CN102821847A - 处理瞬时nox排放的催化剂 - Google Patents
处理瞬时nox排放的催化剂 Download PDFInfo
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- CN102821847A CN102821847A CN201080063236XA CN201080063236A CN102821847A CN 102821847 A CN102821847 A CN 102821847A CN 201080063236X A CN201080063236X A CN 201080063236XA CN 201080063236 A CN201080063236 A CN 201080063236A CN 102821847 A CN102821847 A CN 102821847A
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- molecular sieve
- catalyst
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- combination
- exhaust
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Abstract
一种多相催化剂制品,所述多相催化剂制品具有具中孔、大孔或介孔晶体结构且任选包含第一金属的第一分子筛和具有小孔晶体结构且任选包含第二金属的第二分子筛的至少一种组合;和上面或之内结合所述催化组分的整料基质,其中第一分子筛和第二分子筛的组合为掺合物、多个层和/或多个区域。
Description
本发明涉及一种包含任选金属助催化分子筛组分的选择性催化还原催化剂,所述还原催化剂用于在含氮还原剂存在下使从机动源(如,机动车贫燃内燃机)排放的废气中存在的氮氧化物(NOx)转化。
本文所用术语“选择性催化还原”(SCR)定义为用含氮还原剂使氮氧化物还原成双氮(N2)的催化过程。SCR从处理来自工业固定源应用(如热电厂)的NOx排放了解。更近来,为了处理来自机动源应用(如轿车、卡车和公共汽车)的NOx排放物,已发展了SCR技术。处理来自机动源应用的NOx的难点在于排气中存在的NOx的量是瞬时的,即,随驾驶条件改变,如加速、减速和在不同的速度行驶。机动应用排气中NOx组分的瞬时性质提出一些技术挑战,包括正确计量含氮还原剂,以还原足够的NOx,而不浪费含氮还原剂或排到大气。
实际上,SCR催化剂可吸附(或储存)含氮还原剂,因此对可利用还原剂的适合源提供缓冲。技术人员用此现象校准对排气的适合含氮还原剂注入。
因此,总起来讲,用于机动源应用的SCR催化剂广泛执行三种功能:(i)用例如氨(NH3)作为含氮还原剂转化NOx;(ii)在进气中有过量NH3时储存NH3;和(iii)在进气中没有足够NH3存在的条件下利用储存的NH3完成所需转化。
为了实际应用,例如处理来自机动NOx源的NOx排放,例如机动车,在进气条件快速变化时,合乎需要的SCR催化剂在特定温度(以保证任何过量的NH3不“泄漏”经过催化剂,并允许继续转化,如果在进气中不存在NH3)和独立于NH3填充量部分(填充量相对于饱和NH3储存能力限定)的高活性具有足够的NH3储存能力。NH3填充量可表示为在指定组条件相对于最大填充量在完全催化剂(例如,以升表示)上存在的NH3的量(例如,以克表示)。NH3吸附可根据在现有技术已知的方法测定,例如朗缪尔吸附。应了解,所有SCR催化剂的填充量不与SCR催化剂的最大NOx转化活性成正比,即,不遵循NOx转化活性在100%氨填充量增加到最大限度。实际上,具体SCR催化剂可显示在<100%填充量最大限度NOx转化率,例如<90%、<80%、<50%或<30%。
SCR催化剂的活性可取决于完全催化剂整料已暴露的NH3的量。基于分子筛的SCR催化剂可储存氨,储存容量尤其取决于气流的温度和催化剂、进气组合物、空间速度,特别是NO∶NO2比率等。在催化剂暴露于NH3开始的催化剂活性可实质上低于在催化剂具有相对高暴露或饱和暴露于NH3时的活性。对于实际机动车应用,这意味催化剂需要以适合NH3负载预载,以保证良好活性。然而,此需要提出一些重要问题。具体地讲,对于一些操作条件,不可能达到所需的NH3负载,并且此预载方法有多个限制,因为不可能知道在预载后是什么发动机操作条件。例如,如果催化剂预载NH3但随后发动机负载空闲,NH3就可能泄漏到大气。因此,在实际应用中,预储存的NH3的量必须低于对保证限制NH3泄漏最佳的量,如果发动机在需要NH3预载的高负载条件代替较低负载条件操作。
在机动应用(如汽车)上使用的SCR催化剂需要在低温操作,同时也应耐受烃。低温操作通常意味在进气中有很少的NO2,是有利于使用基于铜的SCR催化剂。然而,基于铁的SCR催化剂一般很擅长处理约50∶50NO∶NO2进气,在可能经历的高温条件也很好,要是排气系统包含催化烟灰过滤器(CSF),则布置系统,以便通过工程强制高温条件定期再生CSF(即,燃烧收集的粒状物质)。
WO 2008/132452公开一种使气体(如机动车贫燃内燃机的排气)中的氮氧化物转化成氮的方法,所述方法包括在含至少一种过渡金属的分子筛催化剂存在下使氮氧化物与含氮还原剂接触,其中分子筛为含8个四面体原子最大环大小的小孔沸石,其中至少一种金属选自Cr、Mn、Fe、Co、Ce、Ni、Cu、Zn、Ga、Mo、Ru、Rh、Pd、Ag、In、Sn、Re、Ir和Pt。适合的小孔分子筛包括(使用国际沸石协会结构委员会(the Structure Commission of the International Zeolite Association)识别的三字母编号)CHA,包括SSZ-13和SAPO-34;LEV,如Nu-3;DDR,例如Sigma-1;和ERI,包括ZSM-34。一般地讲,我们发现用于WO 2008/132452的方法的SCR催化剂显示在相对高填充量的最大NOx转化率。
WO′452解释用ZSM-5和β沸石转化机动源(如机动车)排出的排气中的NOx的某些缺陷,包括,它们在高温水热老化期间容易脱铝,导致酸性损失,尤其利用Cu/β和Cu/ZSM-5催化剂;基于β和ZSM-5的两种催化剂也受在相对低温变得吸附(被称为“焦化”)在催化剂上的烃影响,这些烃可随后在催化系统温度升高时氧化,产生显著放热,这可能热破坏催化剂。在冷起动期间在催化剂上可能吸附显著量烃的机动车柴油机应用中,这一问题特别尖锐。焦化也可减小催化活性,因为活性催化剂部位可能变得堵塞。
