CN101283167B - 用于污染控制元件和污染控制装置的保持材料 - Google Patents
用于污染控制元件和污染控制装置的保持材料 Download PDFInfo
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- CN101283167B CN101283167B CN2006800374658A CN200680037465A CN101283167B CN 101283167 B CN101283167 B CN 101283167B CN 2006800374658 A CN2006800374658 A CN 2006800374658A CN 200680037465 A CN200680037465 A CN 200680037465A CN 101283167 B CN101283167 B CN 101283167B
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Abstract
一种用于在污染控制装置(10)中安装污染控制元件(1)的保持材料(2),该材料提供与所述壳体(4)和/或所述污染控制元件之间的高摩擦系数,且能以良好的稳定性保持所述污染控制元件。所述保持材料包含具有一定厚度且具有摩擦层(3)的纤维材料(例如以垫的形式),该摩擦层包含位于所述纤维材料的外周边表面和/或内周边表面上的无机胶粒(5)。
Description
技术领域
本发明涉及一种污染控制元件安装或保持材料(例如以垫的形式),且更具体地讲涉及一种污染控制元件例如催化剂载体或过滤元件的安装或保持材料。本发明还涉及一种具有这样的污染控制元件保持材料的污染控制装置,更具体地说,涉及一种催化转化器,该催化转化器具有装入其中的催化剂载体保持材料;或一种具有过滤元件保持材料的废气净化装置(例如柴油机废气过滤器)。
背景技术
采用陶瓷催化转化器的废气净化系统作为除去包含在从汽车发动机排出的废气中的一氧化碳(CO)、碳氢化合物(HC)和氮氧化物(NOx)的装置已为人们所熟知。陶瓷催化转化器主要容纳例如蜂窝状的陶瓷催化剂载体(也称为“催化剂元件”),该催化剂位于金属壳体中,换句话讲,位于外壳中。
众所周知,有多种类型的陶瓷催化转化器,但通常只采用这样一种构造,其中壳体和催化器中的催化剂载体之间的间隙填充保持或安装材料(例如以垫的形式),该材料一般由无机纤维与液体或糊状的有机粘结剂组合而成。因此,填充该间隙的安装材料保持催化剂载体,并能防止由撞击、振动等引起的意外施加到催化剂载体上的机械震动。因此,在这样的构造的催化转化器中,催化剂载体不会发生断裂或移动。所以,能在长时间内实现所期望的作用。此外,上述安装材料除具有保持功能外,还具有绝热功能。
当污染控制元件(例如催化剂载体)被装入壳体时,一般采用压力插入系统,使得安装或保持材料缠绕在污染控制元件的外周边上并 与之成为一体,其后该一体化本体在压力作用下被插入圆柱形壳体中。已经提出了各种类型的污染控制元件保持材料,用以提高压力插入系统中的污染控制元件的填塞(也称作“封装”)能力,增强保持材料的减震能力(膨松度),以及防止构成保持材料的无机纤维分散到空气中。参见例如日本专利No.JP-A-2001-259438的权利要求,其中提出了一种催化转化器,包括催化剂载体、覆盖该催化剂载体外围的金属外壳(壳体)和设置在催化剂载体和壳体之间的保持及密封材料。在该催化转化器的情况下,保持及密封材料(对应于本文所称的保持材料)由从50到3000个穿孔每100cm2的针刺的无机纤维垫构成,包含含量远大于0但小于等于2重量%的有机组分,且当以填充密度为0.15到0.45g/cm3加热到3001000C时,产生5到500kPa的表面压力。
此外,参见例如日本专利No.JP-A-2002-4848的权利要求,其中提出了一种催化剂载体保持材料,用于其构造与本文上述的构造类似的催化转化器。在该材料中,将含有0.5到20重量%有机粘结剂的粘结剂或无机粘结剂与垫状布置的无机纤维添加到或连接到垫状材料上,装配后将该填充物密度调整在0.1到0.6g/cm3的范围内,并且在评估沿所述厚度方向的三个相等部分(上部、中部和下部)中,添加和施用到垫状材料上的粘结剂固体比率时,上部和下部中的所述粘结剂固体比例比中部的更高。
此外,参见例如日本专利No.JP-A-2002-206421的权利要求,其中提出了一种用于催化转化器的保持密封材料,该材料包含装配成垫状构造作为组元的陶瓷纤维,并被设置在催化剂载体和覆盖催化剂载体外周边的金属外壳之间的间隙中。其中,在陶瓷纤维的外表面上提供由无机物质组成的峰-谷结构。在此保持密封材料中,由无机物质组成的峰-谷结构优选包含颗粒平均粒度为50到1,000nm的金属氧化物颗粒。
然而,例如,如日本专利No.JP-A-2002-206421中所述,当通过粘附金属氧化物,在构成催化剂保持材料的陶瓷纤维的表面提供峰-谷结构时,使用的是在陶瓷纤维表面上涂布金属氧化物颗粒的悬浮液,然后在高温下烘烤的方法。因此,形成了将陶瓷纤维结合在一起的桥或降低了陶瓷纤维间的滑移,从而硬化保持材料。所以,安装过程中存在保持材料断裂的风险,或者可能降低保持材料在催化剂载体上缠绕时的生产效率。此外,由于涉及高温烘烤工艺,生产工艺会变得复杂,并且增加了生产成本。
发明内容
本发明解决了一个或多个上述问题和其它问题,并提供诸如催化剂载体和过滤元件等污染控制元件的安装中有效的安装或保持材料,
