CN104023843B - 用于处理废气的催化过滤器 - Google Patents
用于处理废气的催化过滤器 Download PDFInfo
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- CN104023843B CN104023843B CN201280053995.7A CN201280053995A CN104023843B CN 104023843 B CN104023843 B CN 104023843B CN 201280053995 A CN201280053995 A CN 201280053995A CN 104023843 B CN104023843 B CN 104023843B
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Classifications
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Abstract
提供了一种涂覆有SCR催化剂组合物的壁流式过滤器,其中该催化剂组合物包含过渡金属助催化的分子筛晶体,和其中:(i)该晶体具有约0.5μm至约15μm的平均晶粒尺寸,(ii)所述晶体作为单个晶体、具有小于约15μm的平均粒度的聚集体或者所述单个晶体和所述聚集体的组合存在于所述组合物中;和(iii)所述分子筛是具有八个四面体原子的最大环尺寸的骨架类型的铝硅酸盐或硅‑铝磷酸盐。
Description
交叉参考相关申请
本申请要求于2011年11月2日提交的美国临时申请61/554,529和于2012年1月19日提交的美国非临时申请13/353,842的优先权,其公开内容通过引用全部并入本文,为了所有目的。
发明背景
1.发明领域
本发明涉及用于处理燃烧废气的制品。更具体地说,本发明涉及用于减少贫燃废气中的烟灰和NOx,涂覆有选择性还原催化剂的颗粒过滤器。
2.相关技术的描述
多数燃烧废气的最大部分包含相对良性的氮气(N2)、水蒸气(H2O)和二氧化碳(CO2);但废气还含有相对小部分的有害和/或有毒的物质,如来自不完全燃烧的一氧化碳(CO),来自未燃烧燃料的烃(HC),来自过高燃烧温度的氮氧化物(NOx)和颗粒物质(主要是烟灰)。为了减轻释放到大气中的废气对环境的影响,需要消除或减少这些不希望的组分的量,优选通过不产生其他有害或有毒物质的方法。
最难以从车辆废气中除去的的组分之一是NOx,其包括一氧化氮(NO)、二氧化氮(NO2)、一氧化二氮(N2O)。将例如由柴油发动机产生的贫燃废气中的NOx还原为N2特别成问题,因为废气含有高浓度的氧,这有利于氧化反应而不是还原。然而,通过通常被称为选择性催化还原(SCR)的方法,NOx可以在柴油机废气中被还原。SCR方法涉及在催化剂的存在下与还原剂的帮助下NOx转化成单质氮(N2)和水。在SCR方法中,将气态还原剂如氨添加到废气流中,然后使废气与SCR催化剂接触。还原剂被吸收到催化剂上,NOx还原反应随着气体穿过或经过催化基底而发生。使用氨的化学计量的SCR反应的化学方程式是:
4NO+4NH3+3O2→4N2+6H2O
2NO2+4NH3+3O2→3N2+6H2O
NO+NO2+2NH3→2N2+3H2O
