CN101678347A - 蜂窝结构体以及废气净化装置 - Google Patents

蜂窝结构体以及废气净化装置 Download PDF

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CN101678347A
CN101678347A CN200880019742A CN200880019742A CN101678347A CN 101678347 A CN101678347 A CN 101678347A CN 200880019742 A CN200880019742 A CN 200880019742A CN 200880019742 A CN200880019742 A CN 200880019742A CN 101678347 A CN101678347 A CN 101678347A
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honeycomb structured
structured body
zeolite
cellular unit
roundness
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CN101678347B (zh
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大野一茂
国枝雅文
井户贵彦
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Ibiden Co Ltd
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Ibiden Co Ltd
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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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Abstract

本发明的蜂窝结构体具有包含无机颗粒和无机粘结剂的蜂窝单元，在所述蜂窝单元内，沿长度方向隔着间壁并列设置了多个贯穿孔，其中：与长度方向大致垂直的两个端面的真圆度是1.5mm以上、4.0mm以下；两个端面中，一个端面的真圆度与另一个端面的真圆度不同。

Description

蜂窝结构体以及废气净化装置
技术领域
本发明涉及一种蜂窝结构体以及废气净化装置。
背景技术
关于汽车废气的净化，已经开发了很多技术，但是，由于交通量也在增加，所以还很难说已经采取了完善的废气应对方法。另外，汽车废气的控制正在被进一步强化。其中，对于柴油废气中的NOX的控制正在变得非常严格。目前为止，一般通过控制发动机的燃烧系统来谋求减少NOx，但是，仅使用该方法并不能百分之百地减少NOx。所以，已经有了一种使用氨将NOx还原为氮和水的SCR(Selective Catalytic Reduction：选择性催化还原)系统。另外，在SCR系统中，作为吸附氨的材料，众所周知的有沸石。
另外，在专利文献1中记载了一种蜂窝结构体，其中，蜂窝单元包含陶瓷颗粒、无机纤维以及/或者须晶，与蜂窝单元的长度方向垂直的截面的面积是5cm2以上、50cm2以下，与长度方向垂直的截面的真圆度是1.0mm以上、2.5mm以下。此时，作为陶瓷，例如是从由氧化铝、二氧化硅、氧化锆、二氧化钛、二氧化铈、莫来石以及沸石组成的组中选择的一种以上的物质。
