元件的垫子 - Google Patents

污染控制装置及用来固定污染控制元件的垫子 Download PDF

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CN100371566C
CN100371566C CNB2003801073813A CN200380107381A CN100371566C CN 100371566 C CN100371566 C CN 100371566C CN B2003801073813 A CNB2003801073813 A CN B2003801073813A CN 200380107381 A CN200380107381 A CN 200380107381A CN 100371566 C CN100371566 C CN 100371566C
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渡边俊行
宫坂宗樹
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3M Innovative Properties Co
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Abstract

本发明提供一种用来固定污染控制元件(如催化转化器、柴油机颗粒过滤器等)的垫子，即使长期暴露在超过800℃的高温，它能保持对支撑体的夹持强度而不影响弹性；本发明还提供一种包含这种垫子的污染控制装置。该垫子至少由两层纤维层组成，一个氧化铝纤维层和一个陶瓷纤维层，这两层构成一单片，无需使用辅助结合手段。

Description

污染控制装置及用来固定污染控制元件的垫子
技术领域
本发明涉及污染控制装置(如催化转化器、柴油机颗粒过滤器等)，涉及用于在此类控制装置中固定污染控制元件的垫子，具体涉及在废气净化装置中使用的催化转化器，并尤其具体涉及在催化转化器外壳上用来固定催化剂支撑体的垫子。
发明背景
汽车和柴油机发动机的废气净化装置使用的催化转化器一般都在金属外壳中含有一个催化剂支撑体，该支撑体是具有许多通孔排列其中成为蜂窝形状的所谓“蜂窝结构”的整料部分。这种整料部分上载有催化剂，诸如贵金属，通过使一氧化碳和碳氢化合物发生氧化以及减少氮氧化物而净化废气。这种整料部分催化剂支撑体由金属或陶瓷材料构成。为了在金属外壳中容纳催化剂支撑体，在金属外壳和催化剂支撑体之间备有一个用来固定催化剂支撑体的垫子(催化剂支撑体固定材料)，该垫子由基于氧化铝-二氧化硅的纤维或其它陶瓷纤维构成，能固定催化剂支撑体并保护其不受损害。
然而，陶瓷催化剂支撑体的热膨胀系数通常几乎不足金属外壳热膨胀系数的十分之一。尽管催化转化器通常都暴露于几百度的高温，但在如此高温之下，由于金属外壳与陶瓷催化剂支撑体的热膨胀系数不同，金属外壳的热膨胀超过陶瓷材料的热膨胀，结果导致金属外壳与催化剂支撑体间的间隙扩大，造成催化剂支撑体的夹持强度下降，从而产生诸如使催化剂支撑体发出卡嗒声的毛病。
因此，人们提出了在用于固定催化剂支撑体的垫子中包含一种膨胀剂而在金属外壳与催化剂支撑体的间隙膨胀时防止催化剂支撑体夹持强度下降的建议。参见例如日本未审查特许公开第2002-514283号(第2页，第16-18页)。即，在该特许公开中，在金属外壳与催化剂支撑体间放置了由柔性膨胀层和含有膨胀物质的柔性膨胀层构成的单片。
发明内容
然而，近年来，由于要求改善汽车的燃料消耗和日益严格的排放控制要求，应用于汽车的催化装置正越来越暴露于更高的温度之下，这是因为发动机排出的废气本身温度升高了，还因为使用了一种系统，在该系统中通过将催化装置紧置于发动机后面而在尽可能高的温度下对废气进行处理以便提高净化效能。例如，众所周知的是，在某些驾驶条件下，使用汽油发动的车辆的废气温度超过1000℃是习以为常的。
然而，当暴露于800-1000℃温度时，日本未审查特许公开第2002-514283号使用的膨胀物质，诸如蛭石、膨胀石墨或膨胀硅酸钠等会变质，其强度也会显著地降低。除了这种热变质之外，还会发生机械震动，致使催化剂支撑体的夹持强度下降。在该特许公开中，虽然膨胀物质的使用能有效地适应金属外壳与催化剂支撑体间隙的变化，但未讨论在超过800℃高温时的耐久性。
本发明提供一种用来固定像催化剂支撑体之类的污染控制元件的垫子，即使长期暴露于超过800℃高温下，它也能维持支撑体夹持强度而不影响其弹性。
为了解决一个或多个上述问题，本发明提供一种用来固定污染控制元件(例如，催化剂支撑体、柴油机颗粒过滤器等)的垫子和包含所述垫子的污染控制装置，其中所述垫子至少包括两层，一个氧化铝纤维层和一个陶瓷纤维层。这些纤维层可以单片的形式提供，勿需使用辅助结合手段。
附图说明
图1是一个催化净化装置的分解透视图。
图2是本发明用来固定催化剂支撑体的垫子构造的截面图。
图3是显示用来固定催化剂支撑体的垫子的试样3所承受的压力随时间变化的图。
