CN100537213C - 高孔隙率蜂窝体及其制造方法 - Google Patents

高孔隙率蜂窝体及其制造方法 Download PDF

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CN100537213C
CN100537213C CNB2004800279264A CN200480027926A CN100537213C CN 100537213 C CN100537213 C CN 100537213C CN B2004800279264 A CNB2004800279264 A CN B2004800279264A CN 200480027926 A CN200480027926 A CN 200480027926A CN 100537213 C CN100537213 C CN 100537213C
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base material
honeycomb
millimeter
honeycomb ceramics
pore former
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CN1856398A (zh
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X·R·福
侯军
J·F·小怀特
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Corning Inc
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Corning Inc
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
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    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C04B2235/3481—Alkaline earth metal alumino-silicates other than clay, e.g. cordierite, beryl, micas such as margarite, plagioclase feldspars such as anorthite, zeolites such as chabazite
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract

本发明提供一种用于汽车催化转化器系统的蜂窝体基材，该基材由于45-75%的高孔隙率而具有改进的点火性能，同时保持壁厚大于2.0密耳(0.0020英寸，0.0508毫米)，优选2.5密耳(0.0025英寸，0.0635毫米)至7密耳(0.0070英寸，0.1778毫米)，更优选2.5密耳(0.0025英寸，0.0635毫米)至3密耳(0.0030英寸，0.0762毫米)。其中值孔径为2-10微米，热膨胀系数(CTE)(25-800℃)小于15×10-7/℃。