已知的SCR催化剂包括沸石和其他分子筛。这种分子筛的例子包括具有CHA(菱沸石)、BEA(β),MOR(丝光沸石)等骨架类型的铝硅酸盐和硅-铝磷酸盐。为了提高材料的催化性能和水热稳定性,用于SCR应用的分子筛常常由一种或多种过渡金属如铜或铁(松散地保持到分子筛的骨架作为交换的金属离子)助催化。例如,WO2010/043891描述了大晶体的、铜助催化的、具有CHA骨架的沸石。
因为SCR催化剂通常用作非均相催化剂(即与气体和/或液体反应物接触的固体催化剂),催化剂通常通过基底承载。在移动应用中使用的优选的基底包括具有所谓蜂窝状几何形状的流通式整料,其包括多个相邻的平行通道,这些通道在两端开口并通常从该基底的入口面延伸到出口面,由此具有高的表面积与体积之比。催化材料施加到基底上,典型地作为活化涂层(washcoat)或可以包含在基底上和/或基底的壁中的其他浆料。
除了NOx之外,柴油发动机的废气倾向于还具有烟灰和其他颗粒物质。烟灰排放可以通过使含有烟灰的废气经过柴油机颗粒过滤器(DFP)如壁流式过滤器来减轻。壁流式过滤器类似于流通式蜂窝状基底,也包含多个相邻的平行通道。但是,流通式蜂窝状基底的通道在两端开口,而壁流式基底的通道的一端封闭,其中封闭以交替模式发生在相邻通道的相反端部。封闭通道的交替端部防止进入基底入口面的气体直接流过通道并离开。相反,废气进入基底的前部,行进到通道约一半的地方,在此被迫穿过通道壁,然后进入通道的后一半,并离开基底的背面。
为了减少排气系统所需的空间量,通常需要设计单独的排气组件来执行一个以上的功能。例如,将SCR催化剂应用到壁流式过滤器基底,而不是流通式基底,通过允许一个基底有两个功能,即由SCR催化器催化转化NOx并由过滤器除去烟灰,用来减少废气处理系统的总体尺寸(参见例如WO2003/054364)。但是,用可操作量的SCR催化剂涂覆过滤器会不期望地增加跨越过滤器的背压,这又降低了发动机性能和燃料经济性。这对于高性能SCR催化剂如包含过渡金属助催化的沸石的活化涂层尤其如此。
制备用于壁流式过滤器的浆料活化涂层的常规方法包括碾磨小晶体沸石聚集体以减小催化剂晶体的平均粒径,从而实现过滤器壁的孔上涂层的所需的渗透。例如,WO2008/106519的实施例16和17表明,碾磨小晶体CHA沸石的聚集体以得到含有90%的小于3.5μm的颗粒的浆料,与仅碾磨到8.4μm的类似催化剂组合物相比,产生更好的NOx转化率。然而,研磨该催化剂还产生不需要的非常小的颗粒部分,由于其体积小,该部分进入过滤器基底的孔隙使它们更少接触到NOx和NH3的气流,从而降低了催化剂的整体活性。为了防止小的催化剂颗粒进入微裂纹中,过滤器基底典型地例如用聚合物涂层钝化,然后再用催化剂涂覆过滤器。然而,过滤器的钝化有显著缺点。一个缺点是,钝化显著增加了过滤器的成本。另一个缺点是,用聚合物层涂覆基底降低了气体渗透。
WO2010/097638公开了可以通过施加过渡金属助催化的沸石催化剂作为DFP的壁的入口表面和/或出口表面上的涂层,从而与用类似催化剂组合物渗透过滤器壁相比,降低跨越催化DFP的背压。然而,仍然需要对背压和/或催化剂性能的进一步改进。因此,当用有效量的SCR催化剂涂覆时,仍然需要产生相对较低的背压的DFP。
发明概述
申请人已经惊奇地发现,用具有最小聚集的大晶体小孔分子筛催化剂涂覆壁流式过滤器的内部多孔结构,与涂覆有小晶体催化剂的类似过滤器基底相比,产生具有更好性能的SCR过滤器,并且与在过滤器表面上涂覆有大晶体催化剂层的类似过滤器基底相比,也有更好的或类似的性能。本发明的催化剂涂层提供了超越以前已知的催化剂涂层的一些优点,包括改进的热稳定性和改进的SCR性能。不希望受到任何特定理论的束缚,据信用具有很少或几乎没有聚集的大晶体分子筛涂覆壁流式过滤器将催化剂限制在过滤器相对较大的互连孔。如果没有这个限制,催化剂涂层可能会进入更小的孔隙空间,阻塞或转移经过这种小孔的废气流。此外,相对于传统的渗透催化剂,采用具有很少乃至没有聚集的大晶体令人惊奇地改善了(即减少了)背压。
