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CN103133093A - 在柴油机特定的过滤器上的scr及其制备方法 - Google Patents

在柴油机特定的过滤器上的scr及其制备方法 Download PDF

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CN103133093A
CN103133093A CN2012102189860A CN201210218986A CN103133093A CN 103133093 A CN103133093 A CN 103133093A CN 2012102189860 A CN2012102189860 A CN 2012102189860A CN 201210218986 A CN201210218986 A CN 201210218986A CN 103133093 A CN103133093 A CN 103133093A
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scr
sdpf
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崔城茂
李孝京
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Hyundai Motor Co
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Abstract

本发明涉及SDPF（在柴油机特定的过滤器上的SCR）及其制备方法，所述SDPF包括收集柴油机排放气体的PM（微粒材料）的多孔过滤器、涂布在过滤器的排放气体入口上的SCR（选择性催化还原）催化剂层、涂布在过滤器的排放气体出口上的氧化铝层、以及涂布在氧化铝层表面上的贵金属催化剂层。

Description

在柴油机特定的过滤器上的SCR及其制备方法
相关申请的交叉引用
本申请要求2011年11月28日提交的韩国专利申请第10-2011-0125045号的优先权，该申请的全部内容并入此处作为参考用于所有目的。
技术领域
本公开涉及SDPF（在柴油机特定的过滤器上的SCR）及其制备方法，所述SDPF可阻止由于贵金属催化剂的NH3氧化反应，因为SCR催化剂层和贵金属催化剂层是分离的。
背景技术
在SDPF（在柴油机特定的过滤器上的SCR）中，将SCR（选择性催化还原）催化剂（通常为Cu-沸石，Fe-沸石）涂布在多孔DPF（柴油机特定的过滤器）上，在NH3和由整个SDPF供应的排放气体中的NOx在SCR催化剂上反应，并被净化为水和N2。
此外，由于SDPF用作过滤器，其收集排放气体中的烟灰（PM，微粒材料）如DPF，并通过柴油机发动机后喷升高排放气体温度，致使氧化/除去SDPF上收集的烟灰。
现今，SDPF被分为被动型和主动型。被动型为LNT+SDPF型，且当LNT中收集的NOx经受去NOx（DeNOx）工艺（通过后喷）时，会产生NH3作为副产物，而该NH3和排放气体中过量的NOx在SDPF中被净化为NO2。
主动型在整个SDPF上装有脲（脲水）喷射器并提供脲，而从UREA汽化的NH3在SDPF中与NOx反应并被净化为N2。作为SDPF自身功能，被动型和主动型两者均收集烟灰，通过发动机的定期后喷提高排放气体温度，并氧化/燃烧在过滤器中收集的烟灰。
当提高排放气体温度或通过第二喷射产生NH3时，任选地产生第二EM（HC、CO等等）。在现有体系（DOC+DPF或LNT+DPF）中，除去任选地通过涂布在DPF上的催化剂（Pt、Pd等等）产生的第二EM。然而，在被动型/主动型SDPF中，第二EM应当通过涂布在DPF上的SCR催化剂除去，但涂布在DPF上的SCR催化剂通常为沸石类型的，并具有与贵金属催化剂相比很低的对第二EM（HC、CO等等）的氧化性能。
图1为表示常规SDPF分布随时间变化的图。用于通常的SDPF的过滤器材料包括SiC、AT、堇青石等等，且孔隙率介于55和65%之间。此外，孔的平均直径为约10-25μm。当其用于SDPF时，烟灰和SCR催化剂的分布如图1所示。从DPF入口面至出口面涂布SCR催化剂，因为许多SCR催化剂被涂布在多孔DPF上。这样，通过NH3和NOx在SCR催化剂上的SCR反应净化NOx。然而，当后喷产生NH3并再生DPF时，该SCR催化剂不能充分地净化产生的第二EM。