Description

高孔隙率蜂窝体及其制造方法
发明背景
本发明涉及用于汽车催化转化器系统的陶瓷体，具体涉及具有减少的热质量，而且能够提供更快点火操作的高孔隙率蜂窝体基材。
使用烃类气体、汽油或柴油之类烃类燃料的内燃系统排放的废气会严重污染大气。废气中的众多污染物包括烃和含氧化合物，后者包括氧化氮(NOx)和一氧化碳(CO)。汽车工业尝试减少机车发动机系统所产生污染的量已有许多年，在二十世纪七十年代中期开发出了第一批装有催化转化器系统的汽车。
长期以来，优选一般是将蜂窝体结构形式的堇青石基材用作负载催化活性组分的基材，这部分是由于这种结构具有很高的耐热冲击性。近年来愈加严格的规定需要汽车市场中的催化转化器具有更高的转化效率。通过控制点火方法可以显著减少汽车排放物。占总量50％以上的汽车排放物是在进行点火之前产生的。
基材的点火时间很大程度上是由其热质量决定的；具体来说，热质量较低会使得点火较快。一种达到较低热质量的方法是减小孔壁板(cell web)的厚度。因此，对具有很薄壁板(例如小于2.5密耳(0.0025英寸，0.0635毫米))的基材的需求显著增加。除了减少热质量，这些结构还应具有更大的几何表面积以及更低的背压力。
尽管薄壁板的蜂窝体结构具有这些优点，但是减小孔壁板的厚度会显著降低该结构体的强度。这会在催化转化器基材的制造过程中造成问题。如果这种基材强度显著降低，制造时会发生破裂。另外，制造这些材料时也有许多要求。需要使用较小粒度、污染物含量较少的原料以防堵塞筛和模具。另外，将该批料挤压通过很窄的模缝所需的挤出压力可能会达到挤出机的极限。
另一种减小催化转化器基材热质量的方法是在保持孔密度和壁厚基本恒定的同时增加孔隙率。然而，仍然很重要的是保持低的热膨胀系数以防由于热冲击发生破坏。不幸的是，已知高孔隙率和低热膨胀会降低蜂窝体基材的强度。
因此，在保持高强度和低热膨胀的前提下，不需使用很薄的孔壁板便达到高孔隙率，从而改进点火性能的催化转化器基材将被视为本领域的进步。本发明提供了这样的结构及其制备方法。
发明简述
本发明涉及一种用于具有改进的点火性能的汽车催化转化器系统的高孔隙率陶瓷蜂窝体基材。在一个方面，所述由具有进口端、出口端和大量孔的蜂窝体限定的蜂窝体基材的特征还在于，孔壁的厚度大于2.0密耳(0.0020英寸，0.0508毫米)，优选为2.5密耳(0.0025英寸，0.0635毫米)至7密耳(0.0070英寸，0.1778毫米)。在一方面，本发明制品的总孔隙率为45-75％，优选为50-65％，最优选为55％；中值孔径为2-10微米，优选为2-4微米，最优选为3微米。在另一方面，本发明制品的热膨胀系数(CTE)(25-800℃)小于15×10-7/℃，优选小于10×10-7/℃。在另一方面本发明制品在一多孔棒样品上测得的弹性模量(MOR)强度为200-400psi，优选为350psi。
本发明还涉及一种用来形成用于如下文所述催化转化器系统的高孔隙率陶瓷蜂窝体基材的方法。首先配合组分的批料，该批料由陶瓷粉末材料、增塑粘合剂体系以及平均粒径为1-30微米、优选2-18微米的成孔剂组成。然后将这些组分投配制成增塑的混合物。然后通过挤压使该增塑混合物通过模具，形成生坯蜂窝体，然后该结构在一定温度下烧制充足时间，形成所需性质。下面将进一步描述本发明制造方法的优选实施方式。
附图简述
结合以下详细描述、参照附图可完全理解本发明，在附图中：
图1是根据本发明的高孔隙率堇青石蜂窝体基材中预计改进的点火时间的化学反应模型图；
图2是根据本发明的高孔隙率堇青石蜂窝体基材487X倍放大的扫描电子显微照片；
图3是在市场上购得的堇青石蜂窝体基材487X倍放大的扫描电子显微照片。
发明详述
本发明的陶瓷蜂窝体基材将具有由45-75％的高孔隙率造成的具有快点火时间的很薄壁结构吸引人的性质与壁厚度大于2.0密耳(0.0020英寸，0.0508毫米)的更常规的基材结构结合起来。
在一优选实施方式中，孔隙率优选为50-65％，最优选为55％。在另一优选实施方式中，壁厚为2.5密耳(0.0025英寸，0.0635毫米)至7密耳(0.0070英寸，0.1778毫米)，更优选为2.5密耳(0.0025英寸，0.0635毫米)至3密耳(0.0030英寸，0.0762毫米)。
本发明蜂窝体的孔密度并不重要，而是取决于具体用途。通常400孔/平方英寸(62孔/平方厘米)至900孔/平方英寸(140孔/平方厘米)的孔密度适于本发明的目的。
在一个实施方式中，本发明的结构具有小于15×10-7/℃，优选小于10×10-7/℃的低热膨胀系数(CTE)(25-800℃)。这种低热膨胀使蜂窝体具有高耐热冲击性，使其适用于恶劣环境。在另一实施方式中，本发明的结构具有高结构强度，以弹性模量(MOR)表示，在多孔棒样品上测得为200-400psi，优选350psi。