本发明的目的是提供一种催化剂载体保持材料或其它污染控制元件保持材料,该材料在耐热性、表面压力保持性、抗废气腐蚀性和可操纵性上表现优异,以使得当缠绕在污染控制元件周围并对其加以保持的保持材料被压力配合到污染控制装置(例如催化转化器)的壳体中时,能够避免污染控制元件或壳体与该保持材料分离和移位,并且在将污染控制元件装入壳体后可以保持污染控制元件,而不让其移动。
本发明的另一个目的是提供一种包含这种用于污染控制元件的安装或保持材料的污染控制装置,且更具体地提供一种其中填塞了该催化剂保持材料的催化转化器,或具有过滤元件保持材料的废气净化装置。
作为解决现有技术中上述问题而进行的全面研究的结果,本发明的发明人已发现在不使制造工艺复杂化的情况下,使用压缩状体下且被处理为具体微粒的保持材料,采用本发明的独特方法,可以在该保持材料的表面上(即,与催化剂载体和/或壳体接触的表面上)实现催化剂载体保持材料或其它污染控制元件保持材料所需的特性,正是这一发现导致了本发明的产生。该类型的这些具体微粒能够增大(a)保 持或安装材料与污染控制元件(例如催化剂载体)之间和/或(b)保持或安装材料与壳体之间的摩擦系数。
根据本发明的一方面,本发明提供一种污染控制元件保持或安装材料,该材料由具有一定厚度的纤维材料(优选以垫的形式)构成,设置在壳体和污染控制元件之间,缠绕在壳体内的污染控制元件周围并对其加以保持。保持材料在施加至壳体与污染控制元件之间的恒定的压缩力下被设置在壳体与污染控制元件之间,并在壳体一侧的保持材料外周边表面上和/或污染控制元件一侧的内周边表面上具有由无机胶粒构成的摩擦层。
此外,根据本发明的另一方面,本发明提供一种污染控制装置,包括壳体、设置在壳体内的污染控制元件和设置在壳体与污染控制元件之间的污染控制元件保持或安装材料。所述污染控制元件保持材料是指用于根据本发明的污染控制元件的保持材料。
根据本发明的污染控制装置优选为催化转化器或废气净化装置,例如,用于内燃机的废气过滤装置。
当污染控制元件(例如催化剂载体)被保持或安装材料(例如以垫的形式)保持在污染控制装置(例如催化转化器)中时,污染控制元件的保持力由下式表示:
保持力=(保持材料中产生的压力)×(静摩擦系数)。
因此,一般可以采用两种方法来增大污染控制元件的保持力:通过增加保持材料的压缩量来增大由其产生的压力,或者增加保持材料的摩擦系数。根据本发明,在保持材料的表面优选以垫的形式形成包含具体无机胶粒的摩擦层。因此,由于该摩擦层的存在,可以向保持材料的表面赋予一定的表面形状(高度的电、磁和/或化学相互作用下 的分子表面状态),表现出比构成保持材料的陶瓷纤维或其它无机纤维的表面更高的摩擦系数。此外,由于这种表面形状的存在,保持材料表面与污染控制元件表面或壳体表面之间的摩擦系数可得到增大。根据本发明,如果壳体由金属板(例如不锈钢(SS))制成,则可以尤其显著地增大保持材料与壳体间的摩擦系数。
此外,根据本发明,通过使用无机胶粒向安装材料表面赋予精细的峰-谷结构,可以在壳体(例如由SS板制成的)与污染控制元件的表面之间产生动态相互作用。因而能够更加显著地增大摩擦系数。此外,将有机粘结剂与无机胶粒一起使用并用有机粘结剂将所述颗粒相互粘合,可以将无机胶粒有效地固定在保持材料的表面上和防止颗粒从保持材料的表面上脱落或脱离。
本发明可以提供一种催化剂载体保持材料或其它污染控制元件保持材料,该材料在抗废气腐蚀性、表面压力保持性和可操纵性上表现优异,以使得当缠绕在污染控制元件周围并对其加以保持的保持材料被压力配合到相应的壳体中时,能够避免污染控制元件(如催化剂载体)与该保持材料分离和移位,并且在将污染控制元件装入壳体后可以保持污染控制元件,而不让其移动。此外,在将无机胶粒固定到保持材料表面时,根据本发明的污染控制元件保持材料不需要烘烤工艺,因而能简化制造工艺并降低生产成本。
本发明还能提供包含该污染控制元件保持材料的在耐用性和其它特性方面表现优异的污染控制装置,例如一种具有填塞了保持材料的催化剂载体的催化转化器或一种包含过滤元件保持材料的废气净化装置(例如柴油机废气过滤器)。根据本发明的污染控制元件可以有利地用于处理汽车发动机、发电机以及其它内燃机中的废气。
附图说明
图1为图示说明根据本发明的催化转化器构造的剖视图。
图2为图1所示催化转化器沿着线段A-A的剖视图。
图3为示意性地说明图1所示的催化转化器中催化剂载体保持材料的摩擦层的剖视图。
图4为示意性图示地说明催化剂载体保持材料的摩擦系数的测量方法的剖视图。
图5为表示在实例1中制造的催化剂载体保持材料中,有机粘结剂和硅胶的比率与二氧化硅颗粒的脱落比率之间关系的坐标图。
图6为表示硅胶量与摩擦系数之间关系的坐标图,所述摩擦系数是SS板和实例1中制造的催化剂载体保持材料中垫之间的摩擦系数。
图7为表示硅胶量与摩擦系数之间关系的坐标图,所述摩擦系数是催化剂载体与实例1中制造的催化剂载体保持材料中垫之间的摩擦系数。
图8为表示在实例2中制造的催化剂载体保持材料中,有机粘结剂和胶体氧化铝的比率与氧化铝颗粒的脱落比率之间关系的坐标图。
图9为表示胶体氧化铝量与摩擦系数之间关系的坐标图,所述摩擦系数是SS板与实例2中制造的催化剂载体保持材料中垫之间的摩擦系数。
图10为表示胶体氧化铝量与摩擦系数之间关系的坐标图,所述摩擦系数是催化剂载体与实例2中制造的催化剂载体保持材料中垫之间的摩擦系数。
具体实施方式