根据WO′452,含过渡金属的基于小孔分子筛的SCR催化剂显示比含相当过渡金属的中孔、大孔或介孔分子筛催化剂、含过渡金属的小孔分子筛催化剂显著改进的NOx还原活性,尤其在低温。它们也显示对N2的高选择性(例如低N2O生成)和优良的水热稳定性。另外,包含至少一种过渡金属的小孔分子筛比较大孔分子筛更抗烃抑制。
在利用含氮还原剂(脲,NH3前体)还原NOx的WO 2008/132452公开的某些SCR催化剂试验期间,已发现,催化剂的瞬时反应对处理瞬时机动车排气中的NOx达不到最佳。即,SCR催化剂处理瞬时改变排气组合物中NOx的能力不太理想。
SAE 2008-01-1185公开一种选择性催化还原催化剂,所述催化剂包含在流通基质整料上在接连涂覆区域中布置的单独铁沸石和铜沸石催化剂,并且铁沸石区域布置在铜沸石区域的上游。其中未给所用沸石的细节。用于组合铁沸石/铜沸石催化剂的瞬时反应(显示于图17中)的结果不利与单独使用铜沸石相比。
我们现在很惊讶地发现过渡金属/分子筛(例如沸石)催化剂的组合对NOx转化更有活性,但也具有相对快的瞬时反应。我们也发现,铁分子筛催化剂的组合可给予良好的活性,并且能耐受烃。
根据一个方面,本发明提供一种多相催化剂制品,所述催化剂制品包含:(a)催化组分,所述催化组分包括具有中孔、大孔或介孔晶体结构且任选包含约0.01至约20%重量第一金属的第一分子筛和具有小孔晶体结构且任选包含约0.01至约20%重量第二金属的第二分子筛的组合,其中所述第一金属和第二金属与分子筛的晶体框架交换或相对于分子筛的晶体框架游离,并且独立选自Cr、Mn、Fe、Co、Ce、Ni、Cu、Zn、Ga、Mo、Ru、Rh、Pd、Pt、Ag、In、Sn、Re和Ir;和(b)上面或之内结合所述催化组分的整料基质,其中所述第一分子筛和第二分子筛的组合选自掺合物、多个层和多个区域。
用于本发明的催化剂的组合类型包括两种或更多种催化剂的掺合物、其中各层由单一催化剂组成的多个层和其中各区域由单一催化剂组成的多个区域。组合特征为不能通过独立于组合作用的组成部分得到的性质。转向图4a-4d,图4a-4d显示根据本发明的不同组合的某些实施方案。图4a显示掺合物100,包括在基质102上涂覆的两种分子筛104的掺合物。与分子筛相关,本文所用术语“掺合物”是指具有相互遍布体积近似相同比例的一定体积的两种或更多种分子筛。图也显示包含由第一分子筛116组成的第一区域和包含第二分子筛118的第二区域的多个区域110的实施方案,其中第一区域和第二区域涂在基质102上,相互邻接,并且邻接所述整料基质。图也显示排气流的方向114。在图4c中显示包含第一层116和第二层118的多个层120的实施方案,其中第二层邻接所述第一层和基质两者,并且在第一层和基质之间。图4d显示两个组合130,其中第一组合为两个区域(分子筛116和掺合物104),第二组合为掺合物104。对于利用两个或更多个组合的实施方案,各组合的分子筛独立选择。虽然在图中未显示,但其它多个组合也在本发明的范围内。例如,类似于图4d但代替掺合物的布置,第二组合可以为多个层。其它多个组合包括用掺合物作为一个或多个层,用多层作为一个或多个区域等。在使用多个组合时,与排气流通过催化剂组分相关的组合的次序没有特别限制。然而,非常优选至少一个中孔、大孔或介孔分子筛总是布置在任何小孔分子筛的上游。
组合优选具有相对于第二分子筛组分的大部分第一分子筛组分。在某些实施方案中,组合包括约0.1(即,1∶10)至约1(即,(1∶1))的第一分子筛∶第二分子筛重量比的第一分子筛和第二分子筛。在某些实施方案中,第一分子筛与第二分子筛的重量比为约0.25至约0.50。在某些实施方案中,第一分子筛与第二分子筛的重量比为约0.3至约0.4。
根据另一个方面,本发明提供用其组成、流速和温度分别瞬时改变的进气中的含氮还原剂选择性催化氮氧化物转化的催化剂,所述催化剂包含第一分子筛组分和第二分子筛组分的组合,其中在联邦试验方法(Federal Test Procedure)(FTP)75循环试验的直接比较中,催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx累积转化率。
具体地讲,我们在至少一个实施方案中观察到第一分子筛组分和第二分子筛组分之间的协同关系,可这用于改进包含分子筛(例如,小孔分子筛)的SCR催化剂对NOx转化的瞬时反应,同时保持在SCR催化剂中用小孔分子筛作为组分的优点。“用含氮还原剂选择性催化进气中氮氧化物还原的催化剂”在本文中应被称为“选择性催化还原”(或“SCR”)催化剂。为了避免疑虑,包含三种或更多种分子筛的组合的SCR催化剂也在本发明的范围内。
在优选的实施方案中,催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx累积转化率,其中进入所述催化剂的进气中NO∶NO2累积摩尔比等于或小于1。在某些其它优选的实施方案中,进排气流中NO∶NO2比为约0.8至约1.2。在某些其它优选的实施方案中,进排气流中NO∶NO2比小于约0.3,而在其它优选的实施方案中,该比率大于约3。
在其它优选的实施方案中,催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx至双氮累积转化率。
本发明显著改进催化剂活性,以便与目前发展水平的SCR催化剂比较在较低NH3暴露(相对于催化剂的饱和储存容量低暴露)得到较高活性。从0氨暴露到饱和氨暴露的活性增加速率被称为“瞬时反应”。
在一个实施方案中,对于所选择条件,第一分子筛组分在比第二分子筛组分更低的NH3填充量达到最大NOx转化率。例如,第一分子筛组分的氨填充量可以为10-80%,例如20-60%或30-50%。