因此，当使用SDPF时，需要减少由于后喷任选地产生的第二EM的技术。当将SCR催化剂（沸石类型）涂布在多孔DPF的排放气体入口的侧壁上，并将贵金属催化剂涂布在排放气体出口的侧壁上时，涂布在出口面上的贵金属催化剂被涂布至排放气体入口侧壁，供应至排放气体入口的侧壁的NH3被氧化，且干扰了NH3+NOx=N2+H2O反应。因此，当使用通常的涂布方法将贵金属催化剂涂布在排放气体出口的侧壁时，存在其干扰NH3+NOx的SCR反应的问题，且NOx净化速率变低。
公开于这个背景技术部分的信息仅仅旨在加深对本发明的一般背景技术的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域技术人员所公知的现有技术。
发明内容
本发明的多个方面提供SDPF及其制备方法，所述SDPF可阻止由于贵金属催化剂的NH3氧化反应，因为SCR催化剂层和贵金属催化剂层是分离的。
本发明的多个方面提供SDPF（在柴油机特定的过滤器上的SCR），所述SDPF包括收集柴油机排放气体的PM（微粒材料）的多孔过滤器、涂布在过滤器的排放气体入口上的SCR（选择性催化还原）催化剂层、涂布在过滤器的排放气体出口上的氧化铝层、以及涂布在氧化铝层表面上的贵金属催化剂层。
SCR涂层可为包括沸石催化剂的涂层。
氧化铝层可具有为过滤器孔径的80-120%的粒度。
贵金属催化剂层可具有为过滤器孔径的80-120%的粒度。
可通过用氧化铝浸渍贵金属而形成贵金属催化剂层。
过滤器可由层状排列的多个过滤器板组成，且多个过滤器板的相对面可形成排放气体入口和出口，从而交替地形成入口和出口。
本发明的多个方面提供制备SDPF的方法，所述方法包括：过滤器制备步骤，所述步骤为以一定的间隔分离收集柴油机排放气体的PM（微粒材料）的多个多孔过滤器板并以层状排列；排列步骤，所述步骤为用过滤器板的相对面形成排放气体入口和出口，其中交替地形成入口和出口；SCR层涂布步骤，所述步骤为用SCR催化剂溶液浸渍过滤器板入口的面；氧化铝层涂布步骤，所述步骤为用氧化铝溶液浸渍过滤器板出口的面；和贵金属催化剂层涂布步骤，所述步骤为用贵金属催化剂溶液浸渍过滤器板出口的面。
在氧化铝层涂布步骤中，通过碾磨和干燥氧化铝并控制其粘度制备氧化铝溶液，并用所述溶液浸渍过滤器板出口的面，之后将其干燥和涂布。
在贵金属催化剂层涂布步骤中，通过碾磨氧化铝、与贵金属前体混合、煅烧和碾磨，之后控制其粘度来制备贵金属催化剂溶液，并用所述溶液浸渍过滤器板出口的面，之后将其干燥和涂布。
通过纳入本文的附图以及随后与附图一起用于说明本发明的某些原理的具体实施方式，本发明的方法和装置所具有的其它特征和优点将更为具体地变得清楚或得以阐明。
附图说明
图1为表示常规SDPF分布随时间变化的图。
图2为根据本发明的示例性SDPF的具体的横截面的组成图。
图3为根据本发明的示例性SDPF的组成图。
应当了解，所附附图不一定按比例，而是显示了图示本发明的基本原理的各种特征的略微简化的表示法。
在这些图中，附图标记用于贯穿附图的多幅图的本发明的相同的或等同的部分。
具体实施方式
下面将对本发明的各个实施方案详细地作出说明，这些实施方案的实施例被显示在附图中并描述如下。尽管本发明将与示例性实施方案相结合进行描述，但是应当意识到，本说明书并非旨在将本发明限制为那些示例性实施方案。相反，本发明旨在不但覆盖这些示例性实施方案，而且覆盖可以被包括在由所附权利要求所限定的本发明的精神和范围之内的各种选择形式、修改形式、等价形式及其它实施方案。
图2为根据本发明的一个实施方案的SDPF的具体的横截面的组成图，而图3为根据本发明的一个实施方案的整个SDPF的组成图。
本发明的SDPF（在柴油机特定的过滤器上的SCR）包括收集柴油机排放气体的PM（微粒材料）的多孔过滤器100、涂布在过滤器100的排放气体入口上的SCR（选择性催化还原）催化剂层300、涂布在过滤器100的排放气体出口上的氧化铝层500、以及涂布在氧化铝层500表面上的贵金属催化剂层700。
本发明的SDPF通过顺序地在多孔SDPF过滤器的一个面上涂布SCR催化剂（沸石类型）、在其另一面上涂布边界层催化剂、以及然后涂布贵金属催化剂制得。亦即，其为涂布尺寸等于过滤器平均直径的80%~120%的氧化铝（Al2O3）粒子、然后在其上再涂布尺寸等于过滤器平均直径的80%~120%的Al2O3+贵金属混合物的催化剂的方法。该结构很好地描述于图2中