这里，需要说明的是，作为废气净化装置，一般是使用在蜂窝结构体的外周部设置了支撑密封材的状态下将该蜂窝结构体置入不锈钢等金属容器内并进行了罐化(canning，或曰“封装”)的废气净化装置。
专利文献1：国际公开第06/137160号小册子
发明内容
本发明想要解决的课题如下：
但是，在通过对包含沸石的材料进行挤压成型而得到的蜂窝结构体中，如果为了提高NOx的净化率而增大表面面积，则因为不能使其进行充分的烧结，所以强度容易降低。
这样，在制作废气净化装置时，将蜂窝结构体罐化至金属容器内时不能施加很大的压力。因此，在汽车等中使用了这样的废气净化装置时存在着这样的问题，即：排压、振动等导致蜂窝结构体在金属容器内发生偏移。
本发明是鉴于上述课题而提出的，其目的在于提供一种蜂窝结构体和废气净化装置，所述蜂窝结构体在被罐化至金属容器内时可以抑制其在金属容器内发生偏移，所述废气净化装置具有所述蜂窝结构体。
用于解决上述课题的技术手段如下：
本发明的蜂窝结构体具有包含无机颗粒和无机粘结剂的蜂窝单元，在所述蜂窝单元内，沿长度方向隔着间壁并列设置了多个贯穿孔，其中，与长度方向大致垂直的两个端面的真圆度是1.5mm以上、4.0mm以下，两个端面中，一个端面的真圆度与另一个端面的真圆度不同。
另外，所述无机颗粒最好是从由氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化铈、莫来石和它们的前躯体、以及沸石组成的组中选择的一种以上的颗粒。
另外，在所述蜂窝单元中，单位表观体积的所述沸石的含量最好是230g/L以上、270g/L以下。这里，需要说明的是，蜂窝单元的单位表观体积是指包含贯穿孔的体积。
另外，所述沸石最好是从由β型沸石、Y型沸石、镁碱沸石、ZSM-5型沸石、丝光沸石、八面沸石、A型沸石以及L型沸石组成的组中选择的一种以上的沸石。
另外，所述沸石的二氧化硅与氧化铝的摩尔比最好是30以上、50以下。
另外，所述沸石最好是用从由Fe、Cu、Ni、Co、Zn、Mn、Ti、Ag以及V组成的组中选择的一种以上的物质进行了离子交换的沸石。
另外，所述沸石包含二次粒子，该二次粒子的平均粒径最好是0.5μm以上、10μm以下。
另外，所述无机粘结剂最好是包含在从由氧化铝胶体溶液、二氧化硅胶体溶液、二氧化钛胶体溶液、水玻璃、海泡石以及绿坡缕石组成的组中选择的一种以上的物质中的固体成分。
另外，所述蜂窝单元最好还包含无机纤维，该无机纤维最好是从由氧化铝、二氧化硅、碳化硅、硅铝、玻璃、钛酸钾以及硼酸铝组成的组中选择的一种以上的纤维。
另外，所述蜂窝结构体的外周最好具有涂层。
另外，所述蜂窝结构体最好具有一个蜂窝单元。
另外，在所述蜂窝结构体中，多个所述蜂窝单元最好通过粘结层粘结在一起。
本发明的废气净化装置具有：所述蜂窝结构体；在蜂窝结构体的外周上设置的支撑密封材；用于容纳在外周上设置了支撑密封材的蜂窝结构体的金属容器。
本发明的效果如下：
根据本发明，可以提供一种蜂窝结构体和废气净化装置，所述蜂窝结构体在被罐化至金属容器内时可以抑制其在金属容器内发生偏移，所述废气净化装置具有所述蜂窝结构体。
附图说明
图1A是用于表示本发明的蜂窝结构体的一个例子的立体图。
图1B是图1A的蜂窝结构体的长度方向的截面图。
图2A是用于表示本发明的蜂窝结构体的其他例子的立体图。
图2B是用于表示图2A的蜂窝单元的立体图。
