CN111278537A - 废气净化装置 - Google Patents
废气净化装置 Download PDFInfo
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- CN111278537A CN111278537A CN201880069964.8A CN201880069964A CN111278537A CN 111278537 A CN111278537 A CN 111278537A CN 201880069964 A CN201880069964 A CN 201880069964A CN 111278537 A CN111278537 A CN 111278537A
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- 238000000746 purification Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 239000003426 co-catalyst Substances 0.000 claims abstract description 32
- 238000002485 combustion reaction Methods 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 96
- 239000000463 material Substances 0.000 claims description 56
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
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- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 70
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
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Abstract
本实施方式的废气净化装置(1)设于内燃机的废气流路(100)。废气净化装置(1)具备蜂窝催化剂(10)与PM捕集用过滤器(20)。蜂窝催化剂(10)通过在由助催化剂构成并且具有蜂窝结构的第一基材(11)担载催化剂而成。PM捕集用过滤器(20)构成为,位于比该蜂窝催化剂(10)靠废气下游侧(X2)的位置,并且由具有蜂窝结构的第二基材(21)构成并能够捕集PM。
Description
相关申请的相互参照
本申请基于2017年11月3日提出申请的日本申请第2017-213339号,在此引用其记载内容。
技术领域
本公开涉及废气净化装置。
背景技术
作为内燃机的废气净化装置,在废气流路内设置了通过催化剂反应净化废气的催化剂过滤器、以及捕集颗粒状物质(Particulate Matter:PM)的PM过滤器。而且,通过将催化剂过滤器与PM过滤器串联配置,将PM过滤器设于靠近内燃机的位置,使利用内燃机的排热将堆积于PM过滤器的PM烧掉的自然再生成为可能。
例如,在专利文献1中,公开了在第一蜂窝基材上担载了三元催化剂的蜂窝催化剂、以及对第二蜂窝基材中的开口面的一部分进行封孔而成的封孔蜂窝结构体串联排列而设置的废气净化装置。该废气净化装置通过封孔蜂窝结构体来捕集废气所含的PM。