第一分子筛和第二分子筛可独立选自沸石和非沸石分子筛。根据国际沸石协会(International Zeolite Association)的“沸石”一般被认为是铝硅酸盐,而“非沸石分子筛”可以为与相应沸石相同框架类型(或晶体结构)的分子筛,但具有在晶格中存在的一个或多个非铝/非硅阳离子,例如磷、钴和磷两者、铜或铁。因此,例如,SSZ-13为框架类型编号CHA的沸石,而SAPO-34为共有相同CHA框架类型编号的硅铝磷酸盐非沸石分子筛。特别优选的是含铁的铝硅酸盐沸石(本文定义的非沸石分子筛),例如,含铁的ZSM5、β、CHA或FER,例如公开于WO2009/023202和EP2072128A1,这些沸石水热稳定,并且具有相对较高SCR活性。我们也有利地发现,在某些实施方案中,包含这些含铁的铝硅酸盐沸石的催化剂产生很少或不产生硝酸铵,并且显示相对较高选择性,例如低N2O。这些材料的一般SiO2/Al2O3摩尔比为30至100,SiO2/Fe2O3摩尔比为20至300,例如,20至100。
在优选的实施方案中,第一(沸石或非沸石)分子筛组分可以为包含八(8)个四面体原子最大环大小的小孔分子筛,任选选自任何表1中所列。任选第二(沸石或非沸石)分子筛组分也可以为包含八(8)个四面体原子最大环大小的小孔分子筛,并且可独立于第一分子筛组分选自任何表1中所列。
表1:应用于本发明的小孔分子筛的详细资料
在一个实施方案中,小孔分子筛可选自由ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG和ZON组成的框架类型。
具体用于处理贫燃内燃机排气(例如机动车排气)中的NOx的小孔分子筛列于表2中。
表2:用于本发明的SCR催化剂的优选小孔分子筛
结构 | 分子筛 |
CHA | SAPO-34 |
AlPO-34 | |
SSZ-13 | |
LEV | 插晶菱沸石 |
Nu-3 | |
LZ-132 | |
SAPO-35 | |
ZK-20 | |
ERI | 毛沸石 |
ZSM-34 | |
Linde型T | |
DDR | Deca-dodecasil 3R |
Sigma-1 | |
KFI | ZK-5 |
18-冠-6 | |
[Zn-Ga-As-O]-KFI | |
EAB | TMA-E |
PAU | ECR-18 |
MER | 麦钾沸石 |
AEI | SSZ-39 |
GOO | 鵝溪沸石 |
YUG | 汤河原沸石 |
GIS | P1 |
VNI | VPI-9 |
在具体的实施方案中,第二分子筛(沸石或非沸石分子筛)组分可以为中孔、大孔或介孔大小的分子筛。
在特别优选的实施方案中,第一分子筛为CuCHA材料,第二分子筛为FeBEA、FeFER、FeCHA或FeMFI(例如,ZSM-5),其中Fe经浸渍、离子交换和/或存在于分子筛的晶格内。
在本文中,“中孔”是指包含十(10)个最大环大小的分子筛,“大孔”是指包含十二(12)个四面体原子最大环大小的分子筛。介孔分子筛具有>12的最大环大小。
在本发明中用作第二分子筛的适合中孔分子筛包括ZSM-5(MFI)、MCM-22(MWW)、AlPO-11和SAPO-11(AEL)、AlPO-41和SAPO-41(AFO)、镁碱沸石(FER)、片沸石或斜发沸石(HEU)。用于本发明的大孔分子筛包括沸石Y(如ultrastable-Y(或USY))、八面沸石或SAPO-37(FAU)、AlPO-5和SAPO-5(AFI)、SAPO-40(AFR)、AlPO-31和SAPO-31(ATO)、β(BEA)、钠菱沸石(GME)、丝光沸石(MOR)和菱钾沸石(OFF)。
从WO 2008/132452中的说明了解,使用某些中孔和大孔分子筛,如ZSM-5沸石或β沸石,可导致催化剂焦化。某些中孔和大孔分子筛组分的选择可能不适合一些应用:实质上是在改进瞬时反应(一方面)和焦化问题(另一方面)之间取得平衡。然而,利用适合的排气系统设计,可减少或避免这些焦化问题,例如,在SCR催化剂的上游布置氧化催化剂,这些催化剂可转化进气中的一些烃,且另外具有焦化的中孔、大孔或介孔分子筛组分。在小孔分子筛与中孔、大孔或介孔分子筛组合的某些实施方案中,存在小孔分子筛也可能减少中孔、大孔或介孔分子筛上的焦化。此布置的另一个益处是可调节接触催化剂的进气中NO∶NO2之比,以促进在SCR催化剂上完全NOx转化。
用于本发明的分子筛可独立选自一维、二维和三维分子筛。显示三维维度的分子筛具有在所有三个结晶维度中互连的孔结构,而具有二维维度的分子筛具有只在两个结晶维度中互连的孔。具有一维维度的分子筛没有从第二结晶维度互连的孔。
用于本发明的小孔分子筛,特别是铝硅酸盐沸石,可具有2至300的二氧化硅∶氧化铝比率(SAR),任选4至200,如8至150,例如15至50或25至40。应了解,较高SAR优选提高热稳定性(尤其在水热老化后在低温的高催化活性),但这可能负面影响过渡金属交换。因此,在选择优选的材料中,可考虑SAR,以在这两种性质之间取得平衡。关于框架内铁分子筛的SAR在说明书别处讨论。
在优选的实施方案中,第一分子筛、第二分子筛或第一分子筛和第二分子筛两者包含一种或多种独立选自Cr、Mn、Fe、Co、Ce、Ni、Cu、Zn、Ga、Mo、Ru、Rh、Pd、Ag、In、Sn、Re、Ir和Pt的金属。第一分子筛中包含的金属可与第二分子筛中包含的金属相同或不同。因此,例如,第一分子筛可包含铜,第二分子筛可包含铁。在一个实施方案中,两种分子筛可一起离子交换。
应了解,例如从以上表1了解,在本文中,“包含一种或多种过渡金属的分子筛”意指包括其中铝和硅以外的元素代入分子筛的框架的分子筛。这些分子筛被称为“非沸石分子筛”,并且包括用一种或多种金属取代的“SAPO”、“MeAPO”、“FeAPO”、“AlPO4”、“TAPO”、“ELAPO”、“MeAPSO”和“MeAlPO”。适合取代金属包括但不限于一种或多种As、B、Be、Co、Fe、Ga、Ge、Li、Mg、Mn、Ti、Zn和Zr。这些非沸石分子筛可又由以上所列的适合金属浸渍,即Cr、Mn、Fe、Co等。第一分子筛和第二分子筛之一或两者可包含取代框架金属。在第一分子筛和第二分子筛两者均包含取代框架金属时,所述或各取代金属独立选自上列。
在一个具体实施方案中,用于本发明的小孔沸石和非沸石分子筛可选自铝硅酸盐沸石、金属取代的铝硅酸盐分子筛,如优选的含铁铝硅酸盐沸石和铝磷酸盐分子筛。
用于本发明的铝磷酸盐分子筛包括铝磷酸盐(AlPO4)分子筛、金属取代的铝磷酸盐分子筛(MeAlPO)、硅铝磷酸盐(SAPO)分子筛和金属取代的硅铝磷酸盐(MeAPSO)分子筛。
用作第一或第二分子筛组分的分子筛组分的特别有利组分为铁取代的铝硅酸盐,即,当铁存在于分子筛的框架时。在用于本发明的SCR催化剂的优选应用中,即,用于处理来自机动NOx源的排气,铁取代的铝硅酸盐特别有利,因为它们产生相对低或不产生N2O,N2O是强“温室”气体。