根据本发明的用于污染控制元件及污染控制装置的保持或安装材料能以多种形式有利地加以实施。例如,所述污染控制元件可以为催化剂载体(或催化剂元件)、纤维元件(例如用于柴油机或其它发动机的废气净化过滤器)或者任何其它污染控制元件。类似地,所述污染控制装置可以为催化转化器、废气净化装置(例如,用于柴油机或其它发动机的废气净化装置,如柴油机微粒过滤器单元)或者任何其 它污染控制装置(对应于其上安装的污染控制元件)。下面将具体参考催化剂载体保持材料和催化转化器来描述本发明的具体实施,但是本发明并不限于这些实施方式。
根据本发明的催化转化器尤其适合于处理汽车发动机和其它内燃机中的废气,并且被构造为包括至少一个壳体和置于该壳体内的催化剂载体(催化剂元件)。此外,根据本发明的催化剂载体保持材料安装在壳体与所载催化剂之间,以便缠绕在催化剂载体的内周边表面上,该材料将在下文进行更加详细的描述。这样使得壳体的内周边表面与催化剂载体保持材料的外周边表面紧密接触。
优选对催化剂载体保持材料进行适当的压缩,换句话讲,使用时向其施加恒定压缩力,使得当它被安装在壳体中时具有足够的堆积体积密度。已知的压缩方式包括蛤壳式压缩、填充式压缩和绷带式压缩。根据本发明的催化剂载体保持材料可以有利地用于所谓的压力配合结构催化转化器的制造中,其中在填充式压缩的情况下,催化剂载体保持材料在压力作用下被推入例如圆柱形的壳体内。
只要采用压力配合结构,根据本发明的催化转化器就可以包括各种类型的催化转化器。所述催化转化器优选为包含单片式模制的催化剂元件,即,单片催化转化器。由于所述催化转化器包含的催化剂元件具有呈蜂巢式横截面的小通道,其尺寸小于常规颗粒型催化转化器并且可以在确保有足够的与废气接触的表面积的同时,降低废气阻力。因此,可以更为高效地处理废气。
根据本发明的催化转化器可以被有利地用来处理各种具有内燃机的装置中的废气。具体地讲,根据本发明的催化转化器在装入各种车辆(诸如汽车、公共汽车和卡车)的排气系统后,可以充分地展示其优越的运行效果。
图1为图示说明根据本发明的催化转化器的典型实例的侧视图。该图表示催化转化器主要组件的剖视图,以利于了解其结构。图2为图1中催化转化器沿着线段A-A的剖视图。如这些附图所述,催化转化器10包括金属壳体4、设置于金属壳体4内的单片固体催化剂载体1以及设置在金属壳体4和催化剂载体1之间的根据本发明的催化剂载体保持材料2。催化剂载体保持材料2由合适的纤维材料以垫的形式构成,该垫具有指定厚度,并且在催化剂载体一侧的垫内周边表面和/或金属壳体一侧的外周边表面(表面区域)上具有包含无机胶粒的摩擦层,该保持材料将在下文进行更加详细的描述。在催化剂载体保持材料(垫)2的表面区域的图中,如从图3的剖视图中可以清楚看出的,在金属壳体4一侧上的垫外周边表面上选择性地形成包含无机胶粒5的摩擦层3。锥形废气入口12和废气出口13连接到催化转化器10。
在根据本发明的催化转化器10的情况下,在催化剂载体1和催化剂载体保持材料2之间基本不必采用任何连接装置(诸如粘结剂或压敏板)。然而,可附加使用这些连接装置,前提条件是,这种连接装置不对本发明的运行效果产生不利影响,并可改善催化剂载体1与催化剂载体保持材料2之间的接触紧密度,并且可预期其有利于封装操作。通常优选在局部使用连接装置。此外,可以在催化剂载体保持材料2上提供保护性涂层或类似物,用以保护材料表面不受损坏等,虽然一般情况下这不是必需的。例如,在形成摩擦层3后,可在其表面粘贴聚乙烯薄膜、聚酯薄膜或天然橡胶薄膜,或非织造织物。
更具体地讲,位于金属壳体内的固体催化剂载体通常由蜂巢结构的陶瓷催化剂载体构成,并具有多个废气通道。根据本发明的催化剂载体保持材料被设置为缠绕在催化剂载体的周围。除了起到热绝缘体的功能外,所述催化剂载体保持材料将催化剂载体保持在金属壳体内和密封催化剂载体与金属壳体间形成的间隙。因此,它可以防止废气将催化剂载体作为旁路流过,或者至少将这种不良流动减至最小。此 外,所述催化剂载体保持材料在金属壳体内得到稳固而有弹性的支承。
在根据本发明的催化转化器中,可以使用本技术领域中已为人熟知的多种金属材料加工金属壳体,制成符合所需运行效果的任何形状。所述金属壳体优选使用不锈钢板(SS板)制造,并具有图1中所示的形状。不言而喻,如有必要,可以使用诸如铁、铝、钛或它们的合金等金属制造任何适当形状的金属壳体。
与金属壳体类似,固体催化剂载体可以用与常见催化转化器所使用的材料类似的材料制造成类似的形状。适当的催化剂载体包括由金属、陶瓷等制成的催化转化器和已为本领域的技术人员所熟知的催化转化器。在美国再版专利No.27,747中公开了适当的催化剂载体的一个实例。对催化剂单体的详细描述由以下文献提供,例如,Stroom等人的收录于SAE Technical Papers(出版号900500)中的“SystemsApproach to Packaging Design for Automotive Catalytic Converters(针对汽车催化转化器包装设计的系统方法)”、Howitt的收录于SAETechnical Papers(出版号800082)中的“Thin Wall Ceramics asMonolithic Catalyst Support(作为单片催化剂载体的薄壁陶瓷)”和Howitt等人的收录于SAE Technical Papers(出版号740244)中的“Flow Effect in Monolithic Honeycomb Automotive Catalytic Converter(单片蜂巢汽车催化转化器中的流动效应)”。
必须要由上述催化剂载体进行支撑的催化剂通常为金属(例如铂、钌、锇、铑、铱、镍和钯)和金属氧化物(例如五氧化二钒和二氧化钛),并且优选以涂层形式使用。对此类催化剂涂层的详细描述可见于例如美国专利No.3,441,381。