本发明的另一个优点是催化剂与基底如钛酸铝(AT)之间不利的相互作用被减少。例如,催化剂涂层被限制进入基底内的亚微米的热膨胀结点,否则当基底经受热应力时,可能导致过滤器开裂。而本发明的另一个优点是,它消除了对多孔基底的钝化的需要。
因此,提供一种过滤器制品,其包括:(a)壁流式过滤器,其包括具有入口面和出口面的多孔基底;和(b)SCR催化剂组合物,其涂覆在所述入口面和出口面之间的多孔基底上,其中该催化剂组合物包含过渡金属助催化的分子筛晶体,和其中:(i)所述晶体具有约0.5μm至约15μm的平均晶粒尺寸,(ii)所述晶体作为单个晶体、具有小于约15μm的平均粒度的聚集体或者所述单个晶体和所述聚集体的组合存在于所述组合物中;和(iii)所述分子筛是具有八个四面体原子的最大环尺寸的骨架类型的铝硅酸盐或硅-铝磷酸盐。
在本发明的另一个方面中,提供一种用于制造过滤器制品的方法,其包括:(a)用包含过渡金属助催化的分子筛晶体的活化涂层浆料涂覆未钝化的陶瓷壁流式整料的至少一部分,其中:(i)所述晶体具有约0.5μm至约15μm的平均晶粒尺寸,(ii)所述晶体作为单个晶体、具有小于约15μm的平均粒度的聚集体或者所述单个晶体和所述聚集体的组合存在于所述浆料中;及(iii)所述分子筛是具有八个四面体原子的最大环尺寸的骨架类型的铝硅酸盐或硅-铝磷酸盐,(b)从该整料除去过量的活化涂层浆料,以及(c)干燥和煅烧经涂覆的整料。
在本发明的另一个方面中,提供一种用于处理废气的系统,其包括:(a)催化壁流式过滤器,该催化壁流式过滤器包括:(i)具有入口面和出口面的多孔基底;和(ii)SCR催化剂组合物,其涂覆在该多孔基底入口面和/或出口面和/或所述入口面和出口面之间,其中该催化剂组合物包含过渡金属助催化的分子筛晶体,其中:所述晶体具有约0.5至约15μm的平均晶粒尺寸,所述晶体作为单个晶体、具有小于约15μm的平均粒度的聚集体或者所述单个晶体和所述聚集体的组合存在于所述组合物中,和所述分子筛是具有八个四面体原子的最大环尺寸的骨架类型的铝硅酸盐或硅-铝磷酸盐,(b)导管,其将该壁流式过滤器与含有颗粒物质和NOx的贫燃废气的源连接,以及(c)用于将还原剂引入贫燃废气的还原剂供给系统,其中该还原剂供给系统与该催化壁流式过滤器流体连通,并位于该催化壁流式过滤器相对于经过该过滤器的气流的上游。
在本发明的另一个方面中,提供一种用于处理废气的方法,其包括:(a)使含有颗粒物质和NOx的贫燃废气经过催化壁流式过滤器,该催化壁流式过滤器包括:(i)具有入口面和出口面的多孔基底;和(ii)SCR催化剂组合物,其涂覆在该多孔基底入口面和/或出口面和/或所述入口和出口面之间,其中该催化剂组合物包含过渡金属助催化的分子筛晶体,其中:所述晶体具有约0.5μm至约15μm的平均晶粒尺寸,所述晶体作为单个晶体、具有小于约15μm的平均粒度的聚集体或者所述单个晶体和所述聚集体的组合存在于所述组合物中,所述分子筛是具有八个四面体原子的最大环尺寸的骨架类型的铝硅酸盐或硅-铝磷酸盐,其中所述经过从所述废气中分离至少一部分所述颗粒物质,以形成经部分净化的废气;以及(b)在还原剂的存在下,使贫燃废气和/或经部分净化的废气与该SCR催化剂组合物接触,以将至少一部分NOx选择性还原为N2和其他组分。