在一个实施方案中,至少一种过渡金属选自Cr、Ce、Mn、Fe、Co、Ni和Cu。在一个优选的实施方案中,至少一种过渡金属选自Cu、Fe和Ce。在一个具体实施方案中,至少一种过渡金属由Cu组成。在另一个具体实施方案中,至少一种过渡金属由Fe组成。在另一个具体实施方案中,至少一种过渡金属为Cu和/或Fe。
可在含至少一种过渡金属的分子筛中包含的至少一种过渡金属的总量可以为基于含至少一种过渡金属的分子筛催化剂总重量0.01至20.00%重量。在一个实施方案中,可包含的至少一种过渡金属的总量可以为0.1至10.0%重量。在一个具体实施方案中,可包含的至少一种过渡金属的总量为0.5至5.0%重量。在优选的实施方案中,过渡金属负载量为2.0至4.0%重量,SAR为25至50或>40或>60,例如40<100,40<70或60<100,其条件为,对于框架内铁分子筛,满足此SiO2/Fe2O3比(存在时,SiO2/Fe2O3为50至200,优选50至100)。
使用在现有技术熟知的技术,包括液相交换或固体离子交换或通过初始湿润法,可将过渡金属加入到用于本发明的分子筛。关于制造含铁的铝硅酸盐沸石,参见Journal of Catalysis 232(2)318-334(2005)、EP2072128和WO2009/023202及其中参考文献和研究引用。
在一个特别优选的实施方案中,催化组分包括为大孔分子筛的第一分子筛和为小孔分子筛的第二分子筛的组合或由它们组成。在某些优选的实施方案中,小孔分子筛具有CHA框架,更优选SSZ-13框架,并且包含铜。在某些优选的实施方案中,使此小孔分子筛与具有BEA框架的大孔分子筛组合。优选BEA框架包含离子交换或游离铁,或者为铁同晶BEA分子结构(也称为BEA型铁硅酸盐),并且铁同晶BEA分子结构是特别优选的。
在某些优选的实施方案中,铁同晶BEA分子结构为一种结晶硅酸盐,所述硅酸盐具有(1)具有约20至约300的SiO2/Fe2O3摩尔比的含铁BEA框架结构,并且(2)至少80%所含的铁为新鲜态孤立的铁离子Fe3+,并且/或者以摩尔计log(SiO2/Al2O3)为至少约2。
用于本发明的优选BEA型铁硅酸盐具有下式表示的组成:
(x+y)M(2/n)O·x Fe2O3·y Al2O3·z SiO2·w H2O
其中n为阳离子M的原子数;x、y和z分别表示Fe2O3、Al2O3和SiO2的摩尔分数;x+y+z=1;w为至少0的数;z/x为20至300;y可以为0,任选z/y为至少100。
优选含铁的BEA框架结构的SiO2/Fe2O3摩尔比为约25至约300,约20至约150,约24至约150,约25至约100,或约50至约80。以摩尔计log(SiO2/Al2O3)的上限没有特别限制,其条件为以摩尔计log(SiO2/Al2O3)为至少2(即,SiO2/Al2O3摩尔比为至少100)。以摩尔计log(SiO2/Al2O3)优选为至少2.5(即,SiO2/Al2O3摩尔比为至少310),更优选至少3(即,SiO2/Al2O3摩尔比为至少1,000)。在以摩尔计log(SiO2/Al2O3)超过4(即,SiO2/Al2O3摩尔比变成至少10,000)时,用于氮氧化物还原的性能恒定在最高水平。
在某些优选的实施方案中,CHA分子筛表征为具有大于约1微米的平均晶体大小,优选约1至约5微米,约2至约4微米是最优选的。在BEA型铁硅酸盐中,最显著对还原氮氧化物显示催化活性的铁成分不是附聚为Fe2O3,而是在框架结构中分散为孤立的铁离子Fe3+(即,在硅酸盐框架结构或离子交换部位孤立并且分散)。孤立的铁离子Fe3+可通过电子自旋共振检测。用于限定BEA型铁硅酸盐组成的SiO2/Fe2O3摩尔比为限定BEA型铁硅酸盐中全部铁含量(包括孤立的铁离子Fe+3)的方便表达。
与组成组分比较,使用小/大孔沸石掺合物,特别是铜交换SSZ-13/Fe-BEA组合,可增加N2O生成。因此,使用此组合可能在某些应用中不利。然而,使用铜交换SSZ-13/BEA型铁硅酸盐组合意外地克服此难题,因此,给予改进的到氮的选择性。区域化和分层的SCR催化剂给予其它改进,特别在排气具有约50/50的NO∶NO2比时。这种催化剂比掺合的同等物减少N2O排放约75%,同时保持极佳的瞬时反应,和在低NO/NO2气体混合物良好地转化。
意外的是,铜交换SSZ-13/预老化Fe-BEA的组合可产生实质好于具有常规Fe-BEA的组合的结果。
因此,Fe-BEA材料优选在600-900℃(优选650-850℃,更优选700-800℃,甚至更优选725-775℃)老化3-8小时,优选4-6小时,更优选4.5-5.5小时,甚至更优选4.75-5.25小时,而不是在500℃老化1小时的更常规处理。
使用铜交换SSZ-13/预老化Fe-BEA组合的实施方案有利于N2O生成不合乎需要的应用。类似于Cu∶SSZ-13与Fe-BEA和Cu∶SSZ-13与BEA-铁硅酸盐之比的Cu∶SSZ-13与预老化Fe-BEA之比包括在本发明的范围内。类似于Cu∶SSZ-13与Fe-BEA和Cu∶SSZ-13与BEA-铁硅酸盐的组合的Cu∶SSZ-13与预老化Fe-BEA的组合也包括在本发明的范围内。
第一分子筛和第二分子筛两者可存在于相同的催化剂涂层中,即,在洗涂料中涂覆于适合的基质整料,或者,第一分子筛组分和第二分子筛组分可在洗涂层中上下分离,并且层中的第一分子筛组分高于第二分子筛组分,或者反之亦然。或者,第一分子筛和第二分子筛两者可在生成挤出型基质整料的组合物中组合。任选挤出的整料可进一步用包含第一分子筛组分和第二分子筛组分之一或两者的洗涂料涂覆。其它替代包括,形成包含第一分子筛组分和第二分子筛组分之一而非两者的挤出基质整料,用包含挤出物中不存在的另一种分子筛组分的洗涂料涂覆挤出的基质整料,或者,洗涂料可包含第一分子筛和第二分子筛两者。在组合经挤出和涂覆基质整料的所有布置中,应了解,在挤出物和催化剂涂层两者中存在第一和/或第二分子筛组分时,第一分子筛组分可在挤出物和涂层中相同,或者不同。因此,例如,洗涂层可包含SSZ-13沸石,挤出物可包含SAPO-34。同样情况适用于第二分子筛组分,例如,洗涂层可包含ZSM-5沸石,挤出物可包含β沸石。