图3是用于表示本发明的废气净化装置的一个例子的截面图。
图4A是振动装置的正主视图。
图4B是振动装置的侧视图。
符号说明：
10、10’：蜂窝结构体；11：蜂窝单元；12：贯穿孔；13：粘结层；14：外周涂层；20：支撑密封材；30：金属容器；100：废气净化装置；A、B：端面。
具体实施方式
以下参考附图说明本发明的最佳实施方式。
图1A和图1B中示出了本发明的蜂窝结构体的一个例子。在圆柱形状的蜂窝结构体10中，包含沸石和无机粘结剂的一个蜂窝单元11的外周面上形成了外周涂层14，在该蜂窝单元11中，沿长度方向隔着间壁并列设置了多个贯穿孔12。此时，在蜂窝结构体10中，与长度方向大致垂直的端面A和端面B的真圆度是1.5～4.0mm，端面A的真圆度与端面B的真圆度不同。这样，当蜂窝结构体10被罐化至金属容器内时，可以抑制其在金属容器内发生的偏移。如果端面A以及/或者端面B的真圆度小于1.5mm，则难以抑制蜂窝结构体10在金属容器内发生的偏移；如果大于4.0mm，则在将蜂窝结构体罐化至金属容器内时，压力被集中地施加至真圆度大的部分，容易发生破损。
另外，端面A和端面B的真圆度的差(绝对值)最好是1.0～2.0mm。如果端面A和端面B的真圆度的差小于1.0mm，则蜂窝结构体10被罐化至金属容器内时，可能难以抑制其在金属容器内发生的偏移；如果大于4.0mm，则可能难以制作蜂窝结构体10。
一般来说，因为蜂窝结构体10的除端面A和端面B以外的部分的制作比较容易，所以，与长度方向垂直的截面最好是大致圆形。这样的蜂窝结构体10可以通过改变与长度方向垂直的截面为大致圆形的蜂窝结构体的端面A和端面B的真圆度来制作。另外，在蜂窝结构体10中，除端面A和端面B以外的部分也可以具有一处以上的、与长度方向垂直的截面的真圆度较大的部分。
这里，需要说明的是，真圆度是指圆形体偏移几何学上的圆的大小，当圆形体被两个几何学上的圆包夹时，用两个圆的半径差为最小时的半径差来表示。另外，真圆度可以使用激光测量仪、标尺测量仪、照射平行白色光的光学测量仪、电子游标卡尺等来进行自动测量。
在蜂窝单元11中，单位表观体积的沸石含量最好是230～270g/L。如果蜂窝单元11的单位表观体积的沸石含量小于230g/L，则为了得到足够大的NOx净化率，可能必须增大蜂窝单元11的表观体积；如果大于270g/L，则蜂窝单元11的强度可能不足。
作为沸石，对其并无特别限定，可以是β型沸石、ZSM-5型沸石、丝光沸石、八面沸石、A型沸石、L型沸石等，也可以同时使用这些沸石中的两种以上的沸石。
另外，沸石中的二氧化硅与氧化铝的摩尔比最好是30～50。
再有，为了提高氨的吸附率，可以对沸石进行离子交换。作为用于离子交换的阳离子的种类，对其并无特别的限定，可以是Fe、Cu、Ni、Co、Zn、Mn、Ti、Ag、V等，也可以同时使用这些物质中的两种以上的物质。离子交换量较好是1.0～10.0重量％，最好是1.0～5.0重量％。如果离子交换量小于1.0重量％，则由离子交换所引起的氨的吸附率的变化可能不明显；如果大于10.0重量％，则加热时结构可能变得不稳定。这里，需要说明的是，在对沸石进行离子交换时，只要将沸石浸入含有阳离子的水溶液中即可。
另外，沸石最好包含二次粒子，沸石的二次粒子的平均粒径最好是0.5～10μm。如果沸石的二次粒子的平均粒径小于0.5μm，则可能需要添加大量的无机粘结剂，这样可能难以进行挤压成型；如果大于10μm，则沸石的比表面积减小，NOx的净化率可能下降。