发明的优选实施方案详述
在一个优选的实施方案中,本发明涉及用于改善环境空气质量,特别是用于改进由柴油机和其他贫燃发动机产生的废气排放的催化过滤器。至少部分地通过减少贫燃废气中的NOx和颗粒物质的浓度,来改进废气排放。因此,优选的催化过滤器包括多孔基底如柴油机颗粒过滤器(DFP),其既用于机械地从经过该多孔基底的废气流中除去颗粒物质,又用于承载用于在氧化环境中选择性还原NOx的催化剂组合物(即SCR催化剂)。
优选的SCR催化剂组合物包含许多由过渡金属助催化的大分子筛晶体,只要该晶体作为单个晶体和/或晶体的小聚集体存在于催化剂组合物中即可。用于本发明的分子筛包括微孔结晶或假晶性铝硅酸盐、金属取代的铝硅酸盐、硅铝磷酸盐(SAPO)或者具有重复分子骨架的铝磷酸盐,其中该骨架具有八个四面体原子的最大环尺寸。具有八个四面体原子的最大环尺寸的骨架的分子筛通常被称为小孔分子筛。小微孔分子筛的例子是具有标识为以下代码的骨架类型的那些: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或ZON,由国际沸石协会结构委员会规定。催化剂组合物可以包含一种或多种分子筛材料,具有相同或不同的骨架类型。
在某些优选的实施方案中,催化剂包含至少一种具有选自CHA、ERI和LEV的骨架类型的分子筛材料。对于某些应用特别优选的骨架类型是CHA。具有CHA骨架的有用的铝硅酸盐沸石的例子包括CHA同位型Linde-D、Linde-R、SSZ-13、LZ-218、Phi和ZK-14。具有CHA骨架的合适的SAPO的例子包括SAPO-34。在一个具体实施方案中,分子筛是SAPO-34。具有ERI骨架的有用的铝硅酸盐沸石的例子包括ERI同位型毛沸石、ZSM-34和Linde T型。具有LEV骨架的有用的铝硅酸盐沸石的例子包括LEV同位型插晶菱沸石、Nu-3、LZ-132和ZK-20。
对于某些利用CHA沸石的实施方案,沸石优选具有约15至约50的二氧化硅与氧化铝之比(SAR),例如约20至约40或约25至约30。在利用CHA沸石的其他实施方案中,沸石优选具有约10至约25的二氧化硅与氧化铝之比,例如约14至约20或约15至约17。沸石的二氧化硅与氧化铝之比可以通过常规的分析来确定。该比旨在尽可能地代表沸石晶体的刚性原子骨架中的比,并且排除粘合剂中或者通道内的阳离子形式或其他形式的硅或铝。因为在与粘合剂材料特别是氧化铝粘合剂合并后可能难以直接测量沸石中的二氧化硅与氧化铝之比,所以这些二氧化硅与氧化铝之比表示为沸石本身的SAR,即在沸石与其他催化剂组分合并之前。
本发明中应用的分子筛包括已经过处理以提高水热稳定性的那些。用于提高水热稳定性的常规方法包括:(i)使用酸或络合剂(例如EDTA-乙二胺四乙酸)通过汽蒸和酸提取来脱铝;用酸和/或络合剂处理;用SiCl4的气态流处理(用Si置换沸石骨架中的铝);及(ii)阳离子交换——使用多价阳离子如La。