另外,若三元催化剂的催化剂内部的A/F(空燃比)偏离理论配比(stoichiometric),则NOx的净化率、即NOx排放恶化。鉴于此,通过使用A/F传感器进行反馈控制来维持理论配比。除此之外,还进行了将储存释放氧的氧吸藏材料作为助催化剂涂覆在蜂窝催化剂来将催化剂内部的A/F维持在理论配比。
现有技术文献
专利文献
专利文献1:日本专利第5584487号公报
发明内容
在上述构成中,若在内燃机加速时等A/F大幅变动,则难以将三元催化剂的催化剂内部维持在理论配比,NOx排放恶化而废气净化作用降低。为了消除这种情况,需要增加助催化剂的涂覆量来储存吸收过剩、不足的氧。然而,若增加助催化剂的涂覆量,则蜂窝催化剂的热容量增加而预热性能降低。其结果,特别是引起内燃机启动时的NOx排放的恶化。另一方面,若延长蜂窝催化剂而使助催化剂的涂覆量增加,则由于搭载空间的限制,封孔蜂窝结构体变短,PM捕集率降低,并且压损增加而导致内燃机的输出的降低。因此,在谋求PM的捕集率的提高、净化作用的提高、并且压损上升的抑制的方面存在改善的余地。
本公开将提供一种可实现PM的捕集率的提高、压损上升的抑制以及废气净化作用的提高的废气净化装置。
本公开的一方式为一种废气净化装置,设于内燃机的废气流路,其中,该废气净化装置具备:
蜂窝催化剂,在由助催化剂构成并且具有蜂窝结构的第一基材担载催化剂而成;以及
PM捕集用过滤器,位于比该蜂窝催化剂靠废气下游侧的位置,并且由具有蜂窝结构的第二基材构成,并构成为能够捕集PM。
在上述废气净化装置中,构成蜂窝催化剂的第一基材由助催化剂构成。因此,能够在维持高氧吸藏量(OSC量)的同时,减少或不需要涂覆于第一基材的助催化剂。由此,能够在维持废气净化作用的同时,减少蜂窝催化剂的热容量而实现预热性能的提高。由此,特别是能够提高内燃机启动时的废气净化作用。而且,由于废气净化装置是在蜂窝催化剂的下游具备PM捕集用过滤器的串联型,因此容易通过内燃机的排热使PM捕集用过滤器自然再生,能够实现PM的捕集率的提高、压损上升的抑制。
如以上那样,根据本公开,能够提供一种可实现PM的捕集率的提高、压损上升的抑制以及废气净化作用的提高的废气净化装置。
另外,权利要求书所记载的括号内的附图标记表示与后述的实施方式所记载的具体手段的对应关系,并非限定本公开的技术范围。
附图说明
关于本公开的上述目的以及其他目的、特征、优点,通过参照添附的附图和下述的详细记述而更加明确。其附图为,
图1是表示实施方式1中的废气净化装置的构成的概念剖面图,
图2是表示实施方式1中的蜂窝催化剂的构成的概念图,
图3是表示实施方式1中的PM捕集用过滤器的构成的概念图,
图4的(a)是以往构成中的废气净化装置的概念剖面图,(b)是以往构成中的催化剂过滤器的概念剖面图,
图5是表示确认试验1的结果的图,
图6是表示确认试验3的结果的图,
图7是表示确认试验3的结果的图,
图8是表示确认试验4的结果的图,
图9是表示确认试验6的结果的图。
具体实施方式
(实施方式1)
使用图1~图9对上述废气净化装置的实施方式进行说明。
如图1所示,本实施方式的废气净化装置1设于内燃机的废气流路100,并且具备蜂窝催化剂10和PM捕集用过滤器20。
如图2所示,蜂窝催化剂10通过在由助催化剂构成并且具有蜂窝结构的第一基材11担载催化剂而成。
如图1所示,PM捕集用过滤器20构成为,位于比蜂窝催化剂10靠废气下游侧X2的位置,并且由具有蜂窝结构的第二基材21构成并能够捕集PM。
以下,使用图1~图3对本实施方式的废气净化装置1进行详细叙述。如图1所示,废气净化装置1具有金属制的外壳30。在外壳30内,保持有蜂窝催化剂10以及PM捕集用过滤器20。外壳30的第一端部31开口,并连接于废气流路100的上游侧X1。外壳30的第二端部32开口,并连接于废气流路100的下侧X2。由此,废气F1流入废气净化装置1,被净化而作为废气F2排出。