再有，为了提高强度，蜂窝单元11还可以包含除了沸石之外的无机颗粒。作为除了沸石之外的无机颗粒，对其并无特别的限定，可以是氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化铈、莫来石以及它们的前驱体等，也可以同时使用这些颗粒中的两种以上的颗粒。其中，特别地，优选氧化铝、氧化锆。
除了沸石之外的无机颗粒的平均粒径最好是0.5～10μm。如果该平均粒径小于0.5μm，则可能需要添加大量的无机粘结剂，这样就很难进行挤压成型；如果大于10μm，则提高蜂窝单元11的强度的效果可能不明显。这里，需要说明的是，除了沸石之外的无机颗粒也可以包含二次粒子。
另外，除了沸石之外的无机颗粒的二次粒子的平均粒径与沸石的二次粒子的平均粒径之比值较好是1以下，最好是0.1～1。如果该比值大于1，则提高蜂窝单元11的强度的效果可能不明显。
在蜂窝单元11中，除了沸石之外的无机颗粒的含量较好是3～30重量％，最好是5～20重量％。如果该含量小于3重量％，则提高蜂窝单元11的强度的效果可能不明显；如果超过30重量％，则蜂窝单元11中的沸石含量降低，NOx的净化率可能下降。
作为无机粘结剂，对其并无特别的限定，可以是包含在氧化铝胶体溶液、二氧化硅胶体溶液、二氧化钛胶体溶液、水玻璃、海泡石、绿坡缕石等中的固体成分，也可以同时使用这些固体成分中的两种以上的固体成分。
在蜂窝单元11中，无机粘结剂的含量较好是5～30重量％，最好是10～20重量％。如果无机粘结剂的含量小于5重量％，则蜂窝单元11的强度可能下降；如果大于30重量％，则可能难以成型。
为了提高强度，蜂窝单元11最好还包含无机纤维。
作为无机纤维，只要能提高蜂窝单元11的强度，对其并无特别的限定，可以是氧化铝、二氧化硅、碳化硅、硅铝、玻璃、钛酸钾、硼酸铝等，也可以同时使用这些物质中的两种以上的物质。
无机纤维的长径比较好是2～1000，更好是5～800，最好是10～500。如果长径比小于2，则提高蜂窝单元11的强度的效果可能变小。另外，如果长径比大于1000，则通过挤压成型等来成型时可能发生模具网眼的堵塞等，并且，成型时无机纤维折断，提高蜂窝单元11的强度的效果可能变小。
在蜂窝单元11中，无机纤维的含量较好是3～50重量％，更好是3～30重量％，最好是5～20重量％。如果无机纤维的含量小于3重量％，则提高蜂窝单元11的强度的效果可能变小；如果大于50重量％，则蜂窝单元11中的沸石含量降低，NOx的净化率可能下降。
在蜂窝单元11中，与长度方向垂直的截面的开口率最好是50～65％。如果开口率小于50％，则沸石可能不能被有效地用于NOx的净化；如果大于65％，则蜂窝结构体10的强度可能不足。
在蜂窝单元11中，与长度方向垂直的截面的贯穿孔12的密度较好是15.5～124个/cm2，最好是31～93个/cm2。如果贯穿孔12的密度小于15.5个/cm2，则废气很难与沸石接触，蜂窝单元11的NOx净化率可能下降；如果大于124个/cm2，则蜂窝单元11的压力损失可能增大。
用于分隔蜂窝单元11的贯穿孔12的间壁的厚度较好是0.10～0.50mm，最好是0.15～0.35mm。如果间壁的厚度小于0.10mm，则蜂窝单元11的强度可能下降；如果大于0.50mm，则废气很难浸透至间壁的内部，沸石可能不能被有效地用于NOx的净化。
外周涂层14的厚度最好是0.1～2mm。如果外周涂层14的厚度小于0.1mm，则提高蜂窝结构体10的强度的效果可能不明显；如果大于2mm，则蜂窝结构体10的单位体积的沸石含量降低，蜂窝结构体10的NOx净化率可能下降。
