CN105636673A - Co和hc低温氧化催化剂 - Google Patents

Co和hc低温氧化催化剂 Download PDF

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CN105636673A
CN105636673A CN201480055046.1A CN201480055046A CN105636673A CN 105636673 A CN105636673 A CN 105636673A CN 201480055046 A CN201480055046 A CN 201480055046A CN 105636673 A CN105636673 A CN 105636673A
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catalyst
platinum
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palladium
cerium oxide
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R·霍耶
F·温
E·米勒
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Umicore AG and Co KG
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Abstract

本发明提供了一种位于承载体上、用于去除稀空燃比内燃机废气中的一氧化碳和烃类的催化剂，该催化剂在一种或多种耐火载体材料上具有铂和/或钯并且还包含氧化铈，并且所述催化剂的特征在于，经过250℃下还原处理并经过CO吸附后，在漫反射傅立叶变换红外光谱(DRIFTS)中呈现特定的峰；本发明还涉及使用所述催化剂去除稀空燃比内燃机废气中的一氧化碳和烃类的方法。

Description

CO和HC低温氧化催化剂
本发明涉及一种催化剂，该催化剂用于在很低的温度下去除稀空燃比(lean-operated)内燃机(如柴油发动机)废气中的一氧化碳和烃类，以及使用所述催化剂的方法。
用于去除柴油机和稀空燃比内燃机废气中的污染气体一氧化碳(CO)和烃类(HC)的氧化催化剂在现有技术中是公知的，并且主要基于铂和氧化铝。柴油氧化催化剂的例子可见于专利申请DE10308288A1、DE19614540A1、DE19753738A1、DE3940758A1、EP0427970A2和DE4435073A1。它们用柴油废气中包含的大量氧将所述污染气体氧化成二氧化碳(CO2)和水蒸气。WO2013/149881中描述了用于氧化一氧化碳和烃类的含氧化铈催化剂。
作为CO2优化的一部分，未来柴油发动机的废气温度将越来越低，这将导致HC和CO的转化更加困难。通常只有在市区外的驾驶条件下，NEDC循环才能超过200℃的温度，并且大部分的转化必须在<150℃的温度下进行，以符合排放限制。这需要催化剂的CO起燃温度T90(转换率为90％时的温度)<150℃。当前的柴油氧化催化剂老化后通常无法再达到这一要求，因此急需改进。
令人惊奇的是，现已发现，除了铂和/或钯以外还包含氧化铈的柴油氧化催化剂，其起燃温度明显更低，并且吸附CO后在漫反射傅立叶变换红外光谱(DRIFTS)中呈现特定的峰。
因此，本发明涉及一种位于承载体上的催化剂，用于去除稀空燃比内燃机废气中的一氧化碳和烃类，该催化剂：
(i)具有在一种或多种耐火载体材料上的铂，或者铂和钯，并且
(ii)还包含氧化铈，
其特征在于，经过250℃下还原处理并吸附CO后，在漫反射傅立叶变换红外光谱(DRIFTS)中波数2906cm-1(±5cm-1)、2879cm-1(±5cm-1)和2847cm-1(±5cm-1)处呈现特定的峰，并且其中2879cm-1和2906cm-1处的峰高比以及2847cm-1和2906cm-1处的峰高比均大于0.4。
通常，由耐火载体材料承载的铂，或者铂和钯各自相对于组分(i)的量为0.5重量％至10重量％，优选地为1至5重量％。
在本发明的一个实施例中，组分(i)包含铂和钯。在这种情况下，钯的量(例如)选择为使得Pt:Pd的重量比为1:1至20:1。
对于承载铂，或者铂和钯的组分(i)的耐火载体材料，本领域的技术人员所熟悉的用于此类目的的所有材料都是合适的。此类材料具有30至250m2/g(优选地100至200m2/g)的BET表面(根据DIN66132确定)，具体包括氧化铝、氧化硅、氧化镁、氧化钛、氧化铈、沸石，以及它们的混合物或混合氧化物。
优选氧化铝、镁/铝混合氧化物以及铝/硅混合氧化物。如果使用氧化铝，则特别优选其例如采用氧化镧来稳定。
采用已知方法，例如使用水溶性铂或钯化合物按照初湿浸渍法，实现在耐火载体上涂覆铂或钯。
在本发明的一个实施例中，氧化铈包括氧化铈比例>99重量％的非掺杂氧化铈。具体地讲，新鲜(即未老化)氧化铈的BET值(根据DIN66132确定)应大于并接近90m2/g。
