CN102666430A - 蜂窝结构体以及尾气净化装置 - Google Patents

蜂窝结构体以及尾气净化装置 Download PDF

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CN102666430A
CN102666430A CN2009801625074A CN200980162507A CN102666430A CN 102666430 A CN102666430 A CN 102666430A CN 2009801625074 A CN2009801625074 A CN 2009801625074A CN 200980162507 A CN200980162507 A CN 200980162507A CN 102666430 A CN102666430 A CN 102666430A
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structured body
honeycomb structured
cellular unit
zeolite
sapo
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CN102666430B (zh
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松川阳介
后藤真之助
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Ibiden Co Ltd
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Ibiden Co Ltd
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Abstract

本发明的蜂窝结构体，具有蜂窝单元，在该蜂窝单元中，包含磷酸盐系列沸石以及无机粘结剂，并且多个贯穿孔隔着间壁沿长度方向并排设置；在所述蜂窝单元中，宏气孔的平均气孔孔径为0.1μm以上且0.3μm以下，气孔率为30％以上且40％以下。

Description

蜂窝结构体以及尾气净化装置
技术领域
本发明涉及一种蜂窝结构体以及具有蜂窝结构体的尾气净化装置。
背景技术
在现有技术中，作为净化汽车尾气的系统之一，熟知的有一种使用氨将NOx还原为氮和水的SCR(Selective Catalytic Reduction)系统。
另外，在SCR系统中，作为吸收氨的材料，熟知的有沸石。
在专利文献1中公开了一种蜂窝结构体，其中，蜂窝单元包含无机颗粒、无机纤维以及/或者晶须，无机颗粒是从由氧化铝、二氧化硅、锆、二氧化钛、二氧化铈、莫来石、以及沸石所组成的群中所选择的一种以上的无机颗粒。
专利文献1：国际公开第06/137149号小册子
发明内容
本发明想要解决的课题如下：
但是，目前存在着这样一种需求，即：NOx的净化性能要比专利文献1的蜂窝结构体中的无机颗粒为沸石时还高。
本发明是鉴于上述现有技术所具有的问题而提出的，其目的在于提供一种具有优异NOx净化性能的蜂窝结构体以及尾气净化装置。
用于解决上述课题的手段如下：
一种蜂窝结构体，具有蜂窝单元，在该蜂窝单元中，包含磷酸盐系列沸石以及无机粘结剂，并且多个贯穿孔隔着间壁沿长度方向并排设置，该蜂窝结构体的特征在于，在所述蜂窝单元中，宏气孔的平均气孔孔径为0.1μm以上且0.3μm以下，气孔率为30％以上且40％以下。
所述磷酸盐系列沸石优选为从SAPO、MeAPO、以及MeAPSO所组成的群中选择的一种以上的沸石。
所述SAPO优选为从SAPO-5、SAPO-11、以及SAPO-34所组成的群中选择的一种以上的SAPO。