再有，贯穿孔12的形状是四棱柱形状，但是，在本发明中，作为贯穿孔的形状，对其并无特定的限定，可以是三棱柱形状、六棱柱形状等。
以下对蜂窝结构体10的制造方法的一个例子进行说明。首先，使用包含沸石以及无机粘结剂的、根据需要还可以包含除了沸石之外的无机颗粒、无机纤维等的原料浆进行挤压成型等的成型，制成生的蜂窝成型体，其中，沿长度方向隔着间壁并列设置了多个贯穿孔。这样，即使降低烧成温度，也能得到具有充分强度的圆柱形状蜂窝单元11。
这里，需要说明的是，在原料浆中添加作为无机粘结剂的氧化铝胶体溶液、二氧化硅胶体溶液、二氧化钛胶体溶液、水玻璃、海泡石、绿坡缕石等，也可以同时使用这些物质中两种以上的物质。
另外，在原料浆中，根据需要可以适当地添加有机粘结剂、分散介质、成型助剂等。
作为有机粘结剂，对其并无特别的限定，可以是甲基纤维素、羧甲基纤维素、羟乙基纤维素、聚乙二醇、酚醛树脂、环氧树脂等，也可以同时使用这些物质中两种以上的物质。这里，需要说明的是，有机粘结剂的添加量相对于沸石、除了沸石之外的无机颗粒、无机纤维以及无机粘结剂的总重量最好是1～10％。
作为分散介质，对其并无特别的限定，可以是水、苯等有机溶媒、甲醇等醇等，也可以同时使用这些物质中的两种以上的物质。
作为成型助剂，对其并无特别的限定，可以是乙二醇、糊精、脂肪酸、脂肪酸皂、多元醇等，也可以同时使用这些物质中的两种以上的物质。
调制原料浆时，最好进行混合、混炼，可以使用搅拌机、磨碎机等来进行混合，也可以使用捏合机等来进行混炼。
然后，使用微波干燥机、热风干燥机、高频干燥机、减压干燥机、真空干燥机、冷冻干燥机等干燥机，对得到的蜂窝成型体进行干燥。
另外，对得到的蜂窝成型体进行脱脂。对脱脂条件并无特别的限定，可以根据成型体中含有的有机物的种类、含量进行适当的选择，但是，优选是400℃、2个小时。
再有，通过对得到的蜂窝成型体进行烧成，得到圆柱形状的蜂窝单元11。烧成温度较好是600～1200℃，最好是600～1000℃。如果烧成温度小于600℃，则不能进行烧结，蜂窝结构体10的强度可能下降；如果大于1200℃，则烧结过度进行，沸石的反应点可能减少。
这里，需要说明的是，通过对生蜂窝成型体的外周壁进行加压，对干燥、脱脂或烧成后的蜂窝单元11的外周壁进行研磨，可以改变蜂窝结构体10的端面A以及端面B的真圆度。
接下来，在圆柱形状的蜂窝单元11的外周面上涂敷外周涂层用浆体。作为外周涂层用浆体，对其并无特别的限制，可以是无机粘结剂和无机颗粒的混合物、无机粘结剂和无机纤维的混合物、无机粘结剂、无机颗粒和无机纤维的混合物等。
另外，外周涂层用浆体也可以包含有机粘结剂。作为有机粘结剂，对其并无特别的限制，可以是聚乙烯醇、甲基纤维素、乙基纤维素、羧甲基纤维素等，也可以同时使用这些物质中的两种以上的物质。
接下来，通过对涂敷了外周涂层用浆体的蜂窝单元11进行干燥、固化，得到圆柱形状的蜂窝结构体10。此时，如果外周涂层用浆体中含有有机粘结剂，则最好对其进行脱脂。脱脂条件可以根据有机物的种类、含量进行适当的选择，但是，优选是700℃、20分钟。
这里，需要说明的是，通过改变外周涂层14的厚度使其非恒定，可以改变蜂窝结构体10的端面A和端面B的真圆度。作为改变外周涂层14的厚度的方法，可以是改变外周涂层14的涂敷时的厚度的方法、对涂敷后的外周涂层14进行加压的方法、对干燥固化后的外周涂层14进行研磨的方法等。
图2A和图2B中示出了本发明的蜂窝结构体的其他的例子。这里，需要说明的是，蜂窝结构体10’除了是通过粘结层13粘结了多个蜂窝单元11之外，其他与蜂窝结构体10相同，其中，在所述蜂窝单元11中，沿长度方向隔着间壁并排设置了多个贯穿孔12。