在本发明的另一个实施例中，氧化铈以掺杂形式存在或者作为与(例如)氧化锆、氧化铝、氧化镧和/或氧化镨的混合氧化物。具体地讲，掺杂形式或混合氧化物中的氧化铈比例为80至99重量％。
具体地讲，在本发明的催化剂中，氧化铈相对于承载体体积的量为50至150g/L。
在250℃下经还原处理后，本发明的催化剂显示出所描述的DRIFTS峰。这种处理优选地采用三次5秒的燃料脉冲来实现，所述5秒燃料脉冲在250℃下的λ为0.95。如果本发明的催化剂，例如在>400℃的温度下，暴露在氧化环境中，那么可通过还原处理使其再活化。这意味着，如果所述DRIFTS峰已在氧化环境的影响下消失，那么在还原处理后，它们将再次在波数2906cm-1、2879cm-1和2847cm-1处出现。
漫反射傅立叶变换红外光谱(DRIFTS)在文献中已有描述，并且为本领域的技术人员所熟知；参看(例如)CatalysisToday155(2010)164-171(《今日催化》，2010年，第155卷，第164-171页)和CatalysisToday68(2001)263-381(《今日催化》，2001年，第68卷，第263-381页)。
在DRIFTS中，借助反射镜将IR辐射集中到待测试材料的粉末状样品上，由此通过与该样品相互作用产生反射、衍射、折射、透射和吸收的叠加。散射IR辐射的一部分离开DRIFTS室，经由另外的反射镜被传至检测器。该方法使得在接近实际条件下检测室中的粉末样品和检测吸附物质的表面络合物成为可能。
根据本发明，经250℃下还原处理以及CO吸附后，借助DRIFTS观察到催化剂样品表面甲酸盐物质的形成。结果，本发明的催化剂在波数2906cm-1、2879cm-1和2847cm-1处有三个峰，其中2879cm-1处与2906cm-1处以及2847cm-1处与2906cm-1处的峰高比大于0.4。
在本发明催化剂的一个实施例中，其包含NOx储存组分，具体地讲，该储存组分包括碱或碱土化合物，例如氧化钡或氧化锶。具体地讲，相对于承载体的体积，所述NOx储存组分的量为5至50g/L。此外，其通常承载于高表面积耐火氧化物上，(例如)氧化铝、氧化镁和镁/铝均匀混合氧化物可用于所述高表面积耐火氧化物。
此外，储存组分也可承载于氧化铈或铈混合氧化物上。
仅需混合各组分并以载体涂料(washcoat)的形式施用于承载体，即可获得本发明的催化剂。
在后续的250℃下还原处理以及CO吸附后，本领域的技术人员可通过常规DRIFTS测量确定催化剂是否显示出所要求的峰并具有所要求的峰高比，并由此确定其是否与本发明相符。已发现，所要求的DRIFTS峰是由于催化剂表面形成甲酸盐物质而产生的，并且特别依赖于所使用的氧化铈。
一般说来，在铂的量一定，氧化铈的量与钯的量之比大的情况下，催化剂显示出具有所要求峰高比的所要求的峰。
所有用于非均相催化剂的已知承载体都基本上适合作为惰性催化承载体。由陶瓷和金属制成的整体和类整体流式蜂窝结构以及颗粒过滤基体通常被用于清洁柴油发动机的废气，因而是优选的。堇青石、钛酸铝或碳化硅制成的陶瓷流式蜂巢结构和陶瓷壁流式过滤基体是尤其优选的。
用本发明的催化剂涂覆承载体是通过已知的方式实现的，具体地讲是将含有本发明催化剂的组分或其前体的涂料悬浮液(“载体涂料”)施用于承载体上，然后进行干燥和煅烧。所述的施用可根据已知的浸渍、吸收和/或抽吸工艺来实现。
含本发明催化剂的用于涂覆承载体的载体涂料优选地包括水性悬浮液，所述水性悬浮液除了任何必要的辅助材料以外，还视情况包含涂覆有铂和/或钯的耐火载体材料(组分(i))、氧化铈(组分(ii))以及NOx储存组分。
本发明的催化剂可根据已知方式单独地或作为催化剂系统的组分使用，用于去除稀空燃比内燃机废气中的一氧化碳和烃类。
本发明因此还涉及一种方法，用于去除稀空燃比内燃机废气中的一氧化碳和烃类，其特征在于使所述废气经过本发明的催化剂。
以下实例中所检测的催化剂由不同组分构成。这些组分都各自被加工成水性涂覆悬浮液，通过浸渍工艺涂覆流式蜂巢结构，所述流式蜂巢结构由堇青石制成，巢室密度为62cm-2(单位横截面积上蜂巢结构的流道数)。干燥经涂覆的蜂巢结构，随后在500℃下于空气中煅烧2小时，由此获得的成品催化剂在实验室模型气体系统中进行人工老化后，检测其CO起燃行为。为了达到老化的目的，催化剂在800℃的温度下于水热环境(即氮气中含10体积％的O2和10体积％的H2O)中保存16小时。
测试条件：
在以下实例和比较例的实验室模型气体系统中测定了经热预处理(“老化”)的催化剂的CO起燃行为。
测试之前，催化剂在800℃下于含有10体积％的O2和10体积％的H2O的N2中经受16小时热预处理。
为了测试CO转化活性，依序将试样安放在模型气体系统的反应器中，并使其经受以下测试工序：
1.为了表示典型的柴油机工况(其中催化剂仅与稀燃废气接触)，在废气混合物“条件1”(即加热速率为7.5℃每分钟)下将样品加热至550℃，然后冷却至80℃。
2.随后，为了测定CO起燃行为，在废气组合物中将催化剂加热至550℃用于起燃，加热速率为7.5℃每分钟。根据公式