用于本发明的涂覆到整料基质或制造挤出型基质整料的包含分子筛的洗涂料组合物可包括选自氧化铝、二氧化硅、(非沸石)二氧化硅-氧化铝、天然存在的粘土、TiO2、ZrO2和SnO2的粘合剂。
适合的基质整料包括由陶瓷材料(如堇青石)制成的所谓流通基质整料(即,具有轴向通过整个部分的很多小的平行通道的蜂窝状整料催化剂载体结构)或例如由fecralloy制成的金属基质。基质整料可以为过滤器,包括由堇青石、钛酸铝、碳化硅或富铝红柱石制成的壁流过滤器;陶瓷泡沫;熔结的金属过滤器或所谓的分滤器,如EP 1057519或WO 01/080978中公开的那些过滤器。
根据另一方面,本发明提供一种处理流动排气的排气系统,所述流动排气包含来自此排气的机动源的氮氧化物,所述系统包含以流动方向从本发明的SCR催化剂在上游布置的含氮还原剂源。
含氮还原剂源可包含在例如适当编程电子控制装置控制下操作的适合注射器装置,以输送在所需程度转化NOx的适量还原剂或其前体(装在适合的容器或箱中)。液体或固体氨前体可以为例如脲((NH2)2CO)、碳酸铵、氨基甲酸铵、碳酸氢铵或甲酸铵。或者,可使用氨本身或肼。
在供选的实施方案中,含氮还原剂源为与发动机组合的NOx吸收器(也称为NOx捕集器,贫NOx捕集器或NOx吸收催化剂(NAC)),所述发动机经构造,以便至少一个发动机汽缸能够比一般操作条件更富裕地操作,例如,在剩余的发动机汽缸中,例如,以产生具有化学计量平衡氧化还原组合物或富氧化还原组合物的排气,和/或在NOx吸收器上游布置的用于将烃注入流动排气的单独烃注射器装置。通过吸附的NOx与还原环境接触,使在NOx吸收器上吸收的NOx还原成氨。在通过NOx吸收器与例如发动机产生的较富排气接触再生NOx吸收器时,通过在NOx吸收器下游设置本发明的SCR催化剂,可用原位产生的氨在SCR催化剂上还原NOx。
或者,含氮还原剂源可以为单独的催化剂,例如,位于各至少一个发动机汽缸的排气歧管的NOx捕集器或转化催化剂,发动机汽缸构造成比正常富裕地间断或连续操作。
在另一个实施方案中,用于使排气中的一氧化氮氧化成二氧化氮的氧化催化剂可位于含氮还原剂计量进入排气和SCR催化剂的点的上游。
氧化催化剂可包括在流通整料基质上涂覆的至少一种贵金属,优选铂族金属(或这些的某种组合),如铂、钯或铑。在一个实施方案中,至少一种贵金属为铂、钯或铂和钯两者的组合,或Pd-Au的合金,任选与Pt-Pd组合。贵金属可承载于高表面积洗涂组分上,如氧化铝、铝硅酸盐沸石、二氧化硅、非沸石二氧化硅-氧化铝、二氧化铈、二氧化锆、二氧化钛或含二氧化铈和二氧化锆两者的混合或复合氧化物。
在另一个实施方案中,适合的过滤器基质位于氧化催化剂和本发明的催化剂之间。过滤器基质可选自任何以上所述基质,例如壁流过滤器。在催化过滤器时,例如利用以上讨论种类的氧化催化剂,优选含氮还原剂计量的点位于过滤器和本发明的催化剂之间。应了解,此布置公开于WO 99/39809中。或者,如果未催化过滤器,可使计量含氮还原剂的装置位于氧化催化剂和过滤器之间。
在另一个实施方案中,用于本发明的SCR催化剂涂覆于位于氧化催化剂下游的过滤器上,或者以挤出型催化剂形式。在过滤器包含用于本发明的SCR催化剂时,含氮还原剂计量的点优选位于氧化催化剂和过滤器之间。
另一方面,本发明提供一种包括本发明的排气系统的贫燃内燃机。在某些实施方案中,发动机可以为压缩点火发动机或强制点火发动机。强制点火发动机可加多种燃料,包括汽油燃料、掺混含氧剂(包括甲醇和/或乙醇)的汽油燃料、液化石油气或压缩天然气。压缩点火发动机可加柴油燃料、掺混非柴油烃(包括通过气-液方法生产的合成烃)的柴油燃料或生物源组分。
另一方面,本发明提供一种包括本发明的贫燃内燃机的机动车。
另一方面,本发明提供使其组成、流速和其排气温度分别瞬时改变的机动源排气中的氮氧化物(NOx)转化的方法,所述方法包括在包含第一分子筛组分和第二分子筛组分的组合的选择性催化还原催化剂存在下使NOx与含氮还原剂接触的步骤,其中在联邦试验方法(FTP)75循环试验的直接比较中,催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx累积转化率。
在一个实施方案中,催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx累积转化率,其中进入所述催化剂的进气中NO∶NO2累积摩尔比等于或小于1。
在另一个实施方案中,催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx至双氮累积转化率。
在另一个实施方案中,氮氧化物用含氮还原剂在至少100℃的温度还原。在另一个实施方案中,氮氧化物用还原剂在约150℃至750℃的温度还原。后面的实施方案特别用于处理来自重和轻型柴油机的排气,特别是包括含(任选催化)柴油机微粒过滤器的排气系统的发动机,微粒过滤器例如通过将烃注入过滤器上游的排气系统主动再生,其中本发明的催化剂位于过滤器的下游。
在一个具体实施方案中,温度为175至550℃。在另一个实施方案中,温度为175至400℃。
在另一个实施方案中,氮氧化物还原在氧存在下进行。在一个供选的实施方案中,氮氧化物还原在无氧存在下进行。
含氮氧化物的气体可以5,000hr-1至500,000hr-1的气体时空间速度接触本发明的催化剂,任选10,000hr-1至200,000hr-1。
可调解接触SCR催化剂的含氮还原剂的计量,使得以1∶1NH3/NO和4∶3NH3/NO2计算,在进入SCR催化剂的排气中存在理论氨的60%至200%。
在另一个实施方案中,使排气中的一氧化氮氧化成二氧化氮的步骤可在引入任何含氮还原剂之前进行。这些NO氧化步骤可适当用适合氧化催化剂进行。在一个实施方案中,氧化催化剂适应产生一种进入SCR催化剂的气流,所述气流具有约4∶1至约1∶3的NO∶NO2体积比,例如在250℃至450℃的氧化催化剂入口的排气温度。
为了能够更充分地理解本发明,参考以下附图,其中:
图1为本发明的排气系统实施方案的示意图;
图2为本发明的另一个排气系统实施方案的示意图;并且
图3为显示关于实施例1、2和3制备的新催化剂的实施例3中所述试验NOx转化活性结果的曲线图。
图4a-4d显示基质上第一分子筛和第二分子筛的不同类型组合。
图5、6a、6b、7和8a-8c为显示与本发明的某些实施方案相关的数据的曲线图。