在蜂窝单元11中，与长度方向垂直的截面的面积最好是5～50cm2。如果截面的面积小于5cm2，则蜂窝结构体10的比表面积减小的同时，压力损失也可能增大；如果截面的面积大于50cm2，则应对蜂窝单元11中产生的热应力的强度可能不足。
使蜂窝单元11粘结在一起的粘结层13的厚度最好是0.5～2mm。如果粘结层13的厚度小于0.5mm，则粘结强度可能不足。另外，如果粘结层13的厚度大于2mm，则蜂窝结构体10的比表面积减小的同时，压力损失也可能增大。
另外，蜂窝单元11是四棱柱形状，但是，在本发明中，作为蜂窝单元的形状，对其并无特别的限制，最好是使蜂窝单元彼此容易粘结在一起的形状，例如，六棱柱形状等。
以下对蜂窝结构体10’的制造方法的一个例子进行说明。首先，与蜂窝结构体10同样地制成四棱柱形状的蜂窝单元11。然后，通过在蜂窝单元11的外周面上涂敷粘结层用浆体，使蜂窝单元11按顺序地粘结在一起，并使其干燥、固化，制成蜂窝单元11的集合体。此时，制成蜂窝单元11的集合体之后，将其切削加工成圆柱形状，并可以对其进行研磨。另外，也可以将截面为扇形、正方形的蜂窝单元11粘结在一起，制成圆柱形状的蜂窝单元11的集合体。
作为粘结层用浆体，对其并无特别的限制，可以是无机粘结剂和无机颗粒的混合物、无机粘结剂和无机纤维的混合物、无机粘结剂、无机颗粒和无机纤维的混合物等。
另外，粘结层用浆体还可以包含有机粘结剂。作为有机粘结剂，对其并无特别的限定，可以是聚乙烯醇、甲基纤维素、乙基纤维素、羧甲基纤维素等，也可以同时使用这些物质中的两种以上的物质。
这里，需要说明的是，通过对圆柱形状的蜂窝单元11的集合体的外周壁进行研磨，可以改变蜂窝结构体10的端面A和端面B的真圆度。
之后，在圆柱形状的蜂窝单元11的集合体的外周面涂敷外周涂层用浆体。对外周涂层用浆体并无特别的限制，可以包含与粘结层用浆体相同的材料，也可以包含与之不同的材料。另外，外周涂层用浆体也可以与粘结层用浆体具有相同的组成成分。
接下来，通过对涂敷了外周涂层用浆体的蜂窝单元11的集合体进行干燥、固化，得到圆柱形状的蜂窝结构体10’。此时，如果粘结层用浆体和/或外周涂层用浆体中包含有机粘结剂，则最好对其进行脱脂。脱脂条件可以根据有机物的种类、含量进行适当的选择，但是，优选是700℃、20分钟。
这里，需要说明的是，也可以通过使用包含没有进行离子交换的沸石的原料浆制成蜂窝结构体之后，将蜂窝结构体浸渍在含有阳离子的水溶液中对沸石进行离子交换来制得蜂窝结构体10和10’。
在本发明的蜂窝结构体中，可以形成外周涂层，也可以不形成外周涂层，但是，从容易改变两端面的真圆度的方面来考虑，最好是形成外周涂层。
图3中示出了本发明的废气净化装置的一个例子。在废气净化装置100中，蜂窝结构体10(10’)在其外周部设置了氧化铝垫等支撑密封材20的状态下被收纳在金属容器30内。这样，废气净化装置100就可以抑制蜂窝结构体10(10’)在金属容器内发生的偏移。
再有，在废气净化装置100中，在相对于废气流动方向的、蜂窝结构体10(10’)的上游侧设置了喷嘴等的喷射单元(图中未表示)，用于喷射氨或其前躯体。据此，氨被添加至废气中，所以，在蜂窝结构体10(10’)中含有的沸石上，废气中含有的NOx被还原。此时，如果考虑储藏稳定性，则最好使用尿素水作为氨的前躯体。这里，需要说明的是，尿素水通过在废气中被加热，发生水解，生成氨。