图4是显示实施例1和2及比较例1的试样在10年后所承受压力的外推值的图。
具体实施方式
以下是参照附图对本发明的说明。图1是一个典型催化转化器的分解透视图。催化转化器10包括在金属外壳11中的催化剂支撑体20，它是个具有所谓“蜂窝结构”的整料部分，其中许多通孔排列成蜂窝形状。这种整料部分上载有一种能使一氧化碳和碳氢化合物氧化以及减少氮氧化物而净化废气的催化剂。催化剂支撑体20一般由陶瓷材料构成，常常是极脆的。因此，用来固定催化剂支撑体的垫子3置于金属外壳11与催化剂支撑体20之间，以保护催化剂支撑体20不受损害。
如图2所示，本发明用来固定催化剂支撑体的垫子30至少包含由氧化铝纤维层31和陶瓷纤维层32组成的两层，这些纤维层不需要使用辅助结合手段而形成一个单片。
氧化铝纤维层31是用前体纤维化工艺制备成的氧化铝纤维形成的，陶瓷纤维层32是用通过熔化氧化铝(Al2O3)、二氧化硅(SiO2)及其他氧化物的混合物，尔后经过熔体喷射或熔融纺丝制备的陶瓷纤维形成的。这些纤维由80-95重量％的纤维和5-20重量％的粘合剂形成。
这里，在本发明的说明书中，构成氧化铝纤维层31的氧化铝纤维是含有50重量％或更多，最好是70重量％或更多的氧化铝的结晶纤维。另一方面，构成陶瓷纤维层32的陶瓷纤维是含有45重量％或更多二氧化硅的耐火陶瓷纤维(RCF)。氧化铝和二氧化硅以外的其它氧化物包括二氧化锆(ZrO2)、氧化镁(MgO)、氧化钙(CaO)、氧化铬(Cr2O3)、氧化钇(Y2O3)和氧化镧(La2O3)。
构成陶瓷纤维层32的陶瓷纤维优选经过退火。退火处理能改善垫子的弹性并改善夹持强度和耐久性。退火在700-1200℃进行，优选在950-1100℃进行，退火时间优选为0.5-2小时。
丙烯酸树脂、苯乙烯-丁二烯、乙烯基吡啶、丙烯腈、氯乙烯或聚氨酯等可用作粘合剂。此外，垫子除了含有氧化铝纤维和陶瓷纤维和粘合剂外，还可含有无机粘合剂(如玻璃颗粒、碳酸钙、云母或氢氧化镁)或柔性热固性树脂(如不饱和聚酯、环氧树脂或聚乙烯酯)。
本发明用来固定催化剂支撑体的垫子是不使用辅助结合手段形成的一个单片，其方法形成诸如同时在氧化铝纤维层上表面上形成一个陶瓷纤维层。术语“辅助结合手段”是指外用的附着手段，诸如树脂、胶粘剂、胶粘带、缝线或钉子。
现有技术中用来固定催化剂支撑体的垫子是由多层层合物组成的垫子，其形成是：首先单个地制作每一层，然后再用粘合剂、粘结膜、缝线或钉子将各层相互附着起来。可是，用胶粘剂或胶粘膜将各单个层附着起来的多层垫子用于催化转化器时常常会产生讨厌的烟雾或气味。此外，这种胶粘剂或胶粘膜还会影响垫子的抗热性。再者，由于将各层相互附着的成本和使用胶粘剂或胶粘膜的成本，这种垫子的生产成本也增加。另一方面，对于层与层之间用缝线等机械方式附着的垫子而言，在缝线穿透垫子的部位，垫子的机械强度会下降，而且会因要求额外步骤和材料而有成本增加的问题。
由于不采用这种辅助结合手段而是由氧化铝纤维层和陶瓷纤维层组成单片，本发明消除了上述问题。
具体地说，本发明用来固定催化剂支撑体的垫子，其形成是制备一种含有氧化铝纤维的浆料和一种含有陶瓷纤维的浆料(这些浆料的固体含量优选在5重量％或以下)、将第一浆料粘附到滚光机的网子或金属丝网等上面；通过重力和/或真空使该第一浆料部分脱水而形成一个底层、再将第二浆料粘附到上述部分脱水的底层上、通过类似的部分脱水形成上层、然后用压辊加压以增加这二层的密度、随后用加热的滚筒使其完全干燥。虽然氧化铝纤维层或是陶瓷纤维层均可在起始作为底层形成，但在干燥期间优选是最厚的一层应为首先形成的底层。
采用这种方法，由于是将第二浆料粘附到第一浆料部分脱水后形成的层上、随后再将第二浆料脱水，这二种组分会部分地混合，尤其是在这二层的界面处。其结果是，这二层便持久而有效地附着在一起，勿需使用诸如胶粘剂等辅助结合手段，从而可形成一个整体的单片。
在本发明用来固定催化剂支撑体的垫子中，氧化铝纤维层与陶瓷纤维层的重量比优选在3∶11-11∶3。除了由氧化铝纤维层和陶瓷纤维层构成的二层结构外，本发明用来固定催化剂支撑体的垫子还可采用包括由这些材料或其它材料组成的其它层的三层或多层结构。然而，在这种情况下，至少一个最外层必须是氧化铝纤维层。
如图1所示，一个催化净化装置的制造，可将本方法制得的用来固定催化剂支撑体的垫子卷绕在催化剂支撑体上、使氧化铝纤维层与催化剂支撑体接触、然后将其固定在金属外壳上来完成。
实施例
实施例1
将92重量％的含72重量％氧化铝和28重量％二氧化硅的氧化铝纤维与8重量％的粘合剂(丙烯酸乳胶、Nippon Zeon公司的Nippore LX-816)混合，随后加水制备第一浆料。另外，将92重量％的通过熔融形成并含46重量％氧化铝和53重量％二氧化硅的二氧化硅纤维与8重量％的上述粘合剂混合，随后加水制备第二浆料。使用这两种浆料采用上述的普通轧制方法得到具有表1所示的氧化铝纤维层与陶瓷纤维层单位重量比的用来固定催化剂支撑体垫子的试样1至5。
实施例2