在图1中显示设备10,设备10包括轻型柴油机12和排气系统14,排气系统14包括将从发动机排放的排气输送到大气15的导管,其中导管为用NOx吸收器催化剂((NAC),也称为NOx捕集器或贫NOx捕集器)16涂覆的金属基质整料,以流动方向,随后为用本发明的SCR催化剂(用沸石中铁框架BEA掺混的Cu/SSZ-13也与另外的离子交换铁离子交换))涂覆的壁流过滤器18。包含相对低负载量Pt/氧化铝的净化催化剂24布置于壁流过滤器18的下游。
在使用时,发动机贫化学计量运行,其中NOx吸收在NAC中。发动机间断富化学计量运行,以解吸和还原NOx。在富运行操作期间,一些NOx还原成NH3,并储存在下游SCR催化剂,用于进一步NOx还原。在间断富场合下,SCR催化剂也处理NOx。用NO在NAC上氧化成NO2燃烧在过滤器18上被动捕集的烟灰。也用NAC在过滤器的偶然强制(主动)再生期间燃烧另外的烃。
图2显示本发明的包含柴油机12和排气系统13的供选设备11。排气系统13包括导管17,导管17连接催化后处理组件,即,在接近发动机排气歧管(所谓的接近配合位置)布置的惰性陶瓷流通基质19上涂覆的2Au-0.5Pd/Al2O3催化剂。在所谓的地板下位置,接近配合催化剂19的下游是挤出型流通催化剂22,催化剂22包含与Cu离子交换的铝硅酸盐CHA和具有在分子筛框架结构中存在的Fe的FeCHA的混合物。在箱28中提供含氮还原剂源(尿素),含氮还原剂源注入催化剂19和22之间的排气导管17。
在某些实施方案中,本发明提供用其组成、流速和温度分别瞬时改变的进气中的含氮还原剂选择性催化转化氮氧化物的催化剂,所述催化剂包含第一分子筛组分和第二分子筛组分的组合,其中在联邦试验方法(Federal Test Procedure)(FTP)75循环试验的直接比较中,催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx累积转化率。
优选催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx累积转化率(优选转化成元素氮),其中进入所述催化剂的进气中NO∶NO2累积摩尔比等于或小于1。
在某些实施方案中,SCR催化剂具有第一分子筛组分,对于所选择条件,第一分子筛组分在比第二分子筛组分更低的NH3填充量达到最大NOx转化率。优选第一分子筛组分的较低NH3填充量在10-80%的范围内。
在SCR催化剂中的某些实施方案中,第一分子筛和第二分子筛可独立选自沸石和非沸石分子筛。优选分子筛组分之一为包含八(8)个四面体原子最大环大小的小孔分子筛,优选选自由ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG和ZON组成的框架类型编号,CHA、LEV、ERI、DDR、KFI、EAB、PAU、MER、AEI、GOO、YUG、GIS和VNI是特别优选的。优选其它分子筛组分选自小孔、中孔、大孔或介孔大小的分子筛。优选的中孔分子筛包括MFI、MWW、AEL、AFO、FER和HEU。优选的大孔分子筛包括FAU、AFI、AFR、ATO、BEA、GME、MOR和OFF.
在某些实施方案中,第一分子筛和第二分子筛之一或两者包含选自As、B、Be、Co、Fe、Ga、Ge、Li、Mg、Mn、Ti、Zn和Zr的取代框架金属。在某些实施方案中,第一分子筛组分和第二分子筛组分之一或两者包含一种或多种独立选自Cr、Mn、Fe、Co、Ce、Ni、Cu、Zn、Ga、Mo、Ru、Rh、Pd、Ag、In、Sn、Re、Ir和Pt的金属,优选Cr、Ce、Mn、Fe、Co、Ni和Cu。
在本发明的一个方面,本发明提供一种处理流动排气的排气系统,所述流动排气包含来自此排气的机动源的氮氧化物,所述系统包含以流动方向从本文所述选择性催化还原催化剂在上游布置的含氮还原剂源。在某些实施方案中,系统进一步包括在含氮还原剂源和SCR催化剂的上游布置的氧化催化剂。在某些实施方案中,系统进一步包括在氧化催化剂和含氮还原剂源之间布置的过滤器。
在本发明的一个方面,本发明提供一种包含本文所述排气系统的贫燃内燃机,例如压缩点火发动机或强制点火发动机。在某些实施方案中,发动机包含至少部分作为含氮还原剂源的NOx吸收器。
在本发明的一个方面,本发明提供一种包含本文所述贫燃内燃机的机动车。
在本发明的一个方面,本发明提供使其组成、流速和其排气温度分别瞬时改变的机动源排气中的氮氧化物(NOx)转化的方法,所述方法包括在包含第一分子筛组分和第二分子筛组分的组合的选择性催化还原催化剂存在下使NOx与含氮还原剂接触的步骤,其中在联邦试验方法(FTP)75循环试验的直接比较中,催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx累积转化率。在方法的某些实施方案中,催化剂具有比单独采用的任一种分子筛组分在相同或较低NH3泄漏更高的NOx累积转化率(优选转化成双氮),其中进入所述催化剂的进气中NO∶NO2累积摩尔比等于或小于1。在方法的某些实施方案中,NOx在至少100℃(优选约150℃至750℃)的温度转化。在方法的某些实施方案中,含NOx的气体以5,000hr-1至500,000hr-1的气体时空间速度接触SCR催化剂。在某些实施方案中,以1∶1NH3/NO和4∶3NH3/NO2计算,理论氨的约60%至约200%接触SCR催化剂。在方法的某些实施方案中,接触SCR催化剂的气体中NO∶NO2比为约4∶1至约1∶3体积比。
以下实施例仅作为说明提供。
实施例
实施例1-制备新鲜3%重量Cu/SSZ-13(铝硅酸盐CHA)催化剂的方法
使市售SSZ-13沸石(CHA)在NH4NO3溶液中进行NH4 +离子交换,然后过滤。在搅拌下将所得物质加到Cu(NO3)2的水溶液。将浆料过滤,然后洗涤并干燥。重复此过程,以得到所需金属负载。煅烧最终产物。在本文中,将根据此实施例制备的材料称为“新鲜”。
实施例2-制备新鲜5%重量Fe/β催化剂的方法
使市售β沸石在NH4NO3溶液中进行NH4 +离子交换,然后过滤。在搅拌下将所得物质加到Fe(NO3)3的水溶液。将浆料过滤,然后洗涤并干燥。重复此过程,以得到所需金属负载。煅烧最终产物。在本文中,将根据此实施例制备的材料称为“新鲜”。
实施例3-催化剂混合物
由根据实施例1和2制备的样品的物理混合物制备新鲜和老化1∶3重量比Fe/β∶Cu/SSZ-13的单独物理掺合物。同样制备1∶3重量比BEA-铁硅酸盐∶CuSSZ-13的物理掺合物。