以上对包含作为无机颗粒的沸石的蜂窝结构体、以及、包含沸石、除了沸石之外的无机颗粒的蜂窝结构体进行了说明，但是，可以认为，对于仅包含作为无机颗粒的、除了沸石之外的无机颗粒的蜂窝结构体来说，也可以得到相同的效果。
实施例
[实施例1]
首先，通过将用Cu进行了3重量％离子交换的、平均粒径是2μm、二氧化硅/氧化铝之比值是40、比表面积是110m2/g的β型沸石2600g，作为含有无机粘结剂的成分的、以固体成分计是20重量％的氧化铝胶体溶液2600g，作为无机纤维的、平均纤维直径是6μm、平均纤维长度是100μm的氧化铝纤维780g，作为有机粘结剂的甲基纤维素410g进行混合、混炼，得到原料浆。这里，需要说明的是，Cu离子交换是通过将沸石颗粒浸渍在硝酸铜水溶液中来进行的。另外，沸石的离子交换量是使用ICPS-8100(岛津制作所制)通过IPC发光分析来求得的。之后，使用挤压成型机，通过将原料浆挤压成型，得到圆柱形状的生蜂窝成型体。接下来，通过使用微波干燥机和热风干燥机使蜂窝成型体干燥后，在400℃温度下对其进行5个小时的脱脂。然后，在700℃温度下进行5个小时的烧成，得到直径是143.8mm、长度是150mm的圆柱形状的蜂窝单元11。在得到的蜂窝单元11中，与长度方向垂直的截面的开口率是65％，贯穿孔的密度是62个/cm2，间壁的厚度是0.25mm，单位表观体积的沸石含量是250g/L。
这里，与长度方向垂直的截面的开口率是使用光学显微镜通过计算蜂窝结构体的边长是10cm的四边形区域内的贯穿孔的面积来求得的。另外，贯穿孔的密度是使用光学显微镜通过测量蜂窝结构体的边长是10cm的四边形区域内的贯穿孔的数量来求得的。再有，间壁的厚度是使用光学显微镜通过测量蜂窝结构体的间壁的厚度(5处)而得到的平均值。
其次，通过将平均粒径是2μm的γ-氧化铝29重量份，平均纤维直径是6μm、平均纤维长度是100μm的氧化铝纤维7重量份，固体成分计是20重量％的氧化铝胶体溶液34重量份，羧甲基纤维素5重量份，水25重量份进行混合，得到外周涂层用浆体。
再有，在蜂窝单元11的外周面(除了两个端面)上均匀地涂敷外周涂层用浆体，并在120℃温度下对其进行干燥，在700℃温度下对其进行20分钟的脱脂，形成厚度是2mm的外周涂层14，制成圆柱形状的蜂窝结构体10。
接下来，使用砂纸对蜂窝结构体10的外周涂层14进行研磨处理，将端面A和端面B的真圆度分别处理为1.5mm和2.5mm(参考表1)。
[实施例2～6、比较例1～3]
对蜂窝结构体10的外周涂层14的研磨处理进行调整，将端面A和端面B的真圆度改变为表1所示的数据，除此之外，其他与实施例1相同，制成蜂窝结构体10。
[表1]
Figure G2008800197421D00141
Figure G2008800197421D00151
这里，需要说明的是，端面A和端面B的真圆度是使用真圆度测量仪Round Test R A 736(Mitutoyo公司制)来测定的。另外，端面A和端面B的真圆度的差被列在表1中。
[偏移实验]
将作为支撑密封材20的、厚度是6mm的氧化铝垫(46.5cm×15cm)(三菱化学公司制)卷绕在蜂窝结构体10的外周面，在将其置入金属容器210中的状态下，使用英斯特朗(Instron)试验机进行挤压、罐化。之后，将金属容器210固定在振动装置200(参考图4A和图4B)上，以使被罐化了的蜂窝结构体10的长度方向成为水平方向；然后，将频率设为160Hz、加速度设为30G、振幅设为0.58mm、保持时间设为120小时，在室温下沿水平方向使金属容器210振动，测定蜂窝结构体10偏移了标准位置的偏移量。