构成图2所示的蜂窝催化剂10的第一基材11由助催化剂构成。例如,第一基材11能够由以助催化剂为主要成分的原料粒子、以及包含将该原料粒子彼此接合的无机粘合剂的材料构成。作为助催化剂,能够采用氧化铝颗粒,氧化铈-氧化锆(日文:セリア-ジルコニア)复合氧化物等。如图2所示,第一基材11具有蜂窝结构。蜂窝结构是指,具有划分形成成为废气等的流路的多个单元(cell)12的多孔质的隔壁11a、以及位于隔壁的最外周的外周壁11b的结构。
第一基材11的气孔率能够通过变更助催化剂与无机粘合剂的配合比例而变化。例如,第一基材11的气孔率能够为20%以上,优选为50%以上。
在第一基材11中担载有未图示的催化剂。在本实施方式中,作为催化剂,采用了含有Pt、Pd、Rh的三元催化剂。也可以在第一基材11上与催化剂一起涂覆助催化剂。
如图3所示,构成PM捕集用过滤器20的第二基材21具有蜂窝结构。第二基材21的形成材料并未被特别限定,能够采用陶瓷等。第二基材21具有划分形成多个单元22的多孔质的隔壁21a。在第二基材21的两端面设有对单元22的端部进行封孔的封孔部23。封孔部23按每个单元22设于某一方的端部,并且在相邻单元22彼此中设于相互相反的端部。
(评价试验1)
接下来,进行了以下的评价试验1。在评价试验1中,分别计算了后述的比较例1~5中的PM捕集率、压损、NOx排放、氧吸藏量(OSC量)。
PM捕集率的计算通过如下方式进行:在2.0L汽油增压直喷车辆中,将废气净化装置搭载于涡轮增压器的后级,作为由底盘测功机进行的试验,在作为欧州限制运转模式的WLTC模式下行驶,计测其总排出颗粒个数浓度(PN)。
NOx排放的计算通过如下方式进行:在2.0L汽油直喷车辆中,在WLTC模式下行驶,计测氮氧化物的排出量。
关于压损的计算,首先,在发动机的台架试验中对废气净化装置实施加速Ash堆积的耐久试验,使Ash在废气净化装置堆积40g。之后,通过如下方式进行:在2.0L汽油增压直喷车辆中,在排气系统安装Ash堆积后的废气净化装置,在吸入空气量为100g/s的条件下使发动机运转,计测压力的损失。
关于OSC量的计算,首先,通过2.5L的发动机台架,为±2.0Φ%。赋予1Hz的扰动,改变目标A/F,计算NOx/CO的排出成为最小值的点,作为催化剂理论配比A/F。这里,所谓Φ是等量比,是将理论空燃比除以实际的空燃比而得的值。之后,将A/F步长根据计算出的催化剂理论配比设为±5Φ%,使稀气体、浓气体交替地流向催化剂,并将循环保持时间设为60,测定了催化剂前后的氧浓度。然后,计算了目标A/F从浓侧变化为稀侧时的3个周期的平均的氧吸藏量,作为OSC量。
作为比较例1~5,使用了图4(a)所示的以往构成的废气净化装置9。如图4(a)所示,废气净化装置9在外壳930内作为上游侧的Fr侧X1设有Fr催化剂910,在作为Fr催化剂910的下游侧的Rr侧X2设有PM过滤器920。外壳930的上游侧开口部931连接于废气流路100的上游侧X1,下游侧开口部932连接于废气流路100的下游侧。如图4(b)所示,Fr催化剂910具有陶瓷制的蜂窝结构体911,在其隔壁911a的壁面涂覆有助催化剂913。另外,虽未图示,还涂覆有三元催化剂。因此,Fr催化剂910的单元912比图2所示的实施方式1的废气净化装置1中的单元12窄。废气净化装置9中的PM过滤器920具有与实施方式1的情况同等的构成,在PM过滤器920涂覆有三元催化剂以及助催化剂。将比较例1~5的废气净化装置9中的Fr侧以及Rr侧的基材的构成和催化剂的涂覆量等示于表1,将试验结果示于后述的表8。
另外,表中的“Fr基材”是指Fr催化剂910的基材。而且,在Fr基材的栏中,“三元涂覆量”是涂覆在Fr催化剂910的助催化剂的量,“PGM量”是铂族元素的量,“Fr的涂覆量”是Fr催化剂910中的助催化剂的量。在Fr基材由助催化剂构成的情况下,所谓“三元涂覆量”,表示Fr基材的重量。
