CN108204261A - 具有混合孔结构的蜂窝状陶瓷结构 - Google Patents

具有混合孔结构的蜂窝状陶瓷结构 Download PDF

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CN108204261A
CN108204261A CN201611183538.6A CN201611183538A CN108204261A CN 108204261 A CN108204261 A CN 108204261A CN 201611183538 A CN201611183538 A CN 201611183538A CN 108204261 A CN108204261 A CN 108204261A
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ceramic
honey comb
cellular
ceramic honey
comb portion
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黄会波
毛欣
黄利锦
黄黎敏
王俊
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HANGZHOU YICHE VEHICLE DECONTAMINATION MACHINE CO Ltd
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HANGZHOU YICHE VEHICLE DECONTAMINATION MACHINE CO Ltd
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Priority to EP17207494.0A priority patent/EP3339269B1/en
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Abstract

本发明涉及具有混合孔结构的蜂窝状陶瓷结构。具体地，本发明涉及一种具有混合孔结构的蜂窝状陶瓷结构，所述蜂窝状陶瓷结构由位于中央的一个或更多个第一蜂窝陶瓷部和位于所述第一蜂窝陶瓷部周围的一个或更多个第二蜂窝陶瓷部构成，其中所述第一蜂窝陶瓷部为具有对称孔结构的蜂窝陶瓷，具有第一热容量值，其壁厚大于或等于0.28毫米；以及所述第二蜂窝陶瓷部为具有非对称孔结构的蜂窝陶瓷，具有第二热容量值，其壁厚小于0.28毫米，其中所述第一热容量值大于所述第二热容量值。本发明还涉及这样的蜂窝状陶瓷结构在捕集汽车发动机尾气中的碳烟颗粒方面的用途。

