CN101326004A - 常温氮氧化物吸附剂 - Google Patents

常温氮氧化物吸附剂 Download PDF

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CN101326004A
CN101326004A CNA2006800466664A CN200680046666A CN101326004A CN 101326004 A CN101326004 A CN 101326004A CN A2006800466664 A CNA2006800466664 A CN A2006800466664A CN 200680046666 A CN200680046666 A CN 200680046666A CN 101326004 A CN101326004 A CN 101326004A
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metal
adsorbent
metal oxide
oxide
ambient temperature
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金泽孝明
佐藤明美
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Toyota Motor Corp
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Abstract

本发明提供了常温NOx吸附剂。该常温NOx吸附剂包含载体和负载在该载体上的金属。所述载体包含至少一种选自Co、Fe、Cu、Ce、Mn及其组合的氧化物的金属氧化物。所述被负载的金属包含至少一种选自Cu、Co、Ag、Pd及其组合的金属。所述金属氧化物易于改变氧化值，并具有氧吸收/排放性能。被负载的金属具有氧化活性，并对NO具有高吸附性。由金属氧化物提供的氧将被负载的金属转化为被负载金属的过氧化形式。因此，NO易于在室温附近的常温吸附到被负载金属上。在常温气氛中，在不存在氧的情况下，被吸附的NO易于被金属氧化物或处于过氧化状态的被负载金属提供的氧氧化为NO2。然后NO2被有效吸附在金属氧化物上。也就是说，即使在室温附近的常温下，常温NOx吸附剂也可以吸附足量的NOx。