所述磷酸盐系列沸石优选为包含由Cu以及/或者Fe进行了离子交换的沸石。
所述无机粘结剂优选为从氧化铝溶胶、二氧化硅溶胶、二氧化钛溶胶、水玻璃、海泡石、硅镁土、以及伯姆石所组成的群中选择的一种以上的物质中含有的固形成分。
所述蜂窝单元优选为还包含无机纤维以及/或者鳞片状物质。
所述无机纤维优选为从氧化铝、二氧化硅、碳化硅、二氧化硅氧化铝、玻璃、钛酸钾、以及硼酸铝所组成的群中选择的一种以上的无机纤维，所述鳞片状物质优选为从玻璃、白云母、氧化铝、二氧化硅、以及氧化锌所组成的群中选择的一种以上的物质。
本发明的蜂窝结构体优选为具有多个所述蜂窝单元。
本发明的尾气净化装置具有本发明的蜂窝结构体。
本发明的效果如下：
根据本发明，可以提供一种具有优异NOx净化性能的蜂窝结构体以及尾气净化装置。
附图说明
图1是表示本发明的蜂窝结构体的一个例子的立体图。
图2是表示本发明的尾气净化装置的一个例子的截面图。
图3是表示图1的蜂窝结构体的变形例的立体图。
图4是表示用于构成图3的蜂窝结构体的蜂窝单元的立体图。
具体实施方式
下面参考附图对本发明的实施形态进行说明。
图1示出了本发明的蜂窝结构体的一个例子。在蜂窝结构体10中，单一蜂窝单元11的外周面上形成有外周涂层12；该蜂窝单元11包含作为无机颗粒的磷酸盐系列沸石以及无机粘结剂，其中，多个贯穿孔11a隔着间壁11b沿长度方向并排设置。
蜂窝单元11的宏气孔(即：大气孔)的平均气孔孔径为0.1～0.3μm。如果宏气孔的平均气孔孔径不足0.1μm，则因为尾气难以渗透至间壁11b的内部，所以磷酸盐系列沸石就不能有效地用于NOx的净化。而如果宏气孔的平均气孔孔径超过0.3μm，则因为蜂窝单元11中的气孔数量较少，所以尾气难以渗透至间壁11b的内部，导致磷酸盐系列沸石不能有效地用于NOx的净化。
此时，在蜂窝单元11的气孔孔径分布中存在着两个峰值，一个是源于磷酸盐系列沸石的微气孔的峰值，另一个是间壁11b内部的宏气孔的峰值。
蜂窝单元11的气孔率为30～40％。如果蜂窝单元11的气孔率不足30％，则因为尾气难以渗透至间壁11b的内部，所以磷酸盐系列沸石就不能有效地用于NOx的净化。而如果蜂窝单元11的气孔率超过40％，则因为蜂窝单元11中的磷酸盐系列沸石的含量变少，所以NOx的净化率下降。
这里需要说明的是，蜂窝单元11的平均气孔孔径和气孔率可使用水银压入法来测定。
作为磷酸盐系列沸石，可列举出SAPO-5、SAPO-11、SAPO-34等的SAPO；MeAPO；MeAPSO等。
如果考虑到NOx的净化能力，则磷酸盐系列沸石优选为由Cu以及/或者Fe进行了离子交换的磷酸盐系列沸石。这里需要说明的是，磷酸盐沸石还可以包含没有进行离子交换的磷酸盐系列沸石、以及由上述金属之外的金属进行了离子交换的磷酸盐系列沸石。
由Cu以及/或者Fe进行了离子交换的磷酸盐系列沸石的离子交换量优选为1.0～5.0质量％。如果磷酸盐系列沸石的离子交换量不足1.0质量％，则NOx的净化性能有可能不足。而如果磷酸盐系列沸石的离子交换量超过5.0质量％，则应该被离子交换的金属可能作为氧化物而存在，有可能不能被离子交换。
磷酸盐系列沸石的一次颗粒或二次颗粒的平均粒径优选为0.5～10μm，最好为1～5μm。如果磷酸盐系列沸石的一次颗粒或二次颗粒的平均粒径不足0.5μm，则尾气难以渗透至间壁11b的内部，磷酸盐系列沸石有可能不能有效地用于NOx的净化。而如果磷酸盐系列沸石的一次颗粒或二次颗粒的平均粒径超过10μm，则因为蜂窝单元11中的气孔数量变少，所以尾气难以渗透至间壁11b的内部，导致磷酸盐系列沸石有可能不能有效地用于NOx的净化。
蜂窝单元11还可以包含β型沸石、ZSM-5型沸石等除磷酸盐系列沸石以外的沸石。