本发明蜂窝体所用的陶瓷材料并不重要，可包括硅酸盐、氧化物、铝酸盐、氮化物、硼酸盐、碳化物和铝化物中的任一种。本发明特别适于包含堇青石和/或富铝红柱石的陶瓷蜂窝体基材。这些混合物的例子是0-60重量％富铝红柱石和30-100重量％堇青石，可包含通常高达10重量％的其它相。
使用化学反应模型预测得知，使用本发明基材，点火过程可比使用类似产品减少约5.5秒。参见图1，图中显示本发明堇青石基材与对比堇青石基材点火时间的比较。这两种基材的几何结构均为900孔/平方英寸(140孔/平方厘米)、孔壁厚均为2.5密耳(0.0025英寸，0.0635毫米)。本发明的基材以63％的孔隙率为模型，对比基材以25％的孔隙率为模型。可以看到，预测在本发明基材中点火减少了5.5秒。这比相当的较低孔隙率对比基材快得多。
本发明还涉及形成本发明结构的方法。首先配合组合的批料。该批料的组分包括陶瓷粉末材料、增塑粘合剂体系和成孔剂。本发明使用各种无机陶瓷粉末，包括选自硅酸盐、硼酸盐或铝酸盐玻璃或晶体或半晶体硅酸盐、氧化物、铝酸盐、硼酸盐、碳化物、氮化物、硼化物和铝化物的无定形材料、晶体材料或半晶体材料。然而，特别合适的陶瓷粉末材料包括堇青石、尖晶石、粘土、滑石、氧化铝、氢氧化铝、二氧化硅以及以下元素的氧化物：钙、镁、硼、钛、锗和碱金属以及过渡金属。
美国专利第6,506,336B1号揭示了一些用来形成特别适用于实施本发明的堇青石的陶瓷批料组合物，该专利全文参考结合在本文中。一种能够通过烧制最终形成堇青石的组合物具有以下组成：33-41重量％氧化铝，46-53重量％二氧化硅和11-17重量％氧化镁。合适的用来形成堇青石的无机陶瓷粉末原料包括高纯粘土、滑石、二氧化硅、氧化铝、氢氧化铝、和能够生成氧化镁(MgO)的原料。优选的形成堇青石的粉末材料包括高岭土、滑石、氧化铝和二氧化硅。
合适的粘土是KAOPAQUE-10(K10)粘土之类的平均粒度小于2微米的层状生高岭粘土，和Glomax LLTM之类的平均粒度小于2微米、表面积大于10平方米/克的煅烧粘土，它们均可购自Dry Branch Kaolin。合适的滑石的形态指数(参见美国专利第5,141,686号)大于0.8，平均粒度小于2微米(由Sedigraph粒度测定仪测得)，表面积大于5平方米/克，该滑石的一个例子是购自Luzenac America的Artic Mist。
所述氧化铝源的平均粒度等于或小于5微米，优选等于或小于1微米。氧化铝源可以是氧化铝、氢氧化铝、碱式氢氧化铝及其组合中的任何一种，氧化铝源优选包括勃姆石或假勃姆石。合适的氧化铝源包括购自Alcoa的A1000SGDTM和/或购自Sasol North America，Inc.的Dispal Alumina。合适的二氧化硅的平均粒度小于5微米，表面积约为4-6平方米/克，其例子是购自Unimin公司的IMSILTM。
本发明所用的增塑粘合剂体系部分取决于批料中陶瓷粉末材料的组成和形态。对于堇青石蜂窝体的制造，包含纤维素醚粘合剂、硬脂酸或油酸之类的表面活性剂组分、油或油基组分和水赋形剂的水性粘合剂体系可以制得高塑性的批料，所述纤维素醚粘合剂选自甲基纤维素、甲基纤维素衍生物及其组合，所述油或油基组分优选为聚α烯烃之类的低分子量油。在一优选实施方式中，以陶瓷粉末材料为100重量份计，所述粘合剂体系包含2-25重量份纤维素醚粘合剂、0.5-10重量份表面活性剂、2-25重量份油和30-100重量份水赋形剂。该粘合剂体系的组分以额外量加入(supper-addition)的形式加入，其重量含量用(粘合剂、表面活性剂、油或水的质量)/(陶瓷材料质量)×100％计算。
除了陶瓷粉末材料和增塑粘合剂体系以外，该批料还包含大量成孔剂。像粘合剂体系一样，成孔剂以额外量加入的形式加入，其重量含量以(粘合剂、表面活性剂、油或水的质量)/(陶瓷材料的质量)×100％计算。在本发明的实施方式中，成孔剂的加入量为15-85重量％，优选30-70重量％，其平均粒度为2-18微米，优选3-8微米。平均粒度小于2微米的成孔剂是无效的，会产生高收缩而不会产生所需的孔隙率。平均粒度大于18微米的成孔剂会降低所得烧制结构的强度。
所述成孔剂可以是任何能够在烧制过程中通过蒸发或降解形成残余孔穴的天然材料或合成材料，可包括例如碳、石墨、淀粉、纤维素、天然蜡和合成蜡之类的材料。较佳的是，成孔剂是具有至少70℃的高熔点的蜡，例如石蜡、微晶蜡、聚乙烯蜡、合成酰胺、氯化蜡及其分散体。＂分散体＂表示成孔剂处于液体环境中，固体加入量小于50重量％。最优选成孔剂是聚乙烯蜡或其分散体。用真空或惰性气氛除去蜡成孔剂，然后进行烧制。
将所述批料组分，即陶瓷粉末材料、增塑粘合剂体系和成孔剂混合形成增塑的混合物。在一实施方式中，先将一部分粉末状陶瓷材料与成孔剂分散体混合形成均匀混合物。然后干燥该混合物并筛分，制得组成主要为60-85重量％、优选70重量％成孔剂，5-25重量％、优选15重量％陶瓷材料和2-20重量％、优选10重量％水的颗粒成孔材料混合物。然后将剩余的粉末状陶瓷材料与粘合剂干混合，然后将制得的干混合物加入颗粒成孔材料混合物。