在本发明的实践中,在不脱离本发明范围的情况下,可以使用各种方法制造多种构造的催化转化器。特别优选的是,通过在金属壳体中容纳例如蜂巢陶瓷催化剂载体的方式基本制成催化转化器,和通过在 蜂巢陶瓷单体上支承由诸如铂、铑、钯等贵金属构成的催化剂层(催化剂涂层)制成最终的催化剂载体(催化剂元件)。采用这样的构造能在相对较高的温度下表现出有效的催化作用。
根据本发明,根据本发明的催化剂载体保持材料设置在金属壳体和位于其中的催化剂元件之间。所述催化剂载体保持材料是由一定厚度的纤维垫、纤维毯等构成。所述催化剂载体保持材料可以由一个构件以单层垫的形式构造,或者以通过连接(例如通过层合和粘结)两个或更多个构件而得到的复合垫的形式构造。从可操纵性等角度来看,所述催化剂载体保持材料使用垫、毯等形式常常是有利的,但如有必要,催化剂载体保持材料可以采用另一种形式。所述催化剂载体保持材料的尺寸可以根据其目标应用在广泛的范围内变化。例如,当垫状催化剂载体保持材料装入汽车催化转化器中使用时,该保持材料通常具有约1.5到15mm的厚度、约200到500mm的宽度和约100到150mm的长度。如有必要,可以使用剪刀和刀具等将保持材料切割成所需形状和尺寸以供使用。
所述催化剂载体保持材料由纤维材料构成,优选为无机纤维。形成所述催化剂载体保持材料的优选无机纤维包括玻璃纤维、陶瓷纤维、碳纤维、碳化硅纤维和硼纤维,但如有必要,也可使用其它无机纤维。这些无机纤维既可单独使用,又可以两种或更多种的组合使用,并且可以采用复合纤维等形式。在这些无机纤维中,特别优选陶瓷纤维,诸如氧化铝纤维、二氧化硅纤维和氧化铝-二氧化硅纤维。这些陶瓷纤维既可单独使用,又可以两种或更多种的组合使用,并且可以采用复合纤维等形式。其它无机材料可以用作添加材料,与上述陶瓷纤维或其它无机纤维一同使用。适当的添加材料的实例包括氧化锆、氧化镁、氧化钙、氧化铬、氧化钇和氧化镧。这些添加材料通常以粉末或颗粒形式被使用,并且可以单独使用或者两种或更多种混合使用。
在一个具体的实例中,构成催化剂载体保持材料的无机纤维由例 如包含氧化铝(Al2O3)和二氧化硅(SiO2)的无机纤维组成。在这个例子中,无机纤维包含两种组分:氧化铝和二氧化硅,而且在这种情况下,氧化铝和二氧化硅的配比优选在40∶60到96∶4的范围内。超出此范围的氧化铝和二氧化硅的配比(例如氧化铝配比低于40%)将导致诸如耐热性变差等问题。
对无机纤维的厚度(平均直径)没有设置任何具体的限制,但是优选的平均直径为约2到7μm。如果无机纤维具有不到约2μm的平均直径,这些纤维往往变得易碎并且强度不足。反之,如果所述纤维具有大于约7μm的平均直径,则保持材料往往难以成形。
此外,与厚度类似,对无机纤维的长度也不加以限制。然而,所述纤维优选具有约0.5到50mm的平均长度。如果无机纤维的平均长度小于约0.5mm,则由这些纤维形成的保持材料将不会表现出任何效果。相反,如果平均长度大于约50mm,则其可操纵性降低,而且难以顺利实施用于制造保持材料的工序。
按照另一个方法,实施本发明时,氧化铝基纤维垫(主要包含氧化铝纤维层合板)也可以有利地用作催化剂载体保持材料。在该氧化铝基纤维垫中,氧化铝纤维的平均长度通常在约20到200mm的范围内,厚度(平均直径)通常在约1到40μm的范围内。氧化铝纤维优选为莫来石纤维,其Al2O3/SiO2重量比率(Al2O3/SiO2)为约70/30到74/26。
可以通过使用例如纺丝起始溶液制造上述氧化铝基纤维垫,该溶液包含由氧化铝源(诸如氯氧化铝)、二氧化硅源(诸如二氧化硅溶胶)、有机粘结剂(诸如聚乙烯醇)和水组成的混合物。这样,纺成的氧化铝纤维前体经过层合形成薄板,然后优选地受到针刺,其后通常在1000到1300C的高温下进行烘烤。
如图3中示意性示出的,根据本发明的催化剂载体保持材料包含前述厚度的纤维材料垫2,该垫插在壳体4和该壳体内的催化剂载体1之间,缠绕着催化剂载体1的外周边表面。在这个垫状催化剂载体保持材料2中,选择性地设置能够增加与壳体4的摩擦系数的无机胶粒5,并且在壳体4一侧的该保持材料的外周边表面2a上形成摩擦层3,具体地讲,专门在这个表面区域上形成。此外,如有必要,包含无机胶粒的摩擦层也可以设置在催化剂载体1一侧的催化剂载体保持材料2的内周边表面2b上(图中未示)。
在本发明的实践中,虽然可以采用各种技术形成催化剂载体保持材料的摩擦层,但是通过在已制成的纤维材料垫的表面上涂布包含无机材料微粒(优选为金属氧化物)的胶体溶液,可以有利地形成摩擦层。因此,大体构成摩擦层的所述无机胶粒优选地来自含有金属氧化物微粒的胶体溶液。
虽然有多种类型的无机材料微粒可以用来形成无机胶粒,但是优选的无机材料包括金属氧化物、金属氮化物和金属碳化物,并且这些材料优选地具有耐热性。例如,具有耐热性的金属氧化物的优选实例包括二氧化硅、氧化铝、莫来石、氧化锆、氧化镁和二氧化钛,但这份名单并非限制性的。其它适当材料的实例包括氮化硼和碳化硼。这些无机材料既可单独使用,又可以两种或更多种的组合混合使用。
虽然上述无机胶粒可以采用与无机材料类型和所需摩擦改善效果相一致的多种粒度,但通常优选地具有约1到100nm的平均粒度。如果无机胶粒的平均粒度小于1nm,则不可能形成能够有助于增加摩擦效果的摩擦层。相反,如果无机胶粒的平均粒度超过100nm,则颗粒太大,不能有助于适当增加摩擦效果,并且有可能脱落。更优选地,无机胶粒的平均粒度在约10到80nm的范围内,最优选地在约20到50nm的范围内。