蜂窝单元11的单位表观体积的沸石含量优选为230～360g/L。如果单位表观体积的沸石含量不足230g/L，则为了提高NOx的净化率，有可能一定要增大蜂窝单元11的表观体积。而如果单位表观体积的沸石含量超过360g/L，则蜂窝单元11的强度有可能不足、或者蜂窝单元11的开口率有可能变小。
作为包含在蜂窝单元11内的无机粘结剂，对其并无特别限定，可列举出氧化铝溶胶、二氧化硅溶胶、二氧化钛溶胶、水玻璃、海泡石、硅镁土、伯姆石等所含有的固形成分，也可以同时使用其中的两种以上的无机粘结剂。
蜂窝单元11的无机粘结剂的含量优选为5～30质量％，最好为10～20质量％。如果无机粘结剂的含量不足5质量％，则蜂窝单元11的强度有可能下降。而如果无机粘结剂的含量超过30质量％，则有可能难以进行蜂窝单元11的挤压成型。
为了提高强度，蜂窝单元11优选为还包含无机纤维以及/或者鳞片状物质。
作为包含在蜂窝单元11内的无机纤维，只要其可以提高蜂窝单元11的强度，对其并无特别限定，可列举出氧化铝、二氧化硅、碳化硅、二氧化硅氧化铝、玻璃、钛酸钾、硼酸铝等，也可以同时使用其中的两种以上的无机纤维。
无机纤维的纵横比优选为2～1000，较好为5～800，最好为10～500。如果无机纤维的纵横比不足2，则提高蜂窝单元11强度的效果有可能变小。而如果无机纤维的纵横比超过1000，则对蜂窝单元11进行挤压成型时，在模具内有可能发生网眼堵塞等情况，还有可能由于无机纤维发生折断，导致提高蜂窝单元11强度的效果变小。
作为包含在蜂窝单元11内的鳞片状物质，只要其可以提高蜂窝单元11的强度，对其并无特别限定，可列举出玻璃、白云母、氧化铝、二氧化硅、氧化锌等，也可以同时使用其中的两种以上的鳞片状物质。
蜂窝单元11的无机纤维以及鳞片状物质的含量优选为3～50质量％，较好为3～30质量％，最好为5～20质量％。如果无机纤维以及鳞片状物质的含量不足3质量％，则提高蜂窝单元11强度的效果有可能变小。而如果无机纤维以及鳞片状物质的含量超过50质量％，则蜂窝单元11中的磷酸盐系列沸石的含量降低，导致NOx的净化率有可能下降。
蜂窝单元11的与长度方向垂直的截面的开口率优选为50～75％。如果与长度方向垂直的截面的开口率不足50％，则磷酸盐系列沸石有可能不能有效地用于NOx的净化。而如果与长度方向垂直的截面的开口率超过75％，则蜂窝单元11的强度有可能不足。
蜂窝单元11的与长度方向垂直的截面的贯穿孔11a的密度优选为31～124个/cm2。如果与长度方向垂直的截面的贯穿孔11a的密度不足31个/cm2，则废气与磷酸盐系列沸石难以发生接触，NOx的净化率有可能下降。而如果与长度方向垂直的截面的贯穿孔11a的密度超过124个/cm2，则蜂窝结构体10的压力损失可能增大。
蜂窝单元11的间壁11b的厚度优选为0.10～0.50mm，最好为0.15～0.35mm。如果间壁11b的厚度不足0.10mm，则蜂窝单元11的强度有可能降低。而如果间壁11b的厚度超过0.50mm，则废气难以渗透至间壁11b的内部，导致磷酸盐系列沸石有可能不能有效地用于NOx的净化。
外周涂层12的厚度优选为0.1～2mm。如果外周涂层12的厚度不足0.1mm，则提高蜂窝结构体10的强度的效果有可能不足。而如果外周涂层12的厚度超过2mm，则蜂窝结构体10的单位体积的磷酸盐系列沸石的含量降低，导致NOx的净化率有可能下降。
蜂窝结构体10为圆柱状，但并不限定于此，也可为棱柱状、椭圆柱状等。另外，贯穿孔11a的形状为四棱柱状，但并不限定于此，也可为三棱柱状、六棱柱状等。
下面，对蜂窝结构体10的制造方法的一个例子进行说明。首先，使用原料膏进行挤压成型，以制成多个贯穿孔隔着间壁沿长度方向并排设置的圆柱状蜂窝成型体毛坯，其中，该原料膏包含磷酸盐系列沸石以及无机粘结剂，另外，根据需要，还可包含无机纤维以及/或者鳞片状物质、β型沸石、ZSM-5型沸石等磷酸盐系列沸石以外的沸石。据此，即使将烧成温度设为较低，也可以得到具有足够强度的圆柱状蜂窝单元11。