CO转化率[％]＝100％×(c(CO)进–c(CO)出)/c(CO)进
计算CO转化率，其中
c(CO)进指催化剂流入处CO的浓度，而
c(CO)出指催化剂流出处CO的浓度。
3.为了表示CO起燃行为，根据“条件2”检测样品三次，所述“条件2”在下文中也被称为还原处理，其包括200秒的“稀燃”阶段和后续的5秒“浓燃(rich)”阶段。
4.冷却至80℃后，根据上述起燃工序再次测定CO转化率。
先对催化剂样品进行磨碎，以用于DRIFTS测量。N2在所有测量中均用作惰性气体，其中流经DRIFTS室的总体积恒定在6Lh-1。
对于还原预处理，于25℃下在DRIFTS室中先用10％CO冲洗经磨碎的催化剂样品2分钟，然后在250℃下用10％H2处理该催化剂样品10分钟，随后在25℃下向室中施加10％CO6分钟，最后再次在25℃下用N2冲洗该催化剂样品6分钟。在步骤4后记录光谱(分辨率：4cm-1，扫描时间：12s，KBr为背景)作为结果。对于氧化预处理，将H2换成O2即可。
还原预处理：
步骤 气体 T，℃ t,min
1 含10％CO的N2 25 2
2 含10％H2的N2 250 10
3 含10％CO的N2 25 6
4 N2 25 6
氧化预处理：
步骤 气体 T，℃ t,min
1 含10％CO的N2 25 2
2 含10％O的N2 250 10
3 含10％CO的N2 25 6
4 N2 25 6
实例1(样品催化剂K1)
为了生产样品催化剂K1，将镧稳定的氧化铝混入水中形成悬浮液，其中La2O3相对于混合氧化物的总重量为3重量％，所述混合氧化物此前已以“初湿浸渍法”涂覆有来自乙酸四胺合铂的铂。将硝酸钯形式的钯注入该悬浮液并最终与相对于催化剂体积150g/L的高表面积氧化铈混合，所述高表面积氧化铈中氧化铈含量为100重量％。随后，通过浸渍法用该悬浮液涂覆流式蜂巢结构，所述流式蜂巢结构由堇青石制成，巢室密度为62cm-1。然后，干燥该蜂巢结构，并在500℃下于空气中煅烧2小时。由此产生包含3571.5g/m3(100g/ft3)铂和714.3g/m3(20g/ft3)钯的K1催化剂。
比较例1(比较催化剂VK1)
根据实例1中所述的工序将涂有Pt的La稳定氧化铝施用于蜂巢结构。由此产生包含3571.5g/m3(100g/ft3)铂的比较催化剂VK1。
实例2(样品催化剂K2)
为了生产Pt基氧化催化剂，将氧化铈含量为100重量％的市售高表面积氧化铈和相对于混合氧化物的总重量具有3重量％La2O3的镧稳定氧化铝与水混合形成悬浮液，所述混合氧化物此前已以“初湿浸渍法”涂覆有来自乙酸四胺合铂的铂。另外，将硝酸钯形式的钯注入该悬浮液。随后，通过浸渍法用该悬浮液涂覆流式蜂巢结构，所述流式蜂巢结构由堇青石制成，巢室密度为62cm-1。然后，干燥该蜂巢结构，并在500℃下于空气中煅烧2小时。由此获得包含178.57g/m3(5g/ft3)铂和107.14g/m3(3g/ft3)钯的催化剂K2。
实例3(样品催化剂K3)
与实例2类似，生产了一种催化剂，但该催化剂包含氧化铈含量为85重量％的市售掺杂氧化铈，而非包含氧化铈含量为100重量％的氧化铈。该氧化铈包含氧化镧、氧化镨和氧化铝各5重量％作为稳定剂。
比较例VK2
与实例2类似，生产了一种另外的催化剂，该催化剂包含另一种市售氧化铈，该氧化铈的氧化铈含量为85重量％，并由氧化镧、氧化镨和氧化硅各5重量％来稳定。
图1示出了在温度最高至500℃的温度下于氧化环境(条件1；细线)中预处理后以及3次在250℃下于还原环境(条件2；粗线)中预处理5s后，样品催化剂K1和比较催化剂VK1的CO转化率与温度的关系。
VK1的转化行为与预处理的关系相对较弱，而经过在还原环境中预处理，样品催化剂K1的CO转化活性明显提高了，转化率达90％的温度T90降至98℃。
图2中示出了在3000-2600cm-1范围内的CO吸附后催化剂K1和VK1的DRIFTS(漫反射傅立叶变换红外光谱)测量结果，该测量结果与表面上甲酸盐物质的形成有关。氧化预处理(浅色曲线)后的两种催化剂均未形成峰，而在还原预处理(深色曲线)后，两种催化剂的光谱有明显的区别。虽然使用比较催化剂VK1时没有形成甲酸盐物质(仅在波数2906cm-1处可辨认出一个峰)，但波数2879cm-1和2847cm-1处的峰表示样品催化剂1存在反应中心。
图3示出了本发明的样品催化剂K2和K3的CO转化率以及比较催化剂VK2的CO转化率。虽然所有催化剂都具有相似的组成，但可明显看出还原预处理后转化率的差异。其中，K2和K3的T90值为85℃和140℃，而VK2的T90值为215℃。还原预处理和CO吸附后的对应DRIFTS光谱在图4中示出。(新鲜样品的曲线也包括于此。需要移除这些曲线。)本发明的催化剂K2和K3在波数2906cm-1、2879cm-1和2847cm-1范围内明显形成了峰，而在比较催化剂VK2中无法辨认出这些峰。因此，在CO吸附后出现以上所列的DRIFTS峰是本发明催化剂的关键。
下表汇总了所述结果：