除了是使用在1000℃退火60分钟的陶瓷纤维以外，以与实施例1同样的方法得到如表2所示的用来固定催化剂支撑体垫子的试样6至8。
比较例1
除了是由41重量％蛭石、47重量％陶瓷纤维和12重量％粘合剂形成陶瓷纤维层之外，以与实施例1同样的方法得到如表3所示的用来固定催化剂支撑体垫子的试样9至13。
评价方法
试样在高温下的夹持强度(承受压力)和耐久性按下述方法评估。将每份试样切割成直径为45mm，每份经切割的试样随后夹在压缩测试仪的上下两块板之间，使氧化铝纤维层位于高温(900℃)一侧。对试样加压，5分钟后将压力调节到130kPa。接下来，将上下两块板加热，当两块板的温度分别达到900℃和700℃时，该时刻记为0时刻。然后每小时记录一次承受压力的改变，持续20个小时。试样3的结果见图3。根据该图可确定公式Y＝aXb作为承受压力变化的近似表达。然后，应用该近似公式确定承受压力的外推值，见表1至3。
表1
  第一层   第二层   承受压力变化的近似公式   承受压力10年后的外推值(kPa)
  陶瓷纤维(92％)，粘合剂(8％)   氧化铝纤维(92％)，粘合剂(8％)
 试样1   单位重量(g/m<sup>2</sup>)   300   1100   Y＝85.933X<sup>-0.0566</sup>   45.1
  单位重量比   3   11
 试样2   单位重量(g/m<sup>2</sup>)   500   900   Y＝68.21X<sup>-0.0589</sup>   34.9
  单位重量比   5   9
 试样3   单位重量(g/m<sup>2</sup>)   700   700   Y＝65.13X<sup>-0.082</sup>   25.6
  单位重量比   7   7
 试样4   单位重量(g/m<sup>2</sup>)   900   500   Y＝48.132X<sup>-0.0724</sup>   21.1
  单位重量比   9   5
 试样5   单位重量(g/m<sup>2</sup>)   1100   300   Y＝43.803X<sup>-0.1343</sup>   9.5
  单位重量比   11   3
表2
  第一层   第二层   承受压力变化的近似公式   承受压力10年后的外推值(kPa)
  陶瓷纤维(92％)，粘合剂(8％)   氧化铝纤维(92％)，粘合剂(8％)
 试样6   单位重量(g/m<sup>2</sup>)   300   1100   Y＝103.57X<sup>-0.0493</sup>   59.1
  单位重量比   3   11
 试样7   单位重量(g/m<sup>2</sup>)   700   700   Y＝94.206X<sup>-0.0446</sup>   55.5
  单位重量比   7   7
 试样8   单位重量(g/m<sup>2</sup>)   1100   300   Y＝90.317X<sup>-0.0538</sup>   49
  单位重量比   11   3
表3
  第一层   第二层   承受压力变化的近似公式   承受压力10年后的外推值(kPa)
  陶瓷纤维(92％)，粘合剂(8％)   氧化铝纤维(92％)，粘合剂(8％)
  试样9   单位重量(g/m<sup>2</sup>)   300   1100   Y＝150.42X<sup>-0.1143</sup>   41
  单位重量比   3   11
  试样10   单位重量(g/m<sup>2</sup>)   500   900   Y＝196.79X<sup>-0.1574</sup>   32.8
  单位重量比   5   9
  试样11   单位重量(g/m<sup>2</sup>)   700   700   Y＝234.08X<sup>-0.2256</sup>   18
  单位重量比   7   7
  试样12   单位重量(g/m<sup>2</sup>)   900   500   Y＝311.91X<sup>-0.2828</sup>   12.5
  单位重量比   9   5
  试样13   单位重量(g/m<sup>2</sup>)   1100   300   Y＝344.19X<sup>-0.4101</sup>   3.24
  单位重量比   11   3
图4是10年后承受压力外推值曲线的图。图4清楚地显示，10年后本发明用来固定催化剂支撑体垫子的高温夹持强度，比现有技术含有膨胀剂、氧化铝纤维层与陶瓷纤维层之比为7∶7-3∶1的垫子的高温夹持强度提高40％左右。此外，如果使用经退火的陶瓷纤维，当氧化铝纤维层与陶瓷纤维层之比为3∶11时，10年后的高温夹持强度提高大约4-5倍，当氧化铝纤维层与陶瓷纤维层之比为7∶7时，提高2倍左右。
即使长期暴露在超过800℃的高温，本发明用来固定催化剂支撑体的垫子也能保持对支撑的体夹持强度而不影响弹性。