因此，依次涂布顺序是：在多孔过滤器的DPF入口面上涂布SCR催化剂，在DPF出口面上预先涂布尺寸等于过滤器平均直径的80%~120%的Al2O3粒子，然后在DPF出口面上进一步涂布尺寸等于过滤器平均直径的80%～120%的催化剂（其中贵金属沉积在Al2O3上）。这样，可阻止由于贵金属催化剂的NH3氧化反应，因为SCR催化剂层和贵金属催化剂层是彼此分离的。
因此，本发明的SDPF基于收集柴油机排放气体的PM（微粒材料）的多孔过滤器100，且将SCR（选择性催化还原）催化剂层300涂布在过滤器100的排放气体入口上。然后，氧化铝层500和贵金属催化剂层700顺序地涂布在过滤器100的排放气体出口的相对侧上。氧化铝层阻止了贵金属催化剂层的侵入，从而在SCR催化剂层和贵金属催化剂层彼此分离的状态下忠实地实现各自的作用。
另一方面，SCR涂层300为包括沸石催化剂的涂层，氧化铝层500具有为过滤器孔径的80-120%的粒度，且贵金属催化剂层700也具有为过滤器孔径的80-120%的粒度。
氧化铝，Al2O3，为γ-型Al2O3，且由于其可通过在过滤器与Pt/Al2O3涂层之间形成Al2O3涂层，抑制过滤器与Pt/Al2O3涂层之间的相互作用，而用作屏蔽物。并且，为了用作屏蔽物，Al2O3必须具有热稳定性，并应当不发生粒子烧结。γ-型Al2O3具有最高达850℃的温度的热稳定性。
此外，γ-型Al2O3具有高表面积，具有约150m3/g的比表面积，并且其表面非常粗糙，而其形状是非均一的。因此，具有光滑表面和均一表面形状的材料可容易地物理封堵过滤器的孔，粗糙且非均一的γ-型Al2O3提供了通道，在该通道中排放气体流动并减少背压（如果使用具有低表面积和低热稳定性的均一材料，当暴露至高温时其粒子会烧结，而其表面变得光滑，且这会通过封堵过滤器的孔提高背压）。此外，由于Al2O3具有好的涂布性质，其被涂布在过滤器粒子上并表现出高粘附性能。因此，其具有高机械耐久性。
而通过用氧化铝浸渍贵金属而制备贵金属催化剂层700。此外，过滤器100可由层状排列的多个过滤器板120组成，且多个过滤器板120的相对面可形成排放气体入口和出口，从而交替地形成入口和出口。
制备SDPF的这个方法包括：过滤器制备步骤，所述步骤以一定的间隔分离收集柴油机排放气体的PM（微粒材料）的多个多孔过滤器板并以层状排列；排列步骤，所述步骤用过滤器板的相对面形成排放气体入口和出口，其中交替地形成入口和出口；SCR层涂布步骤，所述步骤用SCR催化剂溶液浸渍过滤器板入口的面；氧化铝层涂布步骤，所述步骤用氧化铝溶液浸渍过滤器板出口的面；和贵金属催化剂层涂布步骤，所述步骤用贵金属催化剂溶液浸渍过滤器板出口的面。
此外，在氧化铝层涂布步骤中，通过碾磨和干燥氧化铝并控制其粘度制备氧化铝溶液，并可用所述溶液浸渍过滤器板出口的面，之后将其干燥和涂布。
在贵金属催化剂层涂布步骤中，通过碾磨氧化铝、与贵金属前体混合、煅烧和碾磨，之后控制其粘度来制备贵金属催化剂溶液，并可用所述溶液浸渍过滤器板出口的面，之后将其干燥和涂布。
首先，以一定的间隔分离多个多孔过滤器板并以层状排列以制备过滤器，且将塞220锯齿形布置在每个过滤器板之间。通过塞200，入口向一侧开放，出口向另一侧开放。
且用SCR催化剂溶液浸渍面朝下的入口，以仅在与入口相对的过滤器板的面上涂布SCR催化剂层。
且用氧化铝溶液浸渍面朝下的出口以涂布铝涂层并干燥，然后，用贵金属催化剂溶液浸渍面朝下的出口以涂布贵金属催化剂层。通过该方法，制备如图2和3中所示的本发明的SDPF。
根据由上述结构组成的SDPF及其制备方法，在SCR催化剂（DPF入口面）和贵金属催化剂（DPF出口面）上形成边界层，因此，其可以防止供应至DPF的NH3被氧化而不是对NOx净化速率做出贡献。
为了方便解释和精确限定所附权利要求，术语上或下，前或后，内或外等通过参考附图中所显示的这些特征的位置被用来描述示例性实施方案的特征。
前面对本发明具体示例性实施方案所呈现的描述是出于说明和描述的目的。前面的描述并不想要成为毫无遗漏的，也不是想要把本发明限制为所公开的精确形式，显然，根据上述教导很多改变和变化都是可能的。选择示例性实施方案并进行描述是为了解释本发明的特定原理及其实际应用，从而使得本领域的其它技术人员能够实现并利用本发明的各种示例性实施方案及其不同选择形式和修改形式。本发明的范围意在由所附权利要求书及其等同形式所限定。