另外,表中的“Rr基材”是指PM过滤器920的基材。而且,在Rr基材的栏中,“三元涂覆量”是涂覆在PM过滤器920的助催化剂的量,“PGM量”是铂族元素的量。
另外,表中的“Fr基材+Rr基材”是指,Fr催化剂910与PM过滤器920的合计。而且,在Fr基材+Rr基材的栏中,“Fr涂覆量”是将Fr催化剂910中的第一基材11所含的助催化剂与进一步涂覆了助催化剂的情况下的所涂覆的助催化剂合起来的助催化剂的量。“Rr涂覆量”是PM过滤器920中的助催化剂的量。“Fr+Rr涂覆量”是指,Fr催化剂910与PM过滤器920中的总的助催化剂的量。
[表1]
如表1所示,在比较例1~5中,变更了Fr涂覆量,Rr侧的构成彼此相同且Rr涂覆量未变更。将比较例1~5中的涂覆量与NOx排放的关系示于图5。如图5以及表8所示,在比较例1~5中,比较例3的NOx排放最低。而且,在与比较例3相比Fr涂覆量较少的比较例4以及比较例5中,OSC量不足而NOx排放增加。另一方面,在与比较例3相比Fr涂覆量较多的比较例1以及比较例2中,OSC量充足,但Fr催化剂910的热容量增大而预热性能恶化,使得NOx排放增加。另外,如表8所示,在比较例1~5中,压损均相对较大。
(评价试验2)
接下来,进行了以下的评价试验2。在评价试验2中,作为比较例6~10的废气净化装置,如表2所示,使用在具有上述的比较例3的涂覆量的以往构成的废气净化装置9中一边维持Fr侧以及Rr侧的基材的合计长度L1+L2一边变更Fr侧以及Rr侧的基材的长度L1、L2的废气净化装置9,进行了与评价试验1相同的试验。将比较例6~10的废气净化装置9中的Fr侧以及Rr侧的基材的构成等示于表2,将试验结果示于后述的表8。
[表2]
如表8所示,在Fr侧的基材与Rr侧的基材的长度L1、L2相等的比较例8中,NOx排放最低。而且,在与比较例8相比Fr侧的基材较长的比较例9以及比较例10中,伴随着Fr侧的基材的增加所涂覆的助催化剂的量增加,因此OSC量增加,但Rr侧的基材容积的减少使得PM捕集能力降低。另外,如表8所示,在比较例6~10中,压损相对较大。
(评价试验3)
接下来,进行了以下的评价试验3。在评价试验3中,作为试验例1~5,如表3所示,使用在上述的实施方式1的废气净化装置1中一边维持Fr侧的第一基材11以及Rr侧的第二基材21的合计长度L1+L2一边变更第一基材11的长度L1以及第二基材21的长度L2的废气净化装置1,进行了与评价试验1相同的试验。然后,将试验例1~5的废气净化装置1中的Fr侧以及Rr侧的基材的构成示于表3,将试验结果示于后述的表8。将试验例1~5以及上述的比较例1~10中的NOx排放与PM捕集率的关系示于图6。
[表3]
如表8所示,在试验例1~5的全部中,与比较例1~10相比压损大幅降低。另外,如表8以及图6所示,在试验例1~5的全部中,与比较例1~10相比,NOx排放降低,特别是在试验例1中,NOx排放最低,PM捕集率也充分地降低。而且,在图6中示出了,试验例1~5在整体上,相对于比较例1~10,成为向高PM捕集率且低NOx排放即图表的左上侧偏移的状态,同时实现了PM捕集率的提高与防止废气净化作用的降低。
另外,在图7中示出了,第一基材11的长度L1在试验例1~5中的第一基材11的长度L1与第二基材21的长度L2的合计长度L1+L2中所占的比率、即L1/(L1+L2)与压损的关系。如图7所示,确认到,在L1/(L1+L2)为0.5以下的范围内,压损成为足够低的值。
(评价试验4)