这里需要说明的是，作为原料膏中所包含的无机粘结剂，可添加氧化铝溶胶、二氧化硅溶胶、二氧化钛溶胶、水玻璃、海泡石、硅镁土、伯姆石等，也可以同时使用其中的两种以上的无机粘结剂。
另外，根据需要，在原料膏中还可以适当地添加有机粘结剂、分散介质、成型辅助剂等。
作为有机粘结剂，对其并无特别限定，可列举出甲基纤维素、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，也可以同时使用其中的两种以上的有机粘结剂。这里需要说明的是，有机粘结剂的添加量优选为磷酸盐系列沸石、无机粘结剂、无机纤维、鳞片状物质、以及磷酸盐系列沸石以外的沸石的总质量的1～10％。
作为分散介质，对其并无特别限定，可列举出水、苯等的有机溶液、甲醇等醇等，也可以同时使用其中的两种以上的分散介质。
作为成型辅助剂，对其并无特别限制，可列举出乙二醇、糊精、脂肪酸、脂肪酸肥皂、多元醇等，也可以同时使用其中的两种以上的成型辅助剂。
调制原料膏时，优选为进行混合混炼，可以使用搅拌器、磨碎机等进行混合，也可以使用捏合机等进行混炼。
然后，使用微波干燥机、热风干燥机、电感(高频)干燥机、减压干燥机、真空干燥机、冻结干燥机等干燥机对所得到的蜂窝成型体进行干燥。
接下来，对所得到的蜂窝成型体进行脱脂。对脱脂条件并无特别限定，其可以根据成型体内所包含的有机物的种类和含量进行适当的选择，优选为在400℃下脱脂2个小时。
之后，通过对所得到的蜂窝成型体进行烧成，得到圆柱状蜂窝单元11。烧成温度优选为600～1200℃，最好为600～1000℃。如果烧成温度不足600℃，则烧结不进行，蜂窝单元11的强度有可能变低。而如果烧成温度超过1200℃，则烧结过度进行，磷酸盐系列沸石的反应部位有可能减少。
接下来，在圆柱状蜂窝单元11的外周面上涂敷外周涂层用膏。
作为外周涂层用膏，对其并无特别限制，可列举出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，外周涂层用膏还可以包含有机粘结剂。作为有机粘结剂，对其并无限定，可列举出聚乙烯醇、甲基纤维素、乙基纤维素、羧甲基纤维素等，也可以同时使用其中的两种以上的有机粘结剂。
然后，通过对涂敷了外周涂层用膏的蜂窝单元11进行干燥固化，得到圆柱状蜂窝结构体10。此时，如果外周涂层用膏内包含了有机粘结剂，则优选为进行脱脂。脱脂条件可以根据有机物的种类和含量进行适当的选择，优选为在700℃下脱脂20分钟。
这里需要说明的是，通过将蜂窝单元11浸渍在含有Cu离子或Fe离子的水溶液中，可以对磷酸盐系列沸石进行离子交换。另外，也可以使用包含由Cu以及/或者Fe离子进行了离子交换的磷酸盐系列沸石的原料膏。
图2示出了本发明的尾气净化装置的一个例子。尾气净化装置100是在于蜂窝结构体10的外周部配置了支撑密封材20的状态下，将其封装(canning)至金属管30内所得到的。另外，在尾气净化装置100中还设置有喷射氨或其前躯体的喷射喷嘴等喷射单元(未图示)，其位于相对于尾气流动方向的蜂窝结构体10的上游侧。据此，氨可被添加至尾气中，这样，在蜂窝单元11所包含的磷酸盐系列沸石上，尾气中所包含的NOx被还原。此时，如果考虑到氨或其前躯体的储藏稳定性，则作为氨的前躯体，优选为使用尿素水。这里需要说明的是，尿素水通过在尾气中被加热，发生水解，产生氨。
图3示出了蜂窝结构体10的变形例。这里需要说明的是，在蜂窝结构体10’中，多个蜂窝单元11通过粘结层13被粘结在一起，其中，在每个蜂窝单元11中，多个贯穿孔11a隔着间壁11b沿长度方向并排设置(参照图4)；除此之外，蜂窝结构体10’与蜂窝结构体10相同。
蜂窝单元11的与长度方向垂直的截面的截面面积优选为5～50cm2。如果与长度方向垂直的截面的截面面积不足5cm2，则蜂窝结构体10’的压力损失有可能增大。而如果与长度方向垂直的截面的截面面积超过50cm2，则相对于蜂窝单元11内所产生的热应力的强度有可能不足。