Claims (9)

1.一种在柴油机特定的过滤器上的SCR（SDPF），其包括：
排放气体入口和排放气体出口；
收集柴油机排放气体的微粒材料（PM）的多孔过滤器，所述多孔过滤器具有过滤器孔径；
涂布在过滤器的排放气体入口上的选择性催化还原（SCR）催化剂层；
涂布在过滤器的排放气体出口上的氧化铝层；和
涂布在氧化铝层表面上的贵金属催化剂层。
2.根据权利要求1所述的SDPF，其中所述SCR层为包括沸石催化剂的涂层。
3.根据权利要求1所述的SDPF，其中所述氧化铝层具有为过滤器孔径的80-120%的粒度。
4.根据权利要求1所述的SDPF，其中所述贵金属催化剂层具有为过滤器孔径的80-120%的粒度。
5.根据权利要求1所述的SDPF，其中所述贵金属催化剂层通过用氧化铝浸渍贵金属而形成。
6.根据权利要求1所述的SDPF，其中所述过滤器包括层状排列的多个过滤器板，且多个过滤器板的相对面形成排放气体入口和出口，从而交替地形成入口和出口。
7.一种制备在柴油机特定的过滤器上的SCR（SDPF）的方法，其包括：
过滤器制备步骤，所述步骤为以一定的间隔分离收集柴油机排放气体的微粒材料（PM）的多个多孔过滤器板并以层状排列；
排列步骤，所述步骤为用过滤器板的相对面形成排放气体入口和出口，其中交替地形成入口和出口；
选择性催化还原（SCR）催化剂层涂布步骤，所述步骤为用SCR催化剂溶液浸渍过滤器板入口的面；
氧化铝层涂布步骤，所述步骤为用氧化铝溶液浸渍过滤器板出口的相对面；和
贵金属催化剂层涂布步骤，所述步骤为用贵金属催化剂溶液浸渍过滤器板出口的相对面。
8.根据权利要求7所述的制备SDPF的方法，其中在氧化铝层涂布步骤中，通过碾磨和干燥氧化铝并控制其粘度来制备氧化铝溶液，并用该溶液浸渍过滤器板出口的面，之后将其干燥和涂布。
9.根据权利要求7所述的制备SDPF的方法，其中在贵金属催化剂层涂布步骤中，通过碾磨氧化铝、与贵金属前体混合、煅烧和碾磨之后控制其粘度来制备贵金属催化剂溶液，并用所述溶液浸渍过滤器板出口的面，之后将其干燥和涂布。
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