Claims (10)

1.一种用来在污染控制装置中固定污染控制元件的垫子，所述垫子包含：
一个氧化铝纤维层，所述氧化铝纤维层包含由含有氧化铝和二氧化硅的混合物制成的结晶氧化铝纤维，该纤维的氧化铝含量为50重量％或更高；和
一个陶瓷纤维层，所述陶瓷纤维层包含由含氧化铝和二氧化硅的混合物制成的陶瓷纤维，该纤维的二氧化硅含量是45重量％或更高；
所述氧化铝纤维层和所述陶瓷纤维层的重量比为3∶11-11∶3，所述垫子即使长期暴露在超过800℃的高温，仍保持夹持强度。
2.如权利要求1所述的垫子，其特征在于，所述氧化铝纤维层和所述陶瓷纤维层形成一单个垫片，而无需使用辅助结合手段。
3.如权利要求1所述的垫子，其特征在于，形成陶瓷纤维层的所述陶瓷纤维在700-1200℃进行了退火。
4.如权利要求1所述的垫子，其特征在于，所述氧化铝纤维层和陶瓷纤维层形成为单片的方法是：制备含有氧化铝纤维的浆料和含有陶瓷纤维的浆料；将其中一种浆料粘附到一渗透性衬底上并使所粘附的浆料部分脱水形成第一层；然后将另一种浆料粘附到所述第一层并使该浆料部分脱水形成第二层。
5.如权利要求1至4中任一项所述的垫子，其特征在于，所述两个纤维层都不含膨胀剂。
6.如权利要求1至4中任一项所述的垫子，其特征在于，按外推法确定，所述垫子即使暴露在超过800℃的高温10年，仍能保持其夹持强度。
7.一种污染控制装置，它包括：
一个外壳；
一个固定在所述外壳内的污染控制元件；
如权利要求1至6中任一项所述的一个垫子，它放置在所述外壳与所述污染控制元件之间，以便将所述污染控制元件固定在所述外壳中。
8.如权利要求7所述的污染控制装置，其特征在于，所述污染控制装置是一种催化转化器或一种柴油机颗粒过滤器。
9.一种发动机排气装置，其特征在于，包括如权利要求7或8所述的装置。
10.一种发动机，其特征在于，包括如权利要求7或8所述的装置。
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JP2020033935A (ja) 2018-08-30 2020-03-05 スリーエム イノベイティブ プロパティズ カンパニー 保持材及びその製造方法、並びに、汚染コントロール装置
JP7224156B2 (ja) 2018-11-30 2023-02-17 スリーエム イノベイティブ プロパティズ カンパニー マット材及びその製造方法、並びに、無機接着シート、汚染コントロール装置及び断熱構造体
WO2021124057A1 (en) 2019-12-17 2021-06-24 3M Innovative Properties Company Thermal insulation structure and method of making same

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CN1732331A (zh) 2006-02-08
JP2004204819A (ja) 2004-07-22
ATE399257T1 (de) 2008-07-15
ZA200505966B (en) 2006-10-25
WO2004061279A1 (en) 2004-07-22
DE60321828D1 (de) 2008-08-07
EP1588033A1 (en) 2005-10-26
EP1588033B1 (en) 2008-06-25
AU2003297272A1 (en) 2004-07-29
US20070140929A1 (en) 2007-06-21

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