Claims (7)

1.一种催化剂，所述催化剂位于承载体上，用于去除稀空燃比内燃机废气中的一氧化碳和烃类，所述催化剂
(i)在一种或多种耐火载体材料上具有铂，或者铂和钯，并且
(ii)还包含氧化铈，
其特征在于，经过250℃下还原处理并经过CO吸附后，在漫反射傅立叶变换红外光谱(DRIFTS)中波数为2906cm-1(±5cm-1)、2879cm-1(±5cm-1)和2847cm-1(±5cm-1)处呈现峰值，并且其中2879cm-1和2906cm-1处的峰高比以及2847cm-1和2906cm-1处的峰高比均大于0.4。
2.根据权利要求1所述的催化剂，其特征在于，所述铂，或者铂和钯的量相对于所述组分(i)为0.5至10重量％。
3.根据权利要求1和/或2所述的催化剂，其特征在于，所述铂，或者铂和钯的量相对于所述组分(i)为1至5重量％。
4.根据权利要求1至3中一项或多项所述的催化剂，其特征在于，所述催化剂包含铂和钯，并且Pt:Pd的重量比为1:1至20:1。
5.根据权利要求1至4中一项或多项所述的催化剂，其特征在于，使用氧化铝、氧化硅、氧化镁、氧化钛、氧化铈、沸石，或者它们的混合物或混合氧化物作为组分(i)的耐火基体材料。
6.根据权利要求1至5中一项或多项所述的催化剂，其特征在于，氧化铈相对于所述承载体体积的含量为50至150g/L。
7.一种用于去除稀空燃比内燃机废气中的一氧化碳和烃类的方法，其特征在于，所述废气经过根据权利要求1至6中一项或多项所述的催化剂。
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WO2015059164A1 (de) 2015-04-30
KR20160077115A (ko) 2016-07-01
DE102013221423A1 (de) 2015-04-23
US9757712B2 (en) 2017-09-12
US20160236180A1 (en) 2016-08-18

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