Description

常温氮氧化物吸附剂
背景技术
1.技术领域
本发明涉及在室温范围内的常温吸附NOx的NOx吸附剂。本发明多个实施方案提出的NOx吸附剂在废气通道中位于废气净化催化剂(例如三效催化剂或NOx吸附/还原催化剂)的上游或下游，使得NOx吸附剂能够吸附足量NOx，直至废气净化催化剂达到该催化剂的某一特定范围的活化温度，从而大大地抑制NOx排放到大气中。
2.相关技术的描述
由于有关废气净化催化剂(包括三效催化剂和NOx吸附/还原催化剂)的技术的改进，由车辆排出的废气中所含的有害物质逐渐降低到非常低的程度。但是，由于使用废气净化催化剂通过催化金属(例如铂，Pt)将废气中所含有害物质氧化或还原而净化废气，不利的是，催化金属在低于它们的活化温度的温度保持非活性。
特别地，在发动机启动之后不久，废气中所含的有害物质在没有被净化的情况下排放数十秒，直到废气净化催化剂的温度上升到高于催化金属的活化温度。特别是在冬季，未净化的有害物质的排放常常持续较长的时间。
催化金属的活化温度(在此温度催化金属显示出催化活性)随着待净化的废气中所含物质的种类而变化。例如，NOx可以被净化的NOx活化温度高于HC和CO可以被净化的HC和CO活化温度。因此，NOx的排放时间长于HC和CO的排放时间。
因此，可以预料，通过在发动机刚刚启动之后吸附NOx直至废气净化催化剂的温度升高到高于催化金属的活化温度，可以抑制NOx向大气中的排放。
例如，日本未审专利公开第2001-198455号提出了一种NOx吸附剂，其包含一种选自Co、Fe和Ni的氧化物的金属氧化物。NOx吸附剂在低于40℃的低温区吸附大量的NOx。NOx吸附剂在40℃或更低的温度对气体中的NOx具有10×10-5摩尔/克或更高的饱和吸附量，并在低温具有良好的NOx吸附性能。
另外，日本未审专利公开第2001-289035号描述了一种NOx吸附剂，其包含碱金属氧化物、碱土金属氧化物、Co3O4、NiO2、MnO2、Fe2O3、ZrO2和沸石。该专利公开指出，所述NOx吸附剂通常可以在低温区至中温区吸附废气中所含的NOx。
但是，这些NOx吸附剂在室温范围内的常温对NOx可能具有低的吸附性，并具有局限性，因为在废气净化催化剂的温度达到催化金属的活化温度之前NOx被排放到大气中。
发明概要
鉴于上述局限性提出了本发明，本发明的目的是提供一种NOx吸附剂，其即使在室温范围内的常温也能吸附足量NOx。
根据本发明的一方面，提供了一种常温NOx吸附剂，其包含载体和负载在该载体上的金属(下文简称为“被负载的金属”)，其中所述载体含有至少一种选自Co、Fe、Cu、Ce、Mn及其组合的氧化物的金属氧化物(下文简称为“选择的金属氧化物”)，且被负载金属包含至少一种选自Cu、Co、Ag、Pd及其组合的金属，条件是所述载体包括与所述被负载金属不同的金属。
在一个实施方案中，所述被负载金属可以是选自Ag和Pd中的一种金属。
在一个实施方案中，所述选择的金属氧化物可以选自Co、Fe、Ce及其组合的氧化物。
在一个实施方案中，相对于100重量份所述选择的金属氧化物，所述被负载金属以约1至20重量份的量负载。
附图简述
根据下文详细的描述，联系附图，将更清楚地理解本发明的上述及其它目标、特征和其它优势，其中：
图1是显示本发明一个实施方案的NOx吸附剂的NOx吸附机理的示意图。
图2显示了被实施例和对比例中制备的各种NOx吸附剂吸附的NO的量；
图3显示了测试例1的X射线光电子分光(XPS)光谱；和
图4显示了测试例2的傅里叶变换红外(FT-IR)分光光谱。
具体实施方案的描述
选自Co、Fe、Cu、Ce、Mn及其组合的氧化物的至少一种金属氧化物的氧化值容易改变，并具有氧吸附/排放性能。选自Cu、Co、Ag、Pd及其组合的至少一种被负载金属具有氧化活性，并对NO具有高吸附性。被负载金属通过所述选择的金属氧化物提供的氧转化为其过氧化形式。因此，如图1所示，即使在室温范围内的常温下，存在于气氛中的NO也被吸附到被负载的金属上。即使在常温气氛中在不存在氧的情况下，被吸附的NO也容易被所述选择的金属氧化物或处于过氧化状态的被负载金属提供的氧氧化为NO2。然后NO2被有效吸附在所述选择的金属氧化物上。
因此，根据本发明实施方案的常温NOx吸附剂能够以非常有效的方式吸附存在于气氛中的NO，并能够大大地抑制NOx排放，直到在发动机启动后废气净化催化剂的温度达到催化金属的特定范围的活化温度。