然后向该制得的混合物加入增塑粘合剂体系的剩余组分，即表面活性剂组分、油或油基组份和水赋形剂。水的含量可根据材料的种类而异，使其具有最佳的处理性质以及与混合物中其它组分的相容性。从实际角度来说，以陶瓷粉末材料为100重量份计，该实施方式中水的含量通常约为30-100份，优选43份。然后在任何合适的混合器中对该湿混合物施加剪切作用，在此混合器中对该批料进行增塑。一种合适的成孔剂分散体是购自Michelman Inc.、商品名为Michem Guard 10，15，20，25，55和60的聚乙烯蜡分散体。
在另一实施方式中，先将可烧结的陶瓷材料、粘合剂和粉末状成孔剂干混形成均匀混合物。然后向制得的干混合物加入表面活性剂、油和水赋形剂。然后可在例如Littleford之类的混合器中将该混合物混合。水赋形剂以批料增塑所需的量加入，以陶瓷粉末材料为100重量份计，通常为30-100份。不同材料批料中的水含量可不同，是通过对具体批料的可挤出性进行预先试验而确定的。然后通过已知方法对该湿混合物增塑。合适的成孔剂是购自Michelman Inc.的商品名为MichemWax410,411,436,437,439和492的聚乙烯蜡粉末。其它有用的成孔剂包括购自Honeywell、商品名为ACumist A6，A12，A18，B6，B9，B12，B18，C5，C12，C18，D5，D9，E6，E12，3105，3205，3305，1106，1109，1112，1204，1306和1309的微粉化聚乙烯蜡粉末。
然后优选用挤压法使制得的增塑的批料成形，制成生坯体，例如通过挤出模制成蜂窝体。挤出技术在本领域是众所周知的。所述蜂窝体结构具有进口端即进口面和出口端即出口面，以及大量在进口端和出口端之间延伸的孔。本发明的蜂窝体可制成具有适于所需用途的各种孔密度。本发明特别适于用厚度超过2密耳(0.0020英寸，0.0508毫米)、优选2.5密耳(0.0025英寸，0.0635毫米)至7密耳(0.0070英寸，0.1778毫米)、更优选2.5密耳(0.0025英寸，0.0635毫米)至3密耳(0.0030英寸，0.0762毫米)的孔壁形成高达900孔/平方英寸(140孔/平方厘米)的很高的孔密度。
在烧制之前，在真空或惰性气氛中加热，从生坯体(可任选先将其干燥)中除去成孔剂。在一个实施方式中，可使用可在市场上购得的真空热解器在真空下将生坯体在一定温度加热足够的时间，以基本除去成孔剂。或者可在氮气中将生坯体在一定温度加热足够的时间，以基本除去成孔剂。合适的温度例如可等于或高于500-600℃，加热12小时或更久。
然后，在空气中将生坯体烧制至约1400℃的最大温度，在此最大温度保持8小时，根据需要，整个周期为48小时或更久。对于由堇青石和/或富铝红柱石配合的组合物，会形成化学计量式约为Mg2Al4Si5O18相的陶瓷结构。
提供以下非限制性实施方式来更详细地说明本发明。
实施例
将选自表1的原料依表2所列比例混合起来，制备对比例(非发明例)和发明实施例。
对比例1依照美国专利第6,506,336号所述制备，不含成孔剂。如上所述使用聚乙烯蜡分散体形成颗粒成孔材料混合物以制备本发明实施例1-4。使用制成粉末聚乙烯蜡作为成孔剂制备本发明实施例5.
在合适的条件下将增塑的混合物挤压通过蜂窝体形成模，形成孔密度约为640-960孔/平方英寸(99-149孔/平方厘米)、壁厚约为2.8-4.2密耳(0.0028-0.0042英寸)的整体(monolith)。充分干燥生坯陶瓷蜂窝体，除去其中可能含有的水和其它液相，然后首先在可在市场上购得的真空热解器内，在12小时内从室温加热至500℃以除去成孔剂，然后第二次从室温烧制至1400℃，并保持8小时，总周期时间为48小时或更久，从而烧制形成最终产物；所述合适的条件即适于形成堇青石陶瓷体的烧制条件。
这些样品的性质列于表2。用水银孔隙率测定仪测定孔隙率(％)和孔径(微米)。用膨胀计测定沿轴向(平行于孔道长度)的热膨胀系数。使用四点法测量沿平行于过滤器方向切割的多孔棒样品的弹性模量。
可以发现制得的堇青石蜂窝体结构具有壁厚大于2.0密耳(0.0020英寸，0.0508毫米)的孔，总孔隙率为45-75％，中值孔径为2-10微米，热膨胀系数(CTE)(25-800℃)小于15×10-7/℃，弹性模量(MOR)蜂窝体强度为200-400psi。
现在参见图2，图中显示实施例14抛光基材截面的487X倍放大扫描电子显微照片。使用水银孔隙率测定仪测得，图2的发明结构具有55％的高孔隙率，其中值孔径为1.79微米。作为对比的图3是在市场上购得的孔隙率为33％、中值孔径为1.3微米的堇青石蜂窝体抛光基材截面的487X倍放大扫描电子显微照片。
应当理解尽管就本发明一些说明性的具体实施方式详细描述了本发明，但是本发明并不限于此，可在不背离本发明精神和所附权利要求书范围的前提下通过其它方式应用本发明。
表1陶瓷粉末材料-组成和性质
 