在根据本发明的催化剂载体保持材料中,可以通过在保持材料的表面区域添加不同量的无机胶粒以形成摩擦层,但是通常优选的是,基于保持材料的总重量添加约0.01到30重量%的无机胶粒。如果添加的无机胶粒量小于0.01重量%,则表现不出无机胶粒的添加效果,并且因此不能将摩擦系数增大到预期值。相反,如果添加的无机胶粒量大于30重量%,则垫变硬,并且保持材料在使用过程中会断裂或弯曲。更优选地,添加的无机胶粒量为约0.05到25重量%,最优选地为约0.1到10重量%。
在制成所述催化剂载体保持材料后,可以通过任何方法处理该保持材料以形成由上述无机胶粒构成的所述摩擦层。对催化剂载体保持材料的制造需要说明的是,可以通过包括干法和湿法在内的各种方法制造保持材料。例如,基于干法的制造可以通过针刺无机纤维的层合体来实施。此外,湿法可以通过一系列工序来实施,这些工序包括:混合无机纤维与有机粘结剂、散布无机纤维、制备浆液、通过纸成型方法进行成型以及压制成型体。
可以优选通过例如在催化剂保持材料(纤维材料垫)上涂布包含无机材料(诸如金属氧化物)微粒的胶体溶液,形成包含无机胶粒的摩擦层。适合的涂布方法的实例包括辊涂、喷涂、膜转移和浸涂。一完成涂布工艺,通过在例如约100-200C的温度下进行干燥,就可获得所需的摩擦层。显然,这种制造方法并不需要常规技术中必不可少的高温热处理(诸如烘烤)。因此,从工艺条件的角度来看,单独制备涂布液而与纤维材料垫无关是一项优势所在。
根据本发明,如上文所述,在催化剂载体保持材料的表面上设置包含无机胶粒的摩擦层使得增大催化剂载体表面与壳体(例如由SS板或其它金属板形成的)之间的摩擦系数成为可能。因此,可以改进催化剂载体保持材料以及使用这种材料的催化转化器的性能。如发明人所发现的,在催化剂载体保持材料的表面区域上形成的摩擦层中, 优选将有机粘结剂与上述无机胶粒一同使用。构造摩擦层以使其包含与无机胶粒一同使用的有机粘结剂,这样便有可能进一步增强摩擦层的功能,防止无机胶粒的脱落或脱离,和在加热催化转化器之前和之后增大摩擦系数。
对于与无机胶粒一同使用的有机粘结剂,没有对其种类及数量设置任何具体的限制,因此可以选择具有粘结剂或类似功能的便利材料以供使用。例如,以乳胶或其类似物的形式提供的丙烯酸类树脂、苯乙烯-丁二烯树脂、丙烯腈树脂、聚氨酯树脂、天然橡胶和聚(乙酸乙烯)树脂均可用作有机粘结剂。此外,这样的有机粘结剂还可以包含柔性的热固性树胶,例如,不饱和聚酯树脂、环氧树脂或聚乙烯脂树脂。
当有机粘结剂与无机胶粒一同使用时,虽然可以使用不同量的有机粘结剂,但通常优选的是,应当在无机胶粒中添加1/20或更大量(重量比率)的有机粘结剂来进行使用。这是因为只有在无机胶粒中添加1/20或更大量(重量比率)的有机粘结剂后,才能观察到有机粘结剂的添加效果,并且无机胶粒才能更牢靠地固定在催化剂载体保持材料的表面并保持不动。此外,如果基于保持材料重量的有机粘结剂总量达到15重量%或更高(具体量取决于催化剂载体保持材料的表面积),则在实际车辆中携带和使用催化转化器时,燃烧气体能对气体传感器产生不良影响。因此,优选地,所用的有机粘结剂的量小于15重量%。
根据本发明,如上文所述,在催化剂载体保持材料的表面上同时涂布和设置无机胶粒和有机粘结剂,这样便有可能控制无机胶粒向构成保持材料的纤维材料内部渗透,并在保持材料的表面区域上形成所需的摩擦层。然而,考虑到当保持材料中的纤维材料和无机胶粒中的无机材料具有几乎相同的成分时,很难测量和确定无机胶粒在表面区域中的选择性分配,根据本发明,基于无机胶体溶液和有机粘结剂同 时涂布和同时干燥这一事实,可以将催化剂载体保持材料在900C的烘箱中持续加热1小时,然后通过加热失重法来测量无机胶粒的分配。
实例本文下面将结合本发明的实例对本发明进行描述。不言而喻,本发明并不限于这些实例。
实例1:
在本实例中:测试
(1)无机胶粒和有机粘结剂的配比与无机胶粒的脱落比率之间的关系;
(2)无机胶粒的量与SS板和垫之间的摩擦系数的关系;以及
(3)无机胶粒的量与催化剂载体和垫之间的摩擦系数的关系,
测试是在相对于在催化剂载体保持材料的摩擦层的形成过程中改变无机胶粒和有机粘结剂的配比的情况下进行的。
制备表面密度为0.4g/cm3的针刺氧化铝纤维垫(商品名为MAFTEC,由Mitsubishi Chemical Functional Products,Inc.制造)。该氧化铝纤维垫的尺寸为260mm(长度)×90mm(宽度)×12.5mm(厚度)。此外,无机胶粒:硅胶(由Nissan Chemical Co.,Ltd.制造,商品名为SNOWTEX-O)和有机粘结剂:丙烯酸树脂乳胶(由NipponZeon Co.,Ltd.制造,商品名为NIPOL LX-820A)按如下面表1所述的不同配比在水中搅拌混合,以用于形成摩擦层。制备四种类型的胶状涂层溶液。
然后,将每种涂层溶液喷涂到氧化铝纤维垫的表面上。将涂布后的氧化铝纤维垫置于180C的烘箱中干燥,直至含水量变成约50%,然后再在设置为145C的圆柱体干燥机中进行绝对干燥。在干燥后的氧化铝纤维垫中,确认二氧化硅微粒已附着到氧化铝纤维垫的表面上。
测定二氧化硅微粒的脱落比率
按照下述步骤测量每个氧化铝纤维垫的二氧化硅(SiO2)微粒脱落比率(重量%),其中所述每个氧化铝纤维垫按照上述方式加工而成并具有粘附其上的二氧化硅微粒。
准备日本工业标准(JIS K-6830)中所描述的冲击试验机并遵照该标准中所描述的指导原则实施测试。测试方法如下。
(1)使用冲孔模加工一个样本(尺寸:100mm×100mm),并测量其质量。
(2)将该样本置于JIS K-6830中所描述的冲击试验机中并经受来自30角度的撞击。