实施例4-NOx转化活性试验
在实验室设备中在250℃试验根据实施例1、2和3制备的新鲜粉末样品的活性,试验在60,000hr-1空间速度使用以下气体混合物:125ppm NO、375ppmNO2、750ppm NH3、14%O2、4.5%H2O、4.5%CO2,其余为N2。在样品下游检测20ppm NH3时停止试验。结果显示于图3中。
从结果看到,Fe/β样品具有快瞬时反应,但限制最大转化。与Cu/SSZ-13和Fe/β+Cu/SSZ-13掺合物比较,它也在试验中早期泄漏NH3。瞬时反应定义为在催化剂上的NH3填充量增加时NOx转化增加所在的速率。Cu/SSZ-13具有较好、较高的最大转化率,但有较慢的瞬时反应。Fe/β和Cu/SSZ-13的组合得到快瞬时反应,较高最大转化率,但也比单独组分在中间NH3填充量更高的转化率,这明显为协同作用。预老化1∶3Fe/β∶Cu/SSZ-13也提供改进的结果。
实施例5:掺合物、层和区域组合的比较
制备1∶3重量比BEA-铁硅酸盐∶Cu/SSZ-13组合的三个样品,并单独作为掺合物、区域和层涂在基质上。使三个经涂覆基质暴露于与实施例4中所述类似的试验环境,不同之处在于NO∶NO2比为约50∶50。结果显示于图5中。
从结果可以看到,与掺合物比较,区域和掺合物达到较高NOx转化。
实施例6-N2O生成
制备1∶3重量比FeBEA∶CuSSZ-13组合的一个样品和1∶3重量比BEA-铁硅酸盐∶CuSSZ-13组合的三个样品,并单独涂在基质上。FeBEA∶CuSSZ-13组合作为掺合物涂覆,而BEA-铁硅酸盐∶CuSSZ-13组合的样品作为掺合物、区域和层涂覆。使各样品暴露于与NH3剂量(20ppm泄漏)组合的模拟柴油机排气。记录在暴露期间的平均N2O生成,显示于图6a和6b中。
很明显,FeBEA∶CuSSZ-13掺合物产生显著N2O,导致最大转化和“N2选择性”瞬时反应明显减小。此转化减小也超过对独立评价的两种组分观察的减小。意外的是,BEA-铁硅酸盐∶CuSSZ-13掺合物产生实质小于对任何其它CuSSZ-13/沸石掺合物观察的N2O。然而,BEA-铁硅酸盐∶CuSSZ-13的层和区域不仅保持对掺合物观察的低N2O产生,而且在不同N2O量下显示改善的瞬时反应(参见图7)。
实施例7-NO∶NO2比的作用
制备BEA-铁硅酸盐∶CuSSZ-13的4个样品,并试验暴露于与NH3还原剂组合的模拟柴油机排气期间的NOx转化能力。试验在250℃和约60,000/小时的气体时空间速度进行。结果提供于下表中。在此,参照(“ref”)催化剂为CuSSZ-13,“低填充”是指小于约0.5g/L排气的NH3量,“高填充”是指大于约1g/L排气的NH3。
实施例8-多种组合
制备FeBEA、CuSSZ-13和BEA-铁硅酸盐的样品,并以指示组合组合,多种组合显示于图8a-8c中。在图例中,比率以重量给出,掺合物显示于括号中,区域由“//”指示,并且第一命名组分相对于通过催化剂的气流在上游布置。使各组合和多种组合暴露于包含NH3还原剂的模拟柴油机排气流。排气中的NO∶NO2比从只NO、50∶50NO∶NO2(以重量计)和75%NO2(以重量计)改变,以在不同条件试验催化剂。作为NH3填充量的函数评价各组合或多种组合的NOx转化率(关于N2O生成校正)。
Claims (40)
1.一种多相催化剂制品,所述催化剂制品包含:
催化组分,所述催化组分包括具有中孔、大孔或介孔晶体结构且任选包含约0.01至约20%重量第一金属的第一分子筛和具有小孔晶体结构且任选包含约0.01至约20%重量第二金属的第二分子筛的至少一种组合,其中所述第一金属和第二金属与分子筛的晶体框架交换或相对于分子筛的晶体框架游离,并且独立选自Cr、Mn、Fe、Co、Ce、Ni、Cu、Zn、Ga、Mo、Ru、Rh、Pd、Pt、Ag、In、Sn、Re和Ir;和
上面或之内结合所述催化组分的整料基质,
其中所述第一分子筛和第二分子筛的组合选自掺合物、多个层和多个区域,其中所述组合包括基于所述第一分子筛和第二分子筛的组合重量的多数所述第二分子筛。
2.权利要求1的多相催化剂,其中所述组合由所述多个区域组成,其中所述多个区域包含具有所述第一催化剂的第一区域和具有所述第二催化剂的第二区域,其中所述第一区域相对于经过或通过所述催化组分的气流方向在所述第二区域的上游,并且多数所述第一区域不相对于所述基质重叠所述第二区域,多数所述第二区域不相对于所述基质重叠所述第一区域。
3.权利要求1的多相催化剂,其中所述组合由所述多个层组成,其中所述多个层包含具有所述第一催化剂的第一层和具有所述第二催化剂的第二层,其中所述第二层邻接所述第一层和所述整料基质两者,并且在所述第一层和所述整料基质之间。
4.权利要求1的多相催化剂,其中所述组合包括所述第一分子筛和所述第二分子筛的所述掺合物。
5.权利要求1的多相催化剂,其中所述催化组分涂在所述整料基质上。
6.权利要求5的多相催化剂,其中所述第二分子筛具有CHA晶体结构,并且包含约0.5至约5%重量铜,所述第一分子筛具有BEA分子结构,并且包含约0.5至约5%重量铁。
7.权利要求5的多相催化剂,其中所述第二分子筛具有CHA晶体结构,并且包含约0.5至约5%重量铜,所述第一分子筛具有预老化的BEA分子结构,并且包含约0.5至约5%重量铁。
8.权利要求7的多相催化剂,其中所述组合包括约0.1至约1.0重量比的所述第一分子筛和所述第二分子筛。
9.权利要求7的多相催化剂,其中所述第二分子筛具有约8至约150的二氧化硅-氧化铝比率。
10.权利要求9的多相催化剂,其中所述第二分子筛具有SSZ-13晶体结构。
11.权利要求10的多相催化剂,其中所述第二分子筛包含约2.0至约4.0%重量铜。
12.权利要求5的多相催化剂,其中所述第二分子筛具有CHA晶体结构,并且包含约0.5至约5%重量铜,所述第一分子筛具有铁同晶BEA分子结构。
13.权利要求12的多相催化剂,其中所述组合包括约0.1至约1第一分子筛与第二分子筛重量比的所述第一分子筛和所述第二分子筛。
14.权利要求13的多相催化剂,其中所述CHA晶体结构具有约8至约150的二氧化硅-氧化铝比率,所述铁同晶BEA分子结构具有约50至约200的二氧化硅-氧化铁比率。
15.权利要求14的多相催化剂,其中所述第二分子筛包含约2.0至约4.0%重量铜。