常温NOx吸附剂包含含有所述选择的金属氧化物的载体和负载在所述选择的金属氧化物上的负载金属。所述选择的金属氧化物包括至少一种选自Co、Fe、Cu、Ce、Mn及其组合的氧化物的金属氧化物。特别地，由于其易于变化的氧化值和高的氧发射能，至少一种选自Co、Fe、Cu、Ce、Mn及其组合的氧化物的金属氧化物表现出高的NOx吸附性能。
虽然载体仅在预设实施方案中才包括所述选择的金属氧化物，但载体还可以包含选自氧化铝、氧化锆、二氧化钛、二氧化硅、沸石和其它氧化物的其它氧化物。由于每单位体积的NOx吸附量随着其它氧化物的量的增大而减少，因此所述其它氧化物的量优选尽可能小。
被负载金属包括至少一种选自Cu、Co、Ag、Pd及其组合的金属，并且不同于构成所述选择的金属氧化物的金属。至于所述被负载金属，特别优选是Pd或Ag。Pd或Ag对NO具有高氧化性。特别地，Pd比其它的对于NO具有高得多的氧化性，因为它容易转化为高过氧化形式。Ag被认为对NO有高亲和性。因此，在提高NOx吸附性能方面，使用Pd或Ag作为负载金属是有利的。
被负载金属要求负载在所述选择的金属氧化物上。如果载体中包含不是所述选择的金属氧化物的氧化物，则负载金属可以负载在该额外的氧化物上。
相对于100重量份所述选择的金属氧化物，所述被负载金属优选以约1至20重量份的量负载。如果负载金属的负载量小于1重量份，则根据本发明实施方案的吸附剂的NOx吸附性能可能降低到与常规NOx吸附剂类似的程度。而由于本发明实施方案的吸附剂的NOx吸附性能通常在被负载金属的20重量份的量时饱和，因此以超过20重量份的量加入被负载金属可能导致NOx吸附性能的平台。
通过将含被负载金属的化合物溶于某溶液中、用预定量的所获溶液浸渍所述选择的金属氧化物、并煅烧被浸渍的金属氧化物，可以实现被负载金属在所述选择的金属氧化物上的负载。或者，可以通过使被负载金属的硝酸盐和所述选择的金属氧化物的构成金属的硝酸盐的水溶液共沉淀，由此制备氧化物前体，并煅烧该氧化物前体，从而将被负载金属负载在所述选择的金属氧化物上。
可以将根据本发明实施方案的NOx吸附剂放置在废气通道中废气净化催化剂(例如三效催化剂或NOx吸附/还原催化剂)的上游或下游。例如，如果NOx吸附剂包含CeO2作为载体、Pd作为负载金属，则NOx与NOx吸附剂在约300℃分离，并且所有NOx在约500℃或更高的温度排放。因此，当NOx吸附剂位于废气通道中废气净化催化剂的上游时，在废气的温度(300℃或更高)，NOx从NOx吸附剂上放出，进入废气净化催化剂(其已被加热至高于催化剂的活化温度)中，并被该废气净化催化剂净化。
另一方面，当NOx吸附剂位于废气净化催化剂的下游时，在废气的温度达到约300℃或更高之后从NOx吸附剂上放出的NOx优选返回废气净化催化剂的上游，并被该废气净化催化剂净化。
实施例
下面参考下述示例(包括对比例和测试例)详细解释本发明。
(实施例1)
用预定量的具有给定浓度的硝酸钯水溶液浸渍Fe2O3粉末，在约120℃用约2小时蒸发至干，在约500℃煅烧约2小时，制备NOx吸附剂。在本发明的这个试验方案中，负载在Fe2O3粉末上的Pd的量为约5重量％。
通过规定的方法将所述NOx吸附剂粉末制粒，将一定量的粒装入评测装置。在含约100ppm NO的N2气在室温循环约8分钟后，使用车辆废气分析系统测量吸附在NOx吸附剂上的NO的量。结果显示在图2中。
(对比例1)
进行与实施例1中所述基本相同的过程，不同之处在于通过规定的方法仅将Fe2O3粉末(无Pd)制粒。结果显示在图2中。
(实施例2)
以与实施例1中所述基本相同的方式制备NOx吸附剂粉末，不同之处在于用CeO2粉末代替Fe2O3粉末。根据实施例1中描述的方法测量吸附在NOx吸附剂上的NO的量。结果显示在图2中。
(实施例3)
以与实施例1中所述基本相同的方式制备NOx吸附剂粉末，有两处不同：用CeO2粉末代替Fe2O3粉末，用硝酸银水溶液代替硝酸钯水溶液。负载在CeO2粉末上的Ag的量为约5重量％。根据实施例1中描述的方法测量吸附在NOx吸附剂上的NO的量。结果显示在图2中。
(对比例2)
进行与实施例1中所述基本相同的方法，不同之处在于通过规定的方法仅将实施例2中所用的CeO2粉末(无Pd)制粒。结果显示在图2中。