粘结层13的厚度优选为0.5～2mm。如果粘结层13的厚度不足0.5mm，则粘结强度有可能不足。而如果粘结层13的厚度超过2mm，则蜂窝结构体10’的压力损失有可能增大。
另外，位于蜂窝结构体10’外周部的除了蜂窝单元11之外的蜂窝单元11的形状为四棱柱状，但对其并无特别限定，例如也可为六棱柱等。
下面，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同样地制成四棱柱状蜂窝单元11。接下来，在蜂窝单元11的外周面上涂敷粘结层用膏，然后按顺序对蜂窝单元11进行粘结，并进行干燥固化，以制成蜂窝单元11的集合体。
此时，在制成蜂窝单元11的集合体后，也可以将其切削成圆柱状，并进行研磨。另外，也可以使截面被形成为扇形或正方形的蜂窝单元11进行粘结，以制成圆柱状蜂窝单元11的集合体。
作为粘结层用膏，对其并无特别限定，可列举出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，粘结层用膏还可以包含有机粘结剂。作为有机粘结剂，对其并无特别限定，可列举出聚乙烯醇、甲基纤维素、乙基纤维素、羧甲基纤维素等，也可以同时使用其中的两种以上的有机粘结剂。
接下来，在圆柱状蜂窝单元11的集合体的外周面上涂敷外周涂层用膏。对外周涂层用膏并无特别限定，其可以包含与粘结层用膏相同的材料，也可以包含不同的材料。另外，外周涂层用膏还可以与粘结层用膏具有相同的组成。
之后，通过对涂敷了外周涂层用膏的蜂窝单元11的集合体进行干燥固化，得到圆柱状蜂窝结构体10’。此时，如果粘结层用膏以及/或者外周涂层用膏内包含了有机粘结剂，则优选为进行脱脂。脱脂条件可以根据有机物的种类和含量进行适当的选择，优选为在700℃下实施20分钟。
这里需要说明的是，在蜂窝结构体10以及10’中，也可以不形成外周涂层12。
[实施例1]
首先，将由Cu进行了2.7质量％离子交换且平均粒径为3.3μm的SAPO 3100g、伯姆石895g、平均纤维直径为6μm且平均纤维长度为100μm的氧化铝纤维485g、甲基纤维素380g、油脂酸(olein acid)280g、以及离子交换水2425g进行混合混炼，以制成原料膏1。
然后，使用挤压成型机对原料膏1进行挤压成型，制成正四棱柱状的蜂窝成型体毛坯。接下来，使用微波干燥机以及热风干燥机，在110℃下对蜂窝成型体进行10分钟的干燥处理，之后，在400℃下实施5个小时的脱脂。接下来，在700℃下进行2个小时的烧成，制成边长为34.3mm、长度为150mm的正四棱状蜂窝单元11。
在蜂窝体11中，贯穿孔11a的密度为93个/cm2，间壁11b的厚度为0.23mm，宏气孔的平均气孔孔径为0.20μm，气孔率为35％。这里，宏气孔的平均气孔孔径以及气孔率是通过使用压汞仪(mercuryporosimeter)来测定的。
接下来，将平均纤维直径为0.5μm且平均纤维长度为15μm的氧化铝纤维767g、石英玻璃2500g、羧甲基纤维素17g、固形成分为30质量％的二氧化硅溶胶600g、聚乙烯醇167g、界面活性剂167g、以及氧化铝中空球(alumina balloon)17g进行混合混炼，以制成具有耐热性的粘结层用膏。
涂敷粘结层用膏，以使粘结层的厚度为2mm，然后，使16个蜂窝单元11进行粘结，并对粘结层用膏在150℃下进行10分钟的干燥固化，之后，使用钻石切割器将其切削成与长度方向垂直的截面大致为点对称的圆柱状，以制成蜂窝单元11的集合体。
接下来，在蜂窝单元11的集合体的外周面上涂敷粘结层用膏，以使外周涂层的厚度为1mm，之后，使用微波干燥机和热风干燥机，在150℃下对粘结层用膏进行10分钟的干燥固化，然后，在400℃下实施2个小时的脱脂，以制成直径为143.8mm、高度为150mm的圆柱状蜂窝结构体10’。