优选地,分子筛由至少一种过渡金属助催化。过渡金属助催化的例子包括通过离子交换、浸渍、同晶取代等将过渡金属添加至分子筛。过渡金属可以附着到分子筛的骨架和/或驻留在分子筛内或上作为游离离子。如本文所用的,至少一种过渡金属被定义为包括铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、铈(Ce)、镍(Ni)、铜(Cu)、锌(Zn)、镓(Ga)、钼(Mo)、银(Ag)、铟(In)、钌(Ru)、铑(Rh)、钯(Pd)、铼(Re)、铱(Ir)、铂(Pt)和锡(Sn)及其混合物中的一种或多种。优选地,该一种或多种过渡金属可以是铬(Cr)、铈(Ce)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)和铜(Cu)及其混合物,最优选铜。在一个实施方案中,过渡金属是铜、铁或其组合。特别优选的金属是铜。在一个实施方案中,过渡金属负载量为分子筛的约0.1至约10重量%,例如约0.5重量%至约5重量%,约0.5至约1重量%,和约2至约5重量%。过渡金属的类型和浓度可根据宿主分子筛和应用而变化。
优选地,CHA沸石材料含有约75至约500克铜和/或铁每立方英尺沸石,更优选约100至约200克Cu和/或Fe每立方英尺沸石或约85至约100克Cu和/或Fe每立方英尺沸石。
在本发明的另一个实施方案中,催化剂中过渡金属如铜的量没有特别限制,只要在至少约450℃,更优选至少约550℃,甚至更优选至少约650℃的温度下,该催化剂可实现至少约65%,优选至少约75%,更优选至少约85%的NOx转化率即可。优选地,在这些温度范围的每个的转化率至少为约70%,更优选80%,当该催化剂工作在250℃的温度下时,催化剂的转化能力甚至更优选为90%。优选地,在这些温度范围的一个或更多,催化剂可以达到80%的转化率,对N2的选择性为至少约85%。
令人惊讶的是,当这种催化剂组合物被施加到柴油机微粒烟灰过滤器,例如作为渗透过滤器的活化涂层时,在催化剂组合物中将分子筛晶体的尺寸限制为大于约0.5μm和将晶体聚集体的尺寸限制为小于约15μm的组合使SCR的性能改进。特别是,与类似但具有较小晶粒尺寸的分子筛材料相比,使用含氮还原剂的这些过滤器上的催化剂具有较高的SCR活性。
因此,在优选的实施方案中,催化剂组合物包含具有大于约0.5μm的平均晶体尺寸的分子筛晶体,优选在约0.5μm至约15μm之间,如约0.5μm至约5μm,约0.7μm至约5μm,约1μm至5μm,约1.5μm至5.0μm,约1.5μm至4.0μm,约2μm至5μm,或约1μm至10μm。催化剂组合物中的晶体可以是单个晶体、晶体的聚集体或两者的组合,只要晶体的聚集体具有小于约15μm的平均粒径,优选小于约10μm,更优选小于约5μm即可。聚集体的平均粒度的下限是该组合物的平均单个晶体尺寸。
晶体尺寸(在此也称为作为晶体直径)是晶体的一个面的一个边的长度。例如,菱沸石晶体的形态特征是菱形(但大致为立方体的)面,其中该面的各边长度大致相同。可使用显微镜的方法如SEM和TEM来进行晶体尺寸的直接测量。例如,通过SEM测量包括在高放大倍率(通常1000×至10000×)检查材料的形态。SEM方法可以通过在合适的载片装置上分配沸石粉末的代表性部分而进行,使得单个颗粒被合理地均匀地分散在1000×到10000×的放大倍率视野中。从该粒子群(population),对随机的单个晶体的统计学显著样本(如50-200)进行检查,测量和记录平行于直边的水平线的单个晶体的最长尺寸。(明显为大的多晶聚集体的颗粒不应该被包括在测量中。)基于这些测量,计算样品晶体尺寸的算术平均值。
晶体聚集体的粒度可以以类似的方式来确定,除了测量聚集体最长边的长度而不是测量单个晶体的一个面的边缘。也可以使用用于确定平均粒度的其他技术,如激光衍射和散射。