Description

具有混合孔结构的蜂窝状陶瓷结构
技术领域
本发明涉及用于汽车尾气排放处理的蜂窝状陶瓷过滤器结构。
背景技术
随着欧5排放标准的执行，柴油机颗粒过滤器(DPF)成为柴油车辆中的一种不可或缺的技术。近年来，随着机动车保有量的增加，机动车排放逐渐成为中国大城市空气污染的主要来源。在北京市大气PM2.5的来源中，机动车尾气排放的分担率高达22％。而且，机动车排放的颗粒物主要来自于柴油车。随着中国近年来日趋严格的柴油机动车排放控制法规的出台，DPF的应用将具有广阔的市场前景。
目前应用于DPF的材料包括氧化物与非氧化物，氧化物材料的典型代表为堇青石、钛酸铝、莫来石、三氧化二铝等，非氧化物材料主要是碳化硅和氮化硅。最理想的DPF材料应该具备低的热膨胀系数和高的导热系数，同时机械强度高、耐灰分腐蚀、耐疲劳和热冲击。碳化硅不但机械强度高，高温热稳定性好，而且导热性能非常好，其劣势是具有较高的热膨胀系数，因此在连续的DPF再生高温过程中，容易产生热应力，使DPF壁面形成裂缝，导致DPF失效。具有分割式结构并通过具备高强度和低弹性模量的陶瓷粘合剂组合而成的碳化硅DPF能有效地减少在其再生时产生的拉伸应力和压缩应力。
由于DPF再生时有热重叠显现，所以最高温度及最高温度梯度往往发生在DPF后端的中央位置处。由于这种热重叠效应，目前常规使用的整体式DPF或分割式DPF在温度较高的情况下容易产生局部的热应力，从而导致DPF破裂，尤其是DPF后端的中央容易产生裂纹或甚至裂缝。
因此，在本领域中仍然需要一种在保持良好的储灰容量的同时具有提高的热稳定性的蜂窝状陶瓷结构。
发明内容
为了克服现有的DPF不能在降低不可控再生时后端的温度的同时保持小体积、大的储灰容量的问题，本发明提供了一种具有混合孔结构的蜂窝状DPF结构，该结构通过优化孔结构，使得其背压降低，同时储灰容量基本上保持不变。具体地，该蜂窝状结构具有两种孔结构，其中壁厚比较厚的条状蜂窝部设置在中间，壁厚比较薄的条状蜂窝部设置在壁厚较厚的条状蜂窝部的外围。这种混合孔结构设计能使DPF同时兼顾各种优良的特性如良好的热稳定性和储灰性能，并且能有效降低再生时的最高温度，尤其是DPF后端中央部分的最高温度。
在本发明的一个方面中，提供了一种具有混合孔结构的蜂窝状陶瓷结构，所述蜂窝状陶瓷结构由位于中央的一个或更多个第一蜂窝陶瓷部和位于所述第一蜂窝陶瓷部周围的一个或更多个第二蜂窝陶瓷部构成，其中所述第一蜂窝陶瓷部为具有对称孔结构的蜂窝陶瓷，具有第一热容量值，其壁厚大于或等于0.28毫米；以及所述第二蜂窝陶瓷部为具有非对称孔结构的蜂窝陶瓷，具有第二热容量值，其壁厚小于0.28毫米，其中所述第一热容量值大于所述第二热容量值。
根据前述方面所述的蜂窝状陶瓷结构，所述第一蜂窝陶瓷部和所述第二蜂窝陶瓷部由选自碳化硅、重结晶碳化硅或堇青石中的一种材料制成。优选地，所述第一蜂窝陶瓷部和所述第二蜂窝陶瓷部均由重结晶碳化硅制成。
根据前述方面所述的蜂窝状陶瓷结构，所述第一蜂窝陶瓷部和所述第二蜂窝陶瓷部由选自碳化硅、重结晶碳化硅或堇青石中的两种不同的材料制成。例如，所述第一蜂窝陶瓷部由重结晶碳化硅制成，所述第二蜂窝陶瓷部由堇青石制成。
根据前述方面所述的蜂窝状陶瓷结构，所述第一蜂窝陶瓷部的体积与所述蜂窝状陶瓷结构的总体积比可以为0.10至0.3，优选为0.15至0.3，更优选为0.15至0.25，例如为0.12、0.14、0.16、0.18、0.20、0.22、0.24、0.26或0.28。如果该体积比的值过小，则第一蜂窝陶瓷部的体积过小，这样并不能为整个蜂窝状陶瓷结构提供足够高的耐热冲击性能，因此无法有效避免蜂窝状陶瓷结构在高温下产生裂纹或失效。如果该体积比的值过大，则第一蜂窝陶瓷的体积过大，由于其提供的气体过滤面积较小，因此降低了整体蜂窝状陶瓷结构的过滤能力，这也是不期望的。
根据前述方面所述的蜂窝状陶瓷结构，所述第一热容量值为1000-1200J/L*K，优选为1020-1100J/L*K，更优选为1020-1050J/L*K，例如为1020、1040、1060、1080、1100、1120、1140、1160或1180J/L*K。
根据前述方面所述的蜂窝状陶瓷结构，所述第二热容量值为600-900J/L*K，优选为600-800J/L*K，更优选为650-700J/L*K，例如为620、640、660、680、700、720、740、760、780、800、820、840、860或880J/L*K。
根据前述方面所述的蜂窝状陶瓷结构，所述第一蜂窝陶瓷部的壁厚为0.28-0.4mm，例如为0.30、0.32、0.34、0.36或0.38mm，其目数为200目到350目。由于所述第一蜂窝陶瓷部的壁厚较厚，所以具有较高的耐热冲击性能。
根据前述方面所述的蜂窝状陶瓷结构，所述第二蜂窝陶瓷部的壁厚为0.15-0.28mm，例如为0.17、0.19、0.21、0.23、0.25或0.27mm。
在本发明的另一方面中，将根据前述方面所述的蜂窝状陶瓷结构用于捕集汽车发动机尾气中的碳烟颗粒。由于根据本发明的新型蜂窝状陶瓷结构兼具提高的热稳定性和良好的尾气过滤性能，所以能够用于捕集汽车发动机尾气中的碳烟颗粒，并且在累积了一定量的碳烟颗粒之后通过燃烧将其除去。这样的新型蜂窝状陶瓷结构降低了在高温再生条件下产生裂纹或裂缝的风险。
另外，通过增加DPF中间区域的热熔，可以有效地降低DPF再生时在其后端的温度及温度梯度，进而避免DPF产生裂缝造成其过滤效率下降或甚至失效。
附图说明
以下将参考附图来描述本发明。应当理解，附图仅仅是用来以举例的方式解释和说明本发明的原理，而无意于将本发明限制于附图中所显示的具体方案。在附图中：
图1a和图1b分别是常规使用的具有均一孔结构的整体式蜂窝状陶瓷结构和分割式蜂窝状陶瓷结构的示意图；
图2是具有非对称孔结构的蜂窝状陶瓷结构的截面示意图；
图3是根据本发明的具有混合孔结构的蜂窝状陶瓷结构的示意图，其中1区代表第一蜂窝陶瓷部，2区代表第二蜂窝陶瓷部；