(3)从冲击试验机中取出测试后的样本,并再次测量其质量。
(4)通过测试前后测得的该样本质量的差值计算出分散的二氧化硅微粒的量。获得测量结果(二氧化硅微粒的脱落比率,重量%),并在下面表1中描述和在随附的图5中绘出。
表1
乳胶/SiO2比率 | 脱落比率(重量%) |
0.11 | 0.047 |
0.11 | 0.111 |
0.11 | 0.063 |
0.11 | 0.108 |
1.05 | 0.007 |
1.05 | 0.008 |
1.05 | 0.011 |
6.99 | 0.008 |
6.99 | 0.010 |
6.93 | 0.007 |
6.93 | 0.003 |
如从以上表1和图5中所述测量结果可以了解到的,当乳胶比率(乳胶相对于二氧化硅微粒的比率)高于1/20时,可有效地防止二氧化硅微粒脱落。
SS板和垫之间的摩擦系数
按照下述步骤,使用由Shimazu Corp.制造的AutographAGS100D(商品名)来测量SS板和垫之间的摩擦系数,其中所述垫是以上述方式加工的氧化铝纤维垫,具有粘附其上的二氧化硅微粒。
将各自的样本切割为长50mm、宽25mm和厚12.5mm的样本件。然后,如图4所示,使用双面粘合带42将与摩擦层3所在表面相对的样本件2表面固定到SS板46上。
然后准备一根长约1m的不锈钢绳43并将其一端固定到SS板46上。将滑轮块45设置在测力传感器44的直接下方并且经过滑轮块45将钢绳43的另一端固定到测力传感器44,以使得升起测力传感器44时,固定到样本件2上的SS板46平行于地面移动。
然后将样本件2固定到SS板41上以与地面平行,同时让SS板41的中心轴相对于滑轮块45垂直。在此,用来代替壳体的SS板41经过2B处理(冷轧处理)并被加工成具有约0.2到0.5μm的表面粗糙度。此外,调整测力传感器44的高度,以使得可在离滑轮块45最大距离的位置加载样本件2。
然后将12kg的负载47固定安装到SS板46上,之后升起测力传感器44,并以100cm/min的牵引速率沿箭头所示方向拉动不锈钢绳43。将样本件2在SS板41表面上刚开始滑动前所测量到的负载记录为静摩擦力(kgf),然后通过用它除以施加到样本件2上包括SS板46在内的负载计算出摩擦系数。获得测量结果(SS板与垫之间的摩擦系数),并在下面表2中描述和在随附的图6中绘出。 此外,表中的“SiO2量”及数字表示相对于垫总重量的二氧化硅微粒量。
表2
SiO2量(重量%) | SS板与垫之间的摩擦系数 |
0.0% | 0.196 |
0.1% | 0.208 |
0.2% | 0.221 |
0.5% | 0.213 |
0.6% | 0.229 |
1.3% | 0.225 |
1.3% | 0.238 |
1.4% | 0.233 |
3.2% | 0.242 |
4.1% | 0.233 |
4.5% | 0.246 |
催化剂载体与垫之间的摩擦系数
按照上述关于SS板与垫之间的摩擦系数的步骤,使用由Shimazu Corp.制造的Autograph AGS100D(商品名)测量催化剂载体与垫之间的摩擦系数,该垫为以上述方式加工的氧化铝纤维垫,具有粘附其上的二氧化硅微粒。
切割样本以制成样本件,并将这些样本件安装到图4所示的测试机器上。然而,由于在这种情况下的测量目标是催化剂载体和垫之间的摩擦系数,因此使用催化剂载体(由Nippon Gaishi K.K.制造的单片体,商品名为“HONEYCERAM”)替代用于图4所示壳体中的SS板41。该催化剂载体具有约2.5μm的表面粗糙度Ra。
将12kg的负载47固定安装在SS板46上,之后升起测力传 感器44,并以100cm/min的牵引速率沿箭头所示方向拉动不锈钢绳43。将样本件2在SS板41上刚开始滑动前所测量到的负载记录为静摩擦力(kgf),然后通过用它除以施加到样本件2上包括SS板46在内的负载计算出摩擦系数。获得测量结果(催化剂载体与垫之间的摩擦系数),并在下面表3中描述和在随附的图7中绘出。
表3
SiO2量(重量%) | 载体与垫之间的摩擦系数 |
0.0% | 0.554 |
0.1% | 0.633 |
0.2% | 0.600 |
0.6% | 0.613 |
0.6% | 0.633 |
1.3% | 0.650 |
1.3% | 0.646 |
1.4% | 0.613 |
3.2% | 0.617 |
4.1% | 0.642 |
4.5% | 0.683 |
如从参考图6和图7中所示的摩擦系数逼近曲线所描述的,当基于垫重量所施加的无机胶粒(二氧化硅微粒)的量为0.01重量%或更大时,可观察到SS板与垫之间的摩擦系数和催化剂载体与垫之间的摩擦系数都增大。此外,由于在本实例中用于测量摩擦系数的SS板的表面和单片体的表面都具有约2.5μm的粗糙度Ra,一般来讲,在本发明的情况中,当壳体和催化剂载体具有约2.5μm或更大的表面粗糙度Ra时,就可实现增大摩擦系数的效果。
实例2:
在本实例中:测试
(1)无机胶粒和有机粘结剂的配比与无机胶粒的脱落比率之间的关系;
(2)无机胶粒的量与SS板和垫之间的摩擦系数之间的关系;以及
(3)无机胶粒的量与催化剂载体和垫之间的摩擦系数之间的关系,
测试是在相对于按照实例1所述的步骤在形成催化剂载体保持材料的摩擦层的过程中改变无机胶粒和有机粘接剂的配比的情况下进行的。