如本文所用,涉及晶体尺寸或粒度的术语“平均”旨在表示粒子群的统计学显著样本的算术平均值。例如,包含具有约0.5至约5.0μm的平均晶体尺寸的分子筛晶体的催化剂是具有分子筛晶体的粒子群的催化剂,其中该粒子群(例如50个晶体)的统计学显著样本将产生约0.5至约5.0μm范围内的算术平均值。
除了平均晶体尺寸之外,催化剂组合物优选大部分晶体尺寸大于约0.5μm,优选在约0.5至约15μm之间,如约0.5至约5μm,约0.7至约5μm,约1至约5μm,约1.5至约5.0μm,约1.5至约4.0μm,约2至约5μm,或约1μm至约10μm。优选地,晶体尺寸样品的第一和第三四分值大于约0.5μm,优选在约0.5至约15μm之间,如约0.5至约5μm,约0.7至约5μm,约1至约5μm,约1.5至约5.0μm,约1.5至约4.0μm,约2至约5μm,或约1μm至约10μm。
如本文所用,术语“第一四分值”是指四分之一的元素位于其下的值。例如,当40个晶体的尺寸以从小到大的顺序排列时,40个晶体尺寸样本的第一四分值是第10个晶体的尺寸。类似地,术语“第三四分值”表示四分之三的元素位于其下的值。例如,当40个晶体的尺寸以从小到大的顺序排列时,第40个晶体尺寸样本的第三四分值是第30个晶体的尺寸。
大晶体CHA沸石如同位型的SSZ-13,可通过已知的方法合成,如在WO2010/043891(其通过引用并入本文)和WO2010/074040(其通过引用并入本文)中所述。
在本发明中使用的催化剂组合物可以是活化涂层的形式,优选适合于涂覆多孔基底的活化涂层,如金属或陶瓷壁流式整料。因此,本发明的另一个方面是包含如本文所述的催化剂组分的活化涂层。除了催化剂组分之外,活化涂层组合物可进一步包含选自由氧化铝、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组成的组的粘合剂。在某些实施方案中,催化剂组合物可进一步包含其他组分,包括稀土稳定剂和成孔剂,如石墨、纤维素、淀粉、聚丙烯酸酯和聚乙烯等。
优选地,所述催化剂组合物是未碾磨的。优选地,含有催化剂的活化涂层是未碾磨的。优选地,沸石晶体和聚集体是未碾磨的。如本文所用的,碾磨催化剂指的是机械方法,如研磨,用于减小主要部分或大部分被研磨的催化剂颗粒和/或晶体的尺寸。
在某些实施方案中,催化剂组合物不含或基本不含铂族金属,包括铂、钯、钌、铱和铑。
在某些实施方案中,催化剂组合物不含或基本不含羧酸,包括但不限于酒石酸、柠檬酸、n-乙酰谷氨酸、己二酸、α-酮戊二酸、天冬氨酸、壬二酸、樟脑酸、羧基谷氨酸、柠檬酸、3-羟基-3-甲基戊二酸(dicrotalicacid)、二巯基丁二酸、富马酸、戊烯二酸、谷氨酸、戊二酸、间苯二甲酸、衣康酸、马来酸、苹果酸、丙二酸、中康酸、中草酸、3-甲基戊烯二酸、草酸、草酰乙酸、邻苯二甲酸、邻苯二甲酸类、庚二酸、癸二酸、辛二酸、琥珀酸、丙醇二酸、对苯二甲酸、愈伤酸、苯均三酸、羧基谷氨酸及其衍生物。在某些实施方案中,催化剂组合物不含或基本上不含有机酸。
在本发明的一个实施方案中,催化剂组合物涂覆在多孔基底上,例如作为活化涂层。活化涂层可以通过任何常规方法施涂,包括浸渍、沉浸或注射,或者其某种组合,单独地或与一种或多种真空和/或压力循环进一步结合,用来促进催化剂活化涂层负载在基底上或内,和/或用来在负载后从基底清除多余的活化涂层。优选地,与残留在多孔基底的入口面或出口面上的活化涂层的量(如果有的话)相比,大部分活化涂层渗透大部分或整个多孔基底。在其他实施方案中,大部分活化涂层留在多孔基底的入口面和/或出口面上。