在振动装置200中，将置入了蜂窝结构体10的金属容器210放置在台座220上，通过用螺钉240拧紧大致为U字形状的固定部件230来固定金属容器210。这样，金属壳体210就可以在与台座220、固定部件230成为一体的状态下进行振动。
表1中列出了测定结果。这里，需要说明的是，偏移量小于10mm时用○表示；10mm以上时用×表示。由表1可知，实施例1～6的蜂窝结构体10的偏移量小于比较例1～3的蜂窝结构体10的偏移量。
由以上可知，通过将蜂窝结构体10的端面A和端面B的真圆度设为1.5～4.0mm，并使端面A的真圆度与端面B的真圆度不同，可以抑制蜂窝结构体10在金属容器内发生偏移。

Claims (14)

1、一种蜂窝结构体，其具有包含无机颗粒和无机粘结剂的蜂窝单元，在该蜂窝单元中，沿长度方向隔着间壁并列设置了多个贯穿孔，所述蜂窝结构体的特征在于，
与所述长度方向大致垂直的两个端面的真圆度是1.5mm以上、4.0mm以下，
所述两个端面中，一个端面的真圆度与另一个端面的真圆度不同。
2、根据权利要求1所述的蜂窝结构体，其特征在于，
所述无机颗粒是从由氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化铈、莫来石和它们的前躯体、以及沸石组成的组中选择的一种以上的颗粒。
3、根据权利要求2所述的蜂窝结构体，其特征在于，
在所述蜂窝单元中，单位表观体积的所述沸石的含量是230g/L以上、270g/L以下。
4、根据权利要求2或3所述的蜂窝结构体，其特征在于，
所述沸石是从由β型沸石、Y型沸石、镁碱沸石、ZSM-5型沸石、丝光沸石、八面沸石、A型沸石以及L型沸石组成的组中选择的一种以上的沸石。
5、根据权利要求2或3所述的蜂窝结构体，其特征在于，
所述沸石的二氧化硅与氧化铝的摩尔比是30以上、50以下。
6、根据权利要求2或3所述的蜂窝结构体，其特征在于，
所述沸石是用从由Fe、Cu、Ni、Co、Zn、Mn、Ti、Ag以及V组成的组中选择的一种以上的物质进行了离子交换的沸石。
7、根据权利要求2或3所述的蜂窝结构体，其特征在于，
所述沸石包含二次粒子，该二次粒子的平均粒径是0.5μm以上、10μm以下。
8、根据权利要求1至3中任一项所述的蜂窝结构体，其特征在于，
所述无机粘结剂是包含在从由氧化铝胶体溶液、二氧化硅胶体溶液、二氧化钛胶体溶液、水玻璃、海泡石以及绿坡缕石组成的组中选择的一种以上的物质中的固体成分。
9、根据权利要求1至3中任一项所述的蜂窝结构体，其特征在于，
所述蜂窝单元还包含无机纤维。
10、根据权利要求9所述的蜂窝结构体，其特征在于，
所述无机纤维是从由氧化铝、二氧化硅、碳化硅、硅铝、玻璃、钛酸钾以及硼酸铝组成的组中选择的一种以上的纤维。
11、根据权利要求1至3中任一项所述的蜂窝结构体，其特征在于，
外周具有涂层。
12、根据权利要求1至3中任一项所述的蜂窝结构体，其特征在于，
具有一个蜂窝单元。
13、根据权利要求1至3中任一项所述的蜂窝结构体，其特征在于，
多个所述蜂窝单元通过粘结层粘结在一起。
14、一种废气净化装置，其特征在于，具有：
蜂窝结构体，其是权利要求1至3中任一项所述的蜂窝结构体；
支撑密封材，其设置在所述蜂窝结构体的外周上；
金属容器，其用于容纳在外周上设置了所述支撑密封材的所述蜂窝结构体。
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