接下来,进行了以下的评价试验4。在评价试验4中,如下述的表4所示,作为试验例6~10,使用在上述的实施方式1的废气净化装置1中将Fr侧的第一基材11的气孔率设为60%、一边维持Fr侧的第一基材11以及Rr侧的第二基材21的合计长度L1+L2一边变更第一基材的长度L1以及第二基材的长度L2的废气净化装置1,进行了与评价试验1相同的试验。然后,将试验例6~10的废气净化装置1中的Fr侧以及Rr侧的基材的构成示于表4,将试验结果示于后述的表8。
[表4]
进而,如下述的表5所示,作为试验例11~15,使用在上述的实施方式1的废气净化装置1中将Fr侧的第一基材11的气孔率设为40%、与试验例6~10同样地一边维持Fr侧的第一基材11以及Rr侧的第二基材21的合计长度L1+L2一边变更第一基材的长度L1以及第二基材的长度L2的废气净化装置1,进行了与评价试验1相同的试验。然后,将试验例11~15的废气净化装置1中的Fr侧以及Rr侧的基材的构成示于表5,将试验结果示于后述的表8。
[表5]
然后,在图8中示出了试验例1~15、比较例1~5中的L1/(L1+L2)与NOx排放的关系。如图8以及表8所示,确认到,第一基材11的气孔率越高,NOx排放越向较少的一侧偏移。另一方面,在试验例12、13中NOx排放增加。这是因为,在第一基材11的气孔率小于50%、L1/(L1+L2)小于0.5的情况下,相对于气体穿过第一基材11的时间,气体向助催化剂的扩散恶化,从而氧的吸收释放速度变慢,助催化剂的氧吸藏功能(OSC功能)降低。
(评价试验5)
接下来,进行了以下的评价试验5。在评价试验5中,如下述的表6所示,作为试验例16~19,使用在上述的实施方式1的废气净化装置1中将Fr侧的第一基材11的气孔率设为50%、将L1/(L1+L2)设为0.5、变更了助催化剂中的氧化铈氧化锆(日文:セリアジルコニア)固溶体的比率的废气净化装置1,进行了与评价试验1相同的试验。这里,氧化铈氧化锆固溶体的比率是指,构成基材的助催化剂所含的成分的全部重量中的氧化铈氧化锆固溶体的重量的比率。然后,将试验例16~19的废气净化装置1中的Fr侧以及Rr侧的基材的构成示于表6,将试验结果示于后述的表8。另外,在上述试验例1~15中,如表3~5所示,氧化铈氧化锆固溶体的比率为30wt%。
[表6]
如表8所示,助催化剂中的氧化铈氧化锆固溶体的比率越高,OSC量越多。而且,随着氧化铈氧化锆固溶体的比率降低OSC量降低,伴随于此,NOx排放恶化。由此,确认到,若助催化剂中的氧化铈氧化锆固溶体的比率为40%以上,则可获得更高的废气净化作用。
(评价试验6)
接下来,进行了以下的评价试验6。在评价试验6中,如下述的表7所示,作为参考例1~5,在上述的以往构成的废气净化装置9中变更Rr侧的基材911中的催化剂以及助催化剂的涂覆量,进行了与评价试验1相同的试验。然后,将参考例1~5的废气净化装置中的Fr侧以及Rr侧的基材的构成示于表7,将试验结果示于后述的表8。
[表7]
如表8以及图9所示,确认到,随着增加Rr侧的基材中的催化剂的涂覆量,压损急剧增加。这是因为,Rr侧的基材的气孔、即单元被堵塞。由此,优选不在Rr侧的基材过度地涂覆催化剂。而且,根据表8以及图9所示的该评价试验6的结果,优选Rr侧的基材中的催化剂的涂覆量为100g/L以下。另外,由Rr侧的基材中的催化剂的涂覆量导致的压损的变化不受Fr侧的催化剂过滤器的构成影响,因此在上述试验例1~19中的废气净化装置1中也一样,第二基材21中的催化剂的涂覆量优选为100g/L以下。
在下述的表8中,示出上述评价试验1~6的结果。
[表8]
接下来,对本实施方式的废气净化装置1中的作用效果进行详细叙述。