在某些实施方案中,活化涂层被直接施加至多孔基底,例如没有任何中间的非催化层或涂层如钝化层。在某些实施方案中,活化涂层被施涂到未钝化基底。未钝化基底的例子包括壁流式陶瓷整料,其主要由钛酸铝、堇青石、碳化硅、耐火碱性磷酸锆、低膨胀碱性铝硅酸盐(例如β-锂霞石、β-锂辉石和铯榴石)、α-氧化铝、氮化硅、氧化锆、莫来石、锂辉石、氧化铝-二氧化硅-氧化镁、硅酸锆、陶瓷纤维复合材料或其他陶瓷构成,而没有钝化材料如聚乙烯醇/乙烯胺共聚物、聚乙烯醇/乙烯基甲酰胺共聚物、聚合糠醇、糖类(例如单糖、二糖、低聚糖和多糖,包括右旋糖、蔗糖等)、明胶或基于有机物的聚合物和共聚物,以及相关材料如有机和无机的交联剂,包括多官能碳化二亚胺、醛、酸酐、环氧树脂类、亚胺酸酯(imidates)、异氰酸酯、三聚氰胺甲醛树脂、表氯醇、2,5-二甲氧基四氢呋喃和2-(4-二甲基氨基甲酰基-吡啶并)乙烷-1-磺酸酯、磷酰氯、四丁氧基钛、碳酸锆铵等。因此,在某些实施方案中,催化剂制品基本上由具有至少一个活化涂层组合物的涂层的多孔基底组成,该涂层可以布置在一个或多个层或区域中。
为使本发明的某些实施方案与使用钝化层生产的经活化涂覆的壁流式过滤器相区别,本发明的催化剂制品可包括耐热冲击的经活化涂覆的陶瓷壁流式过滤器,其具有空的(例如不包含催化剂、钝化材料等)微裂纹(例如亚微米裂纹)。在某些实施方案中,微裂纹不含或基本上不含含碳沉积物。在某些实施方案中,具有空微裂纹的催化剂物品没有经过热处理如煅烧或其他将除去或碳化钝化层的加热。这种热处理的例子包括将经活化涂覆的基底暴露于大于350℃、优选约350至约850℃、更优选约500至约600℃的温度,最少15分钟、优选约15至约240分钟、更优选约60至约90分钟。然而,这种催化剂制品可经受后续热处理工艺如煅烧,以从组件中除去水。
过滤器平均孔尺寸、孔隙率、孔隙互连性以及平均晶体/聚集体尺寸和活化涂层负载的具体组合,可以组合以在可接受的背压实现所需水平的颗粒过滤和催化活性。
在某些实施方案中,多孔基底上的活化涂层负载量>0.25g/in3,如>0.50g/in3,或>0.80g/in3,例如0.80至3.00g/in3。在优选的实施方案中,活化涂层负载量>1.00g/in3,如>1.2g/in3,>1.5g/in3,>1.7g/in3或>2.00g/in3或例如1.5至2.5g/in3。
孔隙率是多孔基底中的空隙空间的百分比的量度,并且涉及到排气系统中的背压:一般来说,孔隙率越低,背压越高。优选地,多孔基底具有约30%至约80%的孔隙率,例如约40%至约75%,约40%至约65%,或约50%至约60%。
孔隙互连性,作为基底的总空隙体积的百分比来测定,是基底的孔隙、空隙和/或通道连接以形成穿过多孔基底(即从入口面到出口面)的连续路径的程度。与孔隙互连性相反的是封闭的孔体积和具有到基底的仅一个表面的管道的孔的体积的总和。优选地,多孔基底具有至少约30%的孔隙互连性体积,更优选至少约40%。
多孔基底的平均孔尺寸对过滤来说也是重要的。平均孔尺寸可以通过任何可接受的方式来确定,包括通过水银孔率法。多孔基底的平均孔尺寸应具有足够高的值,以促进低背压,同时通过基底本身、通过促进基底表面上的烟灰滤饼层或者通过两者的组合来提供足够的效率。优选的多孔基底具有约10至约40μm的平均孔尺寸,例如约20至约30μm,约10至约25μm,约10至约20μm,约20至约25μm,约10至约15μm,和约15至约20μm。