之后，在于蜂窝结构体10’的外周部配置了支撑密封材(由无机纤维构成的垫材)20的状态下，将其封装入金属管(外壳)30，以制成尾气净化装置(参照图2)。
[实施例2]
将由Cu进行了2.7质量％离子交换且平均粒径为1.3μm的SAPO3100g、伯姆石895g、平均纤维直径为6μm且平均纤维长度为100μm的氧化铝纤维485g、甲基纤维素420g、油脂酸(olein acid)280g、以及离子交换水2600g进行混合混炼，以制成原料膏2。
除了以原料膏2代替原料膏1之外，与实施例1同样地制成蜂窝结构体10’和尾气净化装置。
这里需要说明的是，在蜂窝单元11中，宏气孔的平均气孔孔径为0.10μm，气孔率为35％。
[实施例3]
将由Cu进行了2.7质量％离子交换且平均粒径为5.0μm的SAPO3100g、伯姆石895g、平均纤维直径为6μm且平均纤维长度为100μm的氧化铝纤维485g、甲基纤维素350g、油脂酸(olein acid)280g、以及离子交换水2250g进行混合混炼，以制成原料膏3。
除了以原料膏3代替原料膏1之外，与实施例1同样地制成蜂窝结构体10’和尾气净化装置。
这里需要说明的是，在蜂窝单元11中，宏气孔的平均气孔孔径为0.30μm，气孔率为35％。
[实施例4]
将由Cu进行了2.7质量％离子交换且平均粒径为3.3μm的SAPO3100g、伯姆石895g、平均纤维直径为6μm且平均纤维长度为100μm的氧化铝纤维485g、甲基纤维素350g、油脂酸(olein acid)280g、以及离子交换水2250g进行混合混炼，以制成原料膏4。
除了以原料膏4代替原料膏1之外，与实施例1同样地制成蜂窝结构体10’和尾气净化装置。
这里需要说明的是，在蜂窝单元11中，宏气孔的平均气孔孔径为0.20μm，气孔率为30％。
[实施例5]
将由Cu进行了2.7质量％离子交换且平均粒径为3.3μm的SAPO3100g、伯姆石895g、平均纤维直径为6μm且平均纤维长度为100μm的氧化铝纤维485g、甲基纤维素420g、油脂酸(olein acid)280g、以及离子交换水2600g进行混合混炼，以制成原料膏5。
除了以原料膏5代替原料膏1之外，与实施例1同样地制成蜂窝结构体10’和尾气净化装置。
这里需要说明的是，在蜂窝单元11中，宏气孔的平均气孔孔径为0.20μm，气孔率为40％。
[比较例1]
将由Cu进行了2.7质量％离子交换且平均粒径为1.3μm的SAPO3100g、伯姆石895g、平均纤维直径为6μm且平均纤维长度为100μm的氧化铝纤维485g、甲基纤维素380g、油脂酸(olein acid)280g、以及离子交换水2425g进行混合混炼，以制成原料膏6。
除了以原料膏6代替原料膏1之外，与实施例1同样地制成蜂窝结构体10’和尾气净化装置。
这里需要说明的是，在蜂窝单元11中，宏气孔的平均气孔孔径为0.08μm，气孔率为32％。
[比较例2]
将由Cu进行了2.7质量％离子交换且平均粒径为5.5μm的SAPO3100g、伯姆石895g、平均纤维直径为6μm且平均纤维长度为100μm的氧化铝纤维485g、甲基纤维素350g、油脂酸(olein acid)280g、以及离子交换水2250g进行混合混炼，以制成原料膏7。
除了以原料膏7代替原料膏1之外，与实施例1同样地制成蜂窝结构体10’和尾气净化装置。
这里需要说明的是，在蜂窝单元11中，宏气孔的平均气孔孔径为0.35μm，气孔率为38％。
[比较例3]
将由Cu进行了2.7质量％离子交换且平均粒径为3.3μm的SAPO3100g、伯姆石895g、平均纤维直径为6μm且平均纤维长度为100μm的氧化铝纤维485g、甲基纤维素450g、油脂酸(olein acid)280g、以及离子交换水2740g进行混合混炼，以制成原料膏8。