细胶粒:胶体氧化铝(由Nissan Chemical Co.,Ltd.制造,商品名为ALUMINA SOL-200)和有机粘结剂:丙烯酸树脂乳胶(由Rohm andHaas Co.,Ltd.制造,商品名为ST-954)按如下面表4中所述的不同配比在水中搅拌混合,以用于形成摩擦层。制备三种类型的胶状涂层溶液。然后将每种涂层溶液喷涂到氧化铝纤维垫的表面上并进行干燥。在干燥后的氧化铝纤维垫中,确认氧化铝已附着到氧化铝纤维垫的表面上。
测定二氧化硅微粒的脱落比率
按照实例1中所述步骤测量每个氧化铝纤维垫的氧化铝(Al2O3)微粒脱落比率(重量%),其中所述每个氧化铝纤维垫按照上述方式加工而成并具有粘附其上的二氧化硅微粒。获得测量结果(氧化铝微粒的脱落比率,重量%),并在下面的表4中描述和在随附的图8中绘出。
表4
乳胶/Al2O3比率 | 脱落比率(重量%) |
0.23 | 0.031 |
0.23 | 0.027 |
0.23 | 0.033 |
2.25 | 0.007 |
2.25 | 0.007 |
2.25 | 0.017 |
2.25 | 0.007 |
11.25 | 0.002 |
11.25 | 0.002 |
11.25 | 0.008 |
如从以上表4和图8中所述测量结果可以了解到的,当乳胶比率(乳胶相对于氧化硅微粒的比率)高于1/20时,可有效地防止氧化铝微粒脱落。
SS板与垫之间的摩擦系数
按照实例1中所述步骤测量SS板与垫之间的摩擦系数,其中所述氧化铝纤维垫按照上述方式加工而成并具有粘附其上的氧化铝微粒。获得测量结果(SS板与垫之间的摩擦系数),并在下面的表5中描述和在随附的图9中绘出。此外,表中的“Al2O3量”及数字表示相对于垫总重量的氧化铝微粒量。
表5
Al2O3量(重量%) | SS板与垫之间的摩擦系数 |
0.0% | 0.188 |
0.1% | 0.208 |
0.1% | 0.200 |
0.1% | 0.196 |
0.1% | 0.196 |
0.3% | 0.200 |
0.3% | 0.204 |
0.7% | 0.213 |
0.7% | 0.217 |
2.6% | 0.208 |
2.7% | 0.213 |
催化剂载体与垫之间的摩擦系数
按照实例1中所述步骤测量催化剂载体与垫之间的摩擦系数,其中所述氧化铝纤维垫按照上述方式加工而成并具有粘附其上的氧化铝微粒。获得测量结果(催化剂载体和垫之间的摩擦系数),并在下面的表6中描述和在随附的图10中绘出。
表6
Al2O3量(重量%) | 载体与垫之间的摩擦系数 |
0.0% | 0.554 |
0.1% | 0.588 |
0.1% | 0.625 |
0.1% | 0.638 |
0.1% | 0.671 |
0.3% | 0.633 |
0.3% | 0.638 |
0.7% | 0.646 |
0.7% | 0.638 |
2.6% | 0.663 |
2.7% | 0.679 |
如从图9和图10中所示的逼近曲线所描述的,当基于垫重量所施加的无机胶粒(氧化铝微粒)的量为0.01重量%或更大时,可观察到SS板与垫之间摩擦系数和催化剂载体与垫之间的摩擦系数都增大。此外,由于在本例子中用于测量摩擦系数的SS板的表面和单片体的表面都具有约2.5μm的粗糙度Ra,一般来讲,在本发明的情况中,当壳体和催化剂载体具有约2.5μm或更大的表面粗糙度Ra时,就可实现增大摩擦系数的效果。
实例3:
生产催化转化器
参照在实例1和实例2的评估试验中获得良好测量结果的样本,制造具有与这些样本相同结构的摩擦层的氧化铝纤维垫。然后在另行制备的催化剂载体(由Nippon Gaishi K.K.制造的单片体,商品名为“HONEYCERAM”)的外周边缠绕氧化铝纤维垫,该催化剂载体具有外径为78mm、长度为100mm的圆柱形形状。通过使用导锥以40mm/sec的速度将缠绕有氧化铝纤维垫的催化剂载体压力配合到圆柱形不锈钢壳体中,该壳体内径为84mm、长度为120mm。在此封装过程中,催化剂载体与壳体之间的间距为约3mm。在催化剂载体一侧和壳体一侧,通过使用催化剂载体一侧、壳体一侧以及在两个表面上都具有摩擦层的氧化铝纤维垫来进行压力配合,而目标催化转化器可在没有任何不便(例如损伤催化剂载体或氧化铝纤维垫和降低装配的可操纵性)的情况下加工而成。此外,催化剂载体和氧化铝纤维垫之间没有发生任何位移。此外,所得催化转化器在实际使用中可充分展示预期的废气净化功能。
Claims (18)
1.一种用于污染控制元件的保持材料,其用于缠绕在壳体内的污染控制元件周围并保持该污染控制元件,且其被设置在所述壳体和所述污染控制元件之间,所述保持材料包括:
无机纤维材料垫,其具有厚度、外周边表面、以及内周边表面;以及
至少一个包含无机胶粒的摩擦层,所述摩擦层只位于所述垫内周边表面和外周边表面中的一个表面上,且所述垫的内周边表面和外周边表面中的另一个表面没有包含无机材料微粒的层,
其中当将所述保持材料设置在污染控制装置中的壳体和污染控制元件之间时,所述摩擦层接触所述壳体和所述污染控制元件中的至少一个。
2.一种污染控制元件保持材料,用于缠绕在壳体内所述污染控制材料的周围并固定该污染控制元件,且其被设置在所述壳体和所述污染控制元件之间,所述保持材料包括:
无机纤维材料垫,其具有厚度、外周边表面、以及内周边表面;以及
至少两个摩擦层,每个所述摩擦层均具有无机胶粒,一个所述摩擦层位于所述垫的外周边表面上,而另一个摩擦层位于所述垫的内周边表面上,
其中当将所述保持材料设置在污染控制装置中的壳体和污染控制元件之间时,所述一个摩擦层接触所述壳体而所述另一个摩擦层接触所述污染控制元件。