在本发明的某些实施方案中,对于单个晶体来说理想的是具有渗透到多孔性基底中但不进入基底的最小孔隙空间(这将导致废气流的堵塞或转向)所需要的尺寸。因此,基底的平均孔尺寸和平均晶体尺寸和SCR催化剂的粒度应相互关联,以实现改进的催化过滤器。在某些实施方案中,平均孔尺寸与平均晶体尺寸之比为约3∶1至约20∶1,例如约5∶1至约10∶1,或约6∶1至约9∶1。在某些实施方案中,平均孔尺寸与平均粒度之比为约3∶1至约20∶1,例如约5∶1至约10∶1,或约6∶1至约9∶1。
用于移动应用的优选的多孔基底包括壁流式过滤器如壁流式陶瓷整料,和流通式过滤器如金属或陶瓷泡沫或纤维过滤器。除了堇青石、碳化硅、陶瓷和金属之外,可用于多孔基底的其他材料包括氮化铝、氮化硅、钛酸铝、α-氧化铝、莫来石例如针状莫来石、铯榴石、金属陶瓷(thermet)如Al2OsZFe、Al2O3/Ni或B4CZFe、或者包含其中任意两种或更多种片段的复合材料。特别优选的基底是钛酸铝(AT),其中AT是占主导地位的晶相。在一个优选的实施方案中,多孔基底是壁流式过滤器如典型的圆柱形过滤器元件,其由许多在轴向方向上延伸、由薄的多孔壁分隔的正方形平行通道组成。该通道一端开口,但另一端堵塞。这样,充满颗粒的废气被迫流过壁。气体能够穿过壁材料中的孔逃脱。然而,颗粒过大而无法逃脱,被捕集在过滤器壁中。
本文所述的催化沸石可以促进还原剂(优选氨)与氮氧化物的反应而选择性地形成单质氮(N2)和水(H2O),而非氧和氨的竞争反应。在一个实施方案中,催化剂可以经配制以有利于用氨(即SCR催化剂)还原氮氧化物。在另一个实施方案中,催化剂可以经配制以有利于用氧(即氨氧化(AMOX)催化剂)氧化氨。在又一个实施方案中,SCR催化器和AMOX催化剂串联使用,其中两种催化剂均包括本文所述的含有金属的沸石,和其中SCR催化剂在AMOX催化剂的上游。在某些实施方案中,AMOX催化剂布置为氧化性底层的顶层,其中该底层包含铂族金属(PGM)催化剂或非铂族金属催化剂。
用于SCR工艺的还原剂概括地指促进废气中的NOx的还原的任何化合物。用于本发明的还原剂的例子包括氨、肼或任何合适的氨前体如尿素((NH2)2CO)、碳酸铵、氨基甲酸铵、碳酸氢铵或甲酸铵,和烃如柴油燃料等。前体可通过水热或催化水解而分解为氨和其他副产物。特别优选的还原剂基于氮的,其中特别优选氨。氨可以原位产生,例如在位于过滤器制品上游的NAC的富再生期间。替代地,含氮还原剂或其前体可以直接注入到废气中。
根据本发明的另一个方面,提供用于在气体中还原NOx化合物或氧化NH3的方法,该方法包括使该气体与本文所述的用于催化还原NOx化合物的催化剂组合物接触足够的时间,以减少该气体中的NOx化合物的水平。在一个实施方案中,在至少100℃的温度用还原剂还原氮氧化物。在另一个实施方案中,在约150至750℃的温度用还原剂还原氮氧化物。在具体的实施方案中,温度范围是175到550℃。在另一个实施方案中,温度范围是175到400℃。在又一个实施方案中,温度范围是450至900℃,优选为500至750℃,500至650℃,450至550℃,或650至850℃。采用高于450℃的温度的实施方案对于处理配备有排气系统的重型和轻型柴油机的废气特别有用,该排气系统包括例如通过将烃注入过滤器上游的排气系统而主动再生的(任选催化)柴油机颗粒过滤器,其中用于本发明的沸石催化剂位于过滤器的下游。
在另一个实施方案中,氮氧化物的还原反应在氧的存在下进行。在替代实施方案中,氮氧化物还原反应在无氧条件下进行。
在另一个方面,本发明提供通过表面和/或深度过滤(优选表面过滤),用于从压缩点火发动机排出的废气中捕集颗粒物质(PM