16.权利要求15的多相催化剂,其中所述组合包括约0.2至约0.60重量比的所述第一分子筛和所述第二分子筛。
17.权利要求11或16的多相催化剂,其中所述组合由具有所述第一催化剂的第一区域和具有所述第二催化剂的第二区域组成,其中所述第一区域相对于经过或通过此区域的排气流在所述第二区域的上游,并且多数所述第一区域不相对于所述基质重叠所述第二区域,多数所述第二区域不相对于所述基质重叠所述第一区域。
18.权利要求11或16的多相催化剂,其中所述组合由具有所述第一催化剂的第一层和具有所述第二催化剂的第二层组成,其中所述第二层邻接所述第一层和所述整料基质两者,并且在所述第一层和所述整料基质之间。
19.权利要求11或16的多相催化剂,其中所述组合由所述第一分子筛和所述第二分子筛的所述掺合物组成。
20.权利要求1的多相催化剂,其中所述催化组分包括第一组合和第二组合,其中所述第一组合由铁同晶BEA分子结构组成的第一区域和由所述第二组合组成的第二区域组成,其中所述第一区域和所述第二区域相互邻接并且邻接所述整料基质,并且所述第一区域相对于经过或通过所述催化组分的气流方向在所述第二区域的上游,并且其中所述第二组合为相同或不同第一分子筛和第二分子筛的掺合物。
21.一种处理排气的方法,所述方法包括在权利要求1的多相催化剂存在下在约150℃至约750℃的温度使进排气流与含氮还原剂接触,以产生经处理排气流,其中所述进排气流具有NOx第一浓度,所述经处理排气流具有NOx第二浓度,并且所述NOx第二浓度小于所述NOx第一浓度。
22.权利要求21的方法,其中:
所述催化组分涂覆在所述整料基质上;
所述第一分子筛具有二氧化硅-氧化铝比率约8至约150的CHA晶体结构,并且包含约0.5至约5%重量铜;
所述第二分子筛具有预老化BEA分子结构,并且包含约0.5至约5%重量铁;
所述组合包括约0.25至约0.50重量比的所述第一分子筛和所述第二分子筛;
所述温度为约175℃至约400℃;并且
所述进排气流在约10,000/小时至约200,000/小时的气体时空间速度接触所述催化剂。
23.权利要求22的方法,其中所述进排气流具有约0.8至约1.2的NO∶NO2比率。
24.权利要求23的方法,其中所述组合由所述第一分子筛和所述第二分子筛的所述掺合物组成。
25.权利要求23的方法,其中所述组合由具有所述第一催化剂的第一层和具有所述第二催化剂的第二层组成,其中所述第二层邻接所述第一层和所述整料基质两者,并且在所述第一层和所述整料基质之间。
26.权利要求23的方法,其中所述组合由具有所述第一催化剂的第一区域和具有所述第二催化剂的第二区域组成,其中所述第一区域和所述第二区域相互邻接,并且邻接所述整料基质,所述第一区域相对于经过或通过区域的排气流在所述第二区域的上游。
27.权利要求22的方法,其中进排气流具有小于约0.3的NO∶NO2比,其中所述含氮还原剂以大于约1克/升进排气的浓度存在,其中所述组合由所述第一分子筛和所述第二分子筛的所述掺合物组成。
28.权利要求22的方法,其中进排气流具有小于约0.3的NO∶NO2比,其中所述含氮还原剂以小于约0.5克/升进排气的浓度存在,其中所述组合由具有所述第一催化剂的第一层和具有所述第二催化剂的第二层组成,其中所述第二层邻接所述第一层和所述整料基质两者,并且在所述第一层和所述整料基质之间。
29.权利要求22的方法,其中进排气流具有小于约0.3的NO∶NO2比,其中所述含氮还原剂以小于约0.5克/升进排气的浓度存在,其中所述组合由具有所述第一催化剂的第一区域和具有所述第二催化剂的第二区域组成,其中所述第一区域和所述第二区域相互邻接,并且邻接所述整料基质,并且所述第一区域相对于经过或通过区域的排气流在所述第二区域的上游。
30.权利要求22的方法,其中进排气流具有大于约3的NO∶NO2比,其中所述组合由所述第一分子筛和所述第二分子筛的所述掺合物组成。
31.权利要求21的方法,其中:
所述催化组分涂覆在所述整料基质上;
所述第一分子筛具有二氧化硅-氧化铝比率约8至约150的CHA晶体结构,并且包含约0.5至约5%重量铜;并且
所述铁同晶BEA分子结构具有约50至约200的二氧化硅-氧化铁比率;
所述组合包括约0.25至约0.50重量比的所述第一分子筛和所述第二分子筛;
所述温度为约175℃至约400℃;并且
所述进排气流在约10,000/小时至约200,000/小时的气体时空间速度接触所述催化剂。
32.权利要求31的方法,其中所述进排气流具有约0.8至约1.2的NO∶NO2比率。
33.权利要求32的方法,其中所述组合由所述第一分子筛和所述第二分子筛的所述掺合物组成。
34.权利要求32的方法,其中所述组合由具有所述第一催化剂的第一层和具有所述第二催化剂的第二层组成,其中所述第二层邻接所述第一层和所述整料基质两者,并且在所述第一层和所述整料基质之间。
35.权利要求32的方法,其中所述组合由具有所述第一催化剂的第一区域和具有所述第二催化剂的第二区域组成,其中所述第一区域和所述第二区域相互邻接,并且邻接所述整料基质,所述第一区域相对于经过或通过区域的排气流在所述第二区域的上游。
36.权利要求31的方法,其中进排气流具有小于约0.3的NO∶NO2比,其中所述含氮还原剂以大于约1克/升进排气的浓度存在,其中所述组合由所述第一分子筛和所述第二分子筛的所述掺合物组成。
37.权利要求31的方法,其中进排气流具有小于约0.3的NO∶NO2比,其中所述含氮还原剂以小于约0.5克/升进排气的浓度存在,其中所述组合由具有所述第一催化剂的第一层和具有所述第二催化剂的第二层组成,其中所述第二层邻接所述第一层和所述整料基质两者,并且在所述第一层和所述整料基质之间。
38.权利要求31的方法,其中进排气流具有小于约0.3的NO∶NO2比,其中所述含氮还原剂以小于约0.5克/升进排气的浓度存在,其中所述组合由具有所述第一催化剂的第一区域和具有所述第二催化剂的第二区域组成,其中所述第一区域和所述第二区域相互邻接,并且邻接所述整料基质,并且所述第一区域相对于经过或通过区域的排气流在所述第二区域的上游。
39.权利要求31的方法,其中进排气流具有大于约3的NO∶NO2比,其中所述组合由所述第一分子筛和所述第二分子筛的所述掺合物组成。
40.权利要求21的方法,其中所述含氮还原剂为氨。
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