图4是根据常规使用的具有均一孔结构的分割式蜂窝状陶瓷结构和根据本发明的具有混合孔结构的蜂窝状陶瓷结构在高温下的各部分温度分布图。
具体实施方式
以下将参考附图详细描述根据本发明的具有混合孔结构的蜂窝状陶瓷结构。然而，本领域的普通技术人员会理解，以下给出的各个实施例仅仅是为了使本领域的普通技术人员能够更好地理解本发明，而没有任何限制的目的。本发明的范围是由权利要求书限定的。
蜂窝状陶瓷结构是用于捕集车辆发动机、尤其是柴油车发动机尾气排放中的颗粒物质的常用手段之一。目前，常用的蜂窝状陶瓷过滤器或颗粒捕集器通常采用具有均一的孔结构的蜂窝状结构，例如整体式的蜂窝状结构或者拼接式的蜂窝状结构，如图1中显示的。这样的蜂窝状结构具有结构简单、制造方法简便等优点，由于温度重叠效应，DPF在不可控再生的过程中容易在中后部形成高温区域，产生热应力，使得DPF壁面容易形成裂缝，导致DPF失效。
与此相比，为了克服现有DPF不能在兼顾降低不可控再生时后端的温度、同时保持小体积、大的储灰容量的缺陷，本发明提供了一种具有混合孔结构的蜂窝状陶瓷结构。下面将参考实施例来对其进行详细描述和说明。
实施例1：制备具有均一孔结构的分割式蜂窝状陶瓷结构(对比例)
根据中国专利申请CN200610106777.1中记载的成形方法制备长条状的重结晶碳化硅蜂窝状陶瓷结构，然后利用粘结剂将多条蜂窝状陶瓷结构粘结成分割式蜂窝状陶瓷结构，并用作对比例。该蜂窝状陶瓷结构的壁厚为0.25mm，目数为300目。利用激光测量方法测得其热容量值为668J/L*K。
实施例2：制备具有混合孔结构的蜂窝状陶瓷结构(本发明)
根据中国专利申请CN200610106777.1中记载的成形方法制备长条状的重结晶碳化硅蜂窝状陶瓷结构，然后利用粘结剂将多条蜂窝状陶瓷结构粘结起来，用作根据本发明的第一蜂窝陶瓷部。第一蜂窝陶瓷部具有两种规格，即第一蜂窝陶瓷部A和第一蜂窝陶瓷部B，以分别用于后续的实验。
第一蜂窝陶瓷部A的壁厚为0.30mm，目数为200目。过滤面积为7451平方厘米每升。第一蜂窝陶瓷部A占蜂窝状陶瓷结构的总体积的15％，具有对称的孔结构。利用激光测量方法测得其热容量值为1025J/L*K。
第一蜂窝陶瓷部B的壁厚为0.35mm，目数为200目。过滤面积为7451平方厘米每升。第一蜂窝陶瓷部B占蜂窝状陶瓷结构的总体积的15％，具有对称的孔结构。利用激光测量方法测得其热容量值为1165J/L*K。
根据Kazuki Nakamura等人(“New Asymmetric Plugging Layout of DieselParticulate Filters for the Pressure Drop Reduction”,SAE:2014-01-1512)提供的方法制备数个条状的具有非对称孔结构的碳化硅蜂窝状陶瓷结构，并用作根据本发明的第一蜂窝陶瓷部C。所述第一蜂窝陶瓷部C的目数为300目，壁厚为0.30mm，过滤面积高达15400平方厘米每升。利用激光测量方法测得其热容量值为1108J/L*K。
根据Kazuki Nakamura等人(“New Asymmetric Plugging Layout of DieselParticulate Filters for the Pressure Drop Reduction”,SAE:2014-01-1512)提供的方法制备数个条状的具有非对称孔结构的碳化硅蜂窝状陶瓷结构，并用作根据本发明的第二蜂窝陶瓷部D。所述第二蜂窝陶瓷部的目数为300目，壁厚为0.25mm，过滤面积高达15400平方厘米每升。利用激光测量方法测得其热容量值为726J/L*K。
利用陶瓷粘结剂将第一蜂窝陶瓷部A、B或C分别和第二蜂窝陶瓷部D粘结在一起形成完整的蜂窝状陶瓷结构A、B或C，其中第一蜂窝陶瓷部A、B或C位于中央，第二蜂窝陶瓷部D分布在第一蜂窝陶瓷部的周围，并且其中第一蜂窝陶瓷部A、B和C占整个蜂窝陶瓷结构的总体积的15％。
实施例3：测试对比例和根据本发明的蜂窝状陶瓷结构在高温下的各区域温度分布
在根据本发明的实施例中，由于第一蜂窝陶瓷部占整个蜂窝陶瓷结构的比例比较低，例如为15％左右，因此其对整个蜂窝陶瓷结构的过滤面积的影响比较小，基本上可以被忽略。也就是说，根据本发明的蜂窝状陶瓷结构与完全采用第二蜂窝陶瓷部的具有非对称孔结构的蜂窝陶瓷结构的过滤面积是相当的，因此它们的碳负载/储灰能力也是大致相当的。
分别将对比例的蜂窝状陶瓷结构和根据本发明的包括蜂窝状陶瓷部A、B和C的蜂窝陶瓷结构封装在钢制外壳体中，然后置于柴油发动机台架的尾气排放管后面，进行碳负载实验，直至蜂窝状陶瓷结构中的碳烟负载到5.5g/L。然后，利用安装在尾气排放路径中的低温升温器(参见中国专利申请CN103104319A)对负载碳的蜂窝状陶瓷结构进行再生，同时利用安装在蜂窝状陶瓷结构周围的温度传感器和压力传感器记录测试过程中的温度和压力。其中根据本发明的蜂窝状陶瓷结构和根据对比例的蜂窝状陶瓷结构的各区域温度分布图示于图4中。在该实验中，经测量，根据本发明的具有混合孔结构的蜂窝状陶瓷结构在再生过程中的最大温度为860度，最大温度梯度为32度每厘米。与此相比，在再生过程中，常规使用的具有均一孔结构的蜂窝状陶瓷结构的最大温度为1020度，最大温度梯度为116度每厘米。
由图4可见，在对比例中，具有均一孔结构的蜂窝陶瓷结构在出口端(中后部)的中心处的温度比较高(深色区域)，与此相比，具有混合孔结构的本发明蜂窝状陶瓷结构的出口端(中后部)的中心处的温度相对较低(浅色区域)。由此可见，通过使用本发明的具有混合孔结构的蜂窝陶瓷结构，大幅降低了其中后部区域的温度，从而能够有效降低蜂窝陶瓷结构因温度过高而导致的产生裂纹或裂缝的风险。另外，在中心温度较高的情况下，由于本发明将具有较大的壁厚和较高热容量值的蜂窝陶瓷部置于中心处，使得其能够耐受较高的温度，从而也有利于降低产生裂纹或裂缝的风险。