根据上述废气净化装置1,构成蜂窝催化剂10的第一基材11由助催化剂构成。因此,能够在维持高OSC量的同时,减少或不需要涂覆于第一基材11的助催化剂。由此,能够维持废气净化功能,并且能够减少蜂窝催化剂10的热容量而实现预热性能的提高,特别是能够提高内燃机启动时的废气净化作用。而且,由于废气净化装置1是在蜂窝催化剂10的下游具备PM捕集用过滤器20的串联型,因此容易通过内燃机的排热使PM捕集用过滤器20自然再生,能够实现PM捕集率的提高、压损上升的抑制。
另外,在本实施方式中,在上述试验例1~3、6~8、11~13、16~19中,废气流路100中的废气F1、F2的流动方向上的第一基材11的长度L1设为第一基材11的长度L1与第二基材21的长度L2的合计的长度的一半以下。在这种情况下,能够使Rr侧的第二基材21的长度相对较长,因此可抑制压损上升,并且可维持PM捕集率。
另外,在本实施方式中,在上述试验例1~10、16~19中,第一基材11的气孔率设为50%以上。在这种情况下,可防止第一基材11变得过度致密,使气体容易向助催化剂扩散。由此,能够充分地发挥助催化剂的OSC功能,提高废气净化作用。
另外,在本实施方式中,在上述试验例1~12、14~18中,第一基材11的OSC量成为0.2g以上。在这种情况下,可确保使OSC功能可靠地发挥所需的OSC量,因此能够提高废气净化作用。
另外,在本实施方式中,在上述试验例1~17中,将第一基材11中的氧化铈氧化锆固溶体的重量比率设为30wt%以上。在这种情况下,可确保使OSC功能可靠地发挥所需的OSC量,因此能够提高废气净化作用。
另外,在本实施方式中,在上述试验例1~19中,在第二基材21涂覆有助催化剂以及催化剂。在这种情况下,整体中的OSC量增加,因此能够提高废气净化作用。
另外,在本实施方式中,如上述参考例所示,优选将第二基材21中的催化剂的涂覆量的合计设为100g/L以下。由此,可防止第二基材21的壁内的气孔被催化剂过度堵塞,能够抑制压损上升。
另外,在本实施方式中,在上述试验例1~19中,在第一基材11涂覆有助催化剂。由此,容易确保第一基材11中的OSC量,因此能够提高废气净化作用。
本公开遵照实施方式进行了记述,但可理解为本公开并不限定于该实施方式、构造。本公开还包含各种变形方式、等效范围内的变形。除此之外,各种组合、方式、以及在它们中仅包含一个要素、其以上、或其以下的其他组合、方式也落入本公开的范畴、思想范围内。
Claims (8)
1.一种废气净化装置,设于内燃机的废气流路(100),其中,该废气净化装置(1)具备:
蜂窝催化剂(10),在由助催化剂构成并且具有蜂窝结构的第一基材(11)担载催化剂而成;以及
PM捕集用过滤器(20),位于比该蜂窝催化剂10靠废气下游侧的位置,并且由具有蜂窝结构的第二基材(21)构成,并构成为能够捕集PM。
2.如权利要求1所述的废气净化装置,其中,
在上述废气流路中的废气的流动方向上,上述第一基材的长度为上述第一基材的长度与上述第二基材的长度的合计长度的一半以下。
3.如权利要求1或2所述的废气净化装置,其中,
上述第一基材的气孔率为50%以上。
4.如权利要求1~3中任一项所述的废气净化装置,其中,
上述第一基材的氧吸藏量为0.2g以上。
5.如权利要求1~4中任一项所述的废气净化装置,其中,
上述第一基材中的氧化铈氧化锆固溶体的重量比率为30wt%以上。
6.如权利要求1~5中任一项所述的废气净化装置,其中,
在上述第二基材涂覆有助催化剂以及催化剂。
7.如权利要求1~6中任一项所述的废气净化装置,其中,
上述第二基材中的上述催化剂的涂覆量的合计为100g/L以下。
8.如权利要求1~7中任一项所述的废气净化装置,其中,
在上述第一基材涂覆有上述助催化剂。
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