原料(平均粒度(毫米)) 密度(克/立方厘米) 组成(重量％)
滑石(1.6毫米) 2.75 39.95
勃姆石 2.65 11.05
氧化铝 3.98 5.31
煅烧粘土 2.74 25.66
生高岭土 2.58 16.55
二氧化硅 2.65 1.50
表2
实施例
 
实施例编号 C1 I1 I2 I3 I4 I5
批料组成 重量％ 重量％ 重量％ 重量％ 重量％ 重量％
陶瓷粉末材料 100 100 100 100 100 100
聚乙烯蜡 0 80.98 45.77 25.0 61.1 79.6
甲基纤维素粘合剂 3.85 12.71 8.95 6.64 10.25 15.61
Durasyn<sup>TM</sup>油 5.39 17.79 12.53 9.29 14.41 20.30
油酸 0.67 2.22 1.57 1.16 1.76 2.53
水 25.8 85.2 60.0 43.74 41.88 54.5
性质
％孔隙率 33.1 69.3 61.5 51.6 55.0 65.9
平均孔径(毫米) 1.29 3.54 2.79 2.19 1.79 3.36
多孔棒上的MOR强度(磅/平方英寸) - - - - 360 -
CTE，25-800℃(10<sup>-7</sup>℃<sup>-1</sup>) 4.1 10.1 9.5 5.5 8.0 5.2

Claims (11)

1.一种用于汽车催化转化器系统的高孔隙率陶瓷蜂窝体基材，该基材具有改进的点火性能，具有进口端、出口端和壁厚大于0.0508毫米的孔，该蜂窝体的总孔隙率为45-75％，中值孔径为2-10微米，25-800℃的热膨胀系数小于15×10-7/℃。
2.如权利要求1所述的蜂窝体基材，其特征在于，所述壁的厚度为0.0635毫米至0.1778毫米。
3.如权利要求2所述的蜂窝体基材，其特征在于，所述壁的厚度为0.0635毫米至0.0762毫米。
4.如权利要求1所述的蜂窝体基材，其特征在于，所述孔隙率为50-65％。
5.如权利要求1所述的蜂窝体基材，其特征在于；所述中值孔径为2-4微米。
6.如权利要求1所述的蜂窝体基材，其特征在于，25-800℃的热膨胀系数小于10×10-7/℃。
7.如权利要求1所述的蜂窝体基材，在多孔棒上测得，该蜂窝体的弹性模量强度为200-400psi。
8.一种制造权利要求1所述的高孔隙率陶瓷蜂窝体基材的方法，该方法包括：
a)混合包含以下组分的批料：
i.陶瓷粉末材料；
ii.增塑粘合剂体系；
iii.15-85重量％的成孔剂，该成孔剂的平均粒度为2-18微米；
b)混合所述组分的批料形成增塑的混合物；
c)将增塑的混合物通过模具挤压形成生坯蜂窝体；
d)在一定的温度下用充分时间加热该生坯蜂窝体，以除去成孔剂并形成权利要求1所述的高孔隙率陶瓷蜂窝体基材。
9.如权利要求8所述的方法，其特征在于，该批料包含30-70重量％的中值粒度为3-8微米的成孔剂。
10.如权利要求8所述的方法，其特征在于，所述陶瓷粉末材料包括选自以下的矿物粉末或精制粉末：堇青石、尖晶石、粘土、滑石、氧化铝、氢氧化铝、二氧化硅以及钙、镁、硼、锗、碱金属和过渡金属的氧化物。
11.如权利要求8所述的方法，其特征在于，所述陶瓷粉末材料包括钛的氧化物的矿物粉末或精制粉末。
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