Claims (10)

1.一种具有混合孔结构的蜂窝状陶瓷结构，所述蜂窝状陶瓷结构由位于中央的一个或更多个第一蜂窝陶瓷部和位于所述第一蜂窝陶瓷部周围的一个或更多个第二蜂窝陶瓷部构成，其中
所述第一蜂窝陶瓷部为具有对称孔结构或非对称孔结构的蜂窝陶瓷，具有第一热容量值，其壁厚大于或等于0.28毫米；以及
所述第二蜂窝陶瓷部为具有非对称孔结构的蜂窝陶瓷，具有第二热容量值，其壁厚小于0.28毫米，
其中所述第一热容量值大于所述第二热容量值。
2.根据权利要求1所述的蜂窝状陶瓷结构，其中所述第一蜂窝陶瓷部和所述第二蜂窝陶瓷部由选自碳化硅、重结晶碳化硅或堇青石中的一种材料制成。
3.根据权利要求1所述的蜂窝状陶瓷结构，其中所述第一蜂窝陶瓷部和所述第二蜂窝陶瓷部由选自碳化硅、重结晶碳化硅或堇青石中的两种不同的材料制成。
4.根据权利要求1所述的蜂窝状陶瓷结构，其中所述第一蜂窝陶瓷部的体积与所述蜂窝状陶瓷结构的总体积比为0.10至0.3，优选为0.15至0.3，更优选为0.15至0.25，例如为0.12、0.14、0.16、0.18、0.20、0.22、0.24、0.26或0.28。
5.根据权利要求1所述的蜂窝状陶瓷结构，其中所述第一热容量值为1000-1200J/L*K，优选为1020-1100J/L*K，更优选为1020-1050J/L*K，例如为1020、1040、1060、1080、1100、1120、1140、1160或1180J/L*K。
6.根据权利要求1所述的蜂窝状陶瓷结构，其中所述第二热容量值为600-900J/L*K，优选为600-800J/L*K，更优选为650-700J/L*K，例如为620、640、660、680、700、720、740、760、780、800、820、840、860或880J/L*K。
7.根据权利要求1所述的蜂窝状陶瓷结构，其中所述第一蜂窝陶瓷部的壁厚为0.28-0.4mm，例如为0.30、0.32、0.34、0.36或0.38mm，其目数为200目到350目。
8.根据权利要求1所述的蜂窝状陶瓷结构，其中所述第二蜂窝陶瓷部的壁厚为0.15-0.28mm，例如为0.17、0.19、0.21、0.23、0.25或0.27mm。
9.根据权利要求1-3中任一项所述的蜂窝状陶瓷结构，其中所述第一蜂窝陶瓷部和第二蜂窝陶瓷部均具有方形或矩形横截面；或者所述第一蜂窝陶瓷部具有圆形横截面，所述第二蜂窝陶瓷部具有环形或扇形横截面。
10.根据权利要求1-9中任一项所述的蜂窝状陶瓷结构用于捕集汽车发动机尾气中的碳烟颗粒的用途。
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