除了以原料膏8代替原料膏1之外，与实施例1同样地制成蜂窝结构体10’和尾气净化装置。
这里需要说明的是，在蜂窝单元11中，宏气孔的平均气孔孔径为0.20μm，气孔率为43％。
[NOx净化率的测定]
从实施例1～5以及比较例1～3所制成的蜂窝结构体10’中各切出边长为34.3mm、长度为40mm的正四棱柱状蜂窝单元11的一部分，将其作为评价用样品。
以35000/hr的空间速度(SV)向各评价用样品中流入150℃的模拟气体，同时，使用触媒(催化剂)评价装置SIGU(“堀场制作所”公司制)，对从评价用样品中流出的一氧化氮(NO)的流出量进行测定，然后，测定由下式所表示的NOx的净化率[％]。
(NO的流入量-NO的流出量)/(NO的流入量)×100
这里需要说明的是，模拟气体的构成成分为175ppm的一氧化氮、175ppm的二氧化氮、350ppm的氨、14体积％的氧气、5体积％的二氧化碳、10体积％的水、以及氮(余量)。测定结果示于表1中。
[表1]
Figure BPA00001562604300141
由表1可知，从实施例1～5所制成的蜂窝结构体10’中切出的评价用样品具有较高的NOx净化率。
由此可以认为，蜂窝单元11的宏气孔平均气孔孔径为0.1～0.3μm、气孔率为30～40％时，蜂窝结构体10’和尾气净化装置具有优异的NOx净化性能。
这里需要说明的是，在本实施例中，尽管示出了蜂窝结构体10’，但是，可以认为，对蜂窝结构体10而言，也可以得到相同的效果。
符号说明
10、10’ 蜂窝结构体
11 蜂窝单元
11a 贯穿孔
11b 间壁
12 外周涂层
13 粘结层
20 支撑密封材
30 金属管
100 尾气净化装置

Claims (9)

1.一种蜂窝结构体，具有蜂窝单元，在该蜂窝单元中，包含磷酸盐系列沸石以及无机粘结剂，并且多个贯穿孔隔着间壁沿长度方向并排设置，该蜂窝结构体的特征在于，
在所述蜂窝单元中，宏气孔的平均气孔孔径为0.1μm以上且0.3μm以下，气孔率为30％以上且40％以下。
2.根据权利要求1所述的蜂窝结构体，其特征在于，
所述磷酸盐系列沸石为从SAPO、MeAPO、以及MeAPSO所组成的群中选择的一种以上的沸石。
3.根据权利要求2所述的蜂窝结构体，其特征在于，
所述SAPO为从SAPO-5、SAPO-11、以及SAPO-34所组成的群中选择的一种以上的SAPO。
4.根据权利要求1至3的任1项所述的蜂窝结构体，其特征在于，
所述磷酸盐系列沸石为包含由Cu以及/或者Fe进行了离子交换的沸石。
5.根据权利要求1至4的任1项所述的蜂窝结构体，其特征在于，
所述无机粘结剂为从氧化铝溶胶、二氧化硅溶胶、二氧化钛溶胶、水玻璃、海泡石、硅镁土、以及伯姆石所组成的群中选择的一种以上的物质中含有的固形成分。
6.根据权利要求1至5的任1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以及/或者鳞片状物质。
7.根据权利要求6所述的蜂窝结构体，其特征在于，
所述无机纤维为从氧化铝、二氧化硅、碳化硅、二氧化硅氧化铝、玻璃、钛酸钾、以及硼酸铝所组成的群中选择的一种以上的无机纤维，
所述鳞片状物质为从玻璃、白云母、氧化铝、二氧化硅、以及氧化锌所组成的群中选择的一种以上的物质。
8.根据权利要求1至7的任1项所述的蜂窝结构体，其特征在于，
具有多个所述蜂窝单元。
9.一种尾气净化装置，其特征在于，
具有权利要求1至8的任1项所述的蜂窝结构体。
CN200980162507.4A 2009-11-19 2009-11-19 蜂窝结构体以及尾气净化装置 Expired - Fee Related CN102666430B (zh)

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