3.根据权利要求1或2所述的保持材料,其中所述纤维材料包含至少一种由选自如下物质组成的组的无机纤维:玻璃纤维、陶瓷纤维、碳纤维、碳化硅纤维以及硼纤维。
4.根据权利要求1或2所述的保持材料,其中所述无机胶粒衍生自包含至少一种无机材料微粒的胶体溶液,这些材料选自由金属氧化物、金属氮化物和金属碳化物组成的组。
5.根据权利要求1或2所述的保持材料,其中所述无机胶粒具有1到100nm的平均粒度。
6.根据权利要求1或2所述的保持材料,其中所述无机胶粒的含量基于所述保持材料的总重量为0.01到30重量%。
7.根据权利要求1或2所述的保持材料,其中每个所述摩擦层除包含所述无机胶粒外,还包含有机粘结剂。
8.根据权利要求7所述的保持材料,其中以1/20或更高的重量比将所述有机粘结剂添加到所述无机胶粒中。
9.根据权利要求1或2所述的保持材料,其中每个所述摩擦层为在所述垫的表面上包含无机材料微粒的胶体溶液的涂层。
10.根据权利要求1或2所述的保持材料,其中对所述保持材料进行可操作性改造,以适合在催化转化器内安装催化剂载体。
11.根据权利要求1或2所述的保持材料,其中对所述保持材料进行可操作性改造,以适合在过滤器内安装过滤元件。
12.一种污染控制装置,包括壳体、设置在所述壳体内的污染控制元件和根据权利要求1至9中任一项权利要求所述的保持材料,所述保持材料被设置在所述壳体和所述污染控制元件之间,以使得在所述污染控制装置内部安装所述污染控制元件。
13.根据权利要求12所述的污染控制装置,其中所述污染控制元件为催化剂载体,且所述污染控制装置为催化转化器。
14.根据权利要求12所述的污染控制装置,其中所述污染控制元件为过滤元件,且所述污染控制装置为废气净化装置。
15.一种用于内燃机的排气系统,包括根据权利要求12至14中任一项权利要求所述的污染控制装置。
16.一种内燃机,包括根据权利要求15所述的排气系统。
17.一种车辆,包括具有根据权利要求15所述的排气系统的内燃机。
18.一种发电机,包括具有根据权利要求15所述的排气系统的内燃机。
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- 2006-09-05 CA CA2621689A patent/CA2621689C/en not_active Expired - Fee Related
- 2006-09-05 WO PCT/US2006/034378 patent/WO2007030410A1/en active Application Filing
-
2008
- 2008-04-07 ZA ZA200803027A patent/ZA200803027B/xx unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3224927A (en) * | 1963-10-04 | 1965-12-21 | Du Pont | Forming inorganic fiber material containing cationic starch and colloidal silica |
EP0004385A2 (en) * | 1978-03-29 | 1979-10-03 | Kennecott Corporation | Process for forming a refractory fiber article and article obtained by said process |
US6444600B1 (en) * | 1999-07-12 | 2002-09-03 | Agency For Defense Development | High strength light-weight ceramic insulator |
Also Published As
Publication number | Publication date |
---|---|
US7854905B2 (en) | 2010-12-21 |
EP1931862B2 (en) | 2013-12-04 |
KR101497865B1 (ko) | 2015-03-04 |
ZA200803027B (en) | 2009-03-25 |
JP5275802B2 (ja) | 2013-08-28 |
CA2621689A1 (en) | 2007-03-15 |
KR20130135401A (ko) | 2013-12-10 |
ATE437298T1 (de) | 2009-08-15 |
BRPI0615571A2 (pt) | 2011-05-24 |
KR101659076B1 (ko) | 2016-09-22 |
KR20080043869A (ko) | 2008-05-19 |
US20090025377A1 (en) | 2009-01-29 |
DE602006008019D1 (de) | 2009-09-03 |
EP1931862B1 (en) | 2009-07-22 |
WO2007030410A1 (en) | 2007-03-15 |
EP1931862A1 (en) | 2008-06-18 |
CA2621689C (en) | 2013-05-14 |
JP2009508044A (ja) | 2009-02-26 |
CN101283167A (zh) | 2008-10-08 |
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