(实施例4)
以与实施例1中所述基本相同的方式制备NOx吸附剂粉末，不同之处在于用Co3O4粉末代替Fe2O3粉末。根据实施例1中描述的方法测量吸附在NOx吸附剂上的NO的量。结果显示在图2中。
(对比例3)
进行与实施例1中所述基本相同的方法，不同之处在于通过规定的方法仅将实施例4中所用的Co3O4粉末(无Ag)制粒。结果显示在图2中。
<评测>
由图2可以看出，在各选择的金属氧化物粉末上负载Pd或Ag增加了吸附在各NOx吸附剂上的NO的量。即，与在对比例1至3中制备的NOx吸附剂相比，在实施例1至4中制备的NOx吸附剂在室温表现出大为提高的NOx吸附性能。
<测试例1>
制备三种具有0.75、0.45和0.39的不同的Ce与Zr摩尔比的CeO2-ZrO2复合氧化物粉末和Al2O3粉末，然后根据实施例1中描述的步骤将约5重量％的Pd负载在它们上面。通过XPS观察负载在金属氧化物粉末上的Pd的状态。结果显示在图3中。CeO2-ZrO2复合氧化物在图3中简称为“CZ”。
图3表明，CeO2含量越高，对应于PdO2键的峰就越高。该图还表明，CeO2含量越低，由PdO键产生的峰就越高。这些结果说明，负载在CeO2上的Pd以四价过氧化形式(PdO2)存在，并具有极高的氧化活性。随着CeO2含量增大，以过氧化形式存在的Pd的量增大。因此，很明显，Pd捕获了CeO2提供的氧。
<测试例2>
在NO吸附到NOx吸附剂上之后，根据实施例1描述的步骤获取在实施例4和对比例3中制备的NOx吸附剂的FT-IR光谱。图谱显示在图4中。
在对比例3制备的NOx吸附剂的光谱中观察到的主峰是对应于存在NO3 -自由离子的吸收峰(约1400cm-1、1040
Figure A20068004666600091
±20cm-1和825cm-1)、对应于Co-NO2键的吸收峰(约1410
Figure A20068004666600092
±10cm-1、1340
Figure A20068004666600093
±10cm-1和835
Figure A20068004666600094
±10cm-1)和对应于存在ONO-自由离子的吸收峰(约1330cm-1、1260cm-1和830cm-1)。
另一方面，在实施例4制备的NOx吸附剂中观察到的主峰是对应于Co-O-NO2键的吸收峰(约1490
Figure A20068004666600095
±10cm-1、1280
Figure A20068004666600096
±10cm-1、1010cm-1和800cm-1)。
总之，吸附到各NOx吸附剂上的NO的状态根据Pd是否负载在各金属氧化物上而变化。在实施例4制备的NOx吸附剂中观察到对应于Co-O-NO2键的吸收峰，表明NO被氧化为NO2，然后NO2即使在不存在氧的情况下也被吸附到金属氧化物上。
基于测试例1的结果，可认为Pd由于捕获了来自Co3O4的氧而被转化为过氧化形式(即PdO2)。NO由于捕获了来自Pd(其处于过氧化形式)的氧而被氧化为NO2，然后NO2被吸附到NOx吸附剂上。NOx吸附剂的NOx吸附机理显示在图1中。
尽管已描述了本发明的具体实施方案，但本领域技术人员可清楚地认识到，在不偏离本发明的实质和所附权利要求书限定的保护范围的情况下，可以作出诸多变化和改变。

Claims (4)

1.常温NOx吸附剂，该NOx吸附剂在室温范围的常温吸附NOx，包含：
载体；和
负载在所述载体上的金属，
其中所述载体包含金属氧化物，该金属氧化物由至少一种选自Co、Fe、Cu、Ce、Mn元素及其两种或以上的元素组合的氧化物构成；且所述被负载的金属包含至少一种选自Cu、Co、Ag、Pd元素及其两种或以上的元素组合，并且，所述被负载的金属不同于构成所述载体的金属氧化物中的金属。
2.根据权利要求1的NOx吸附剂，其中所述被负载的金属至少包含Ag和Pd中之一。
3.根据权利要求1或2的NOx吸附剂，其中所述金属氧化物由至少一种选自Co、Fe、Ce元素及其两种或以上的元素组合的氧化物构成。
4.根据权利要求1或2的NOx吸附剂，其中以重量百分比计算时，相对于载体中的金属氧化物的量，被负载的金属负载量为百分之一至二十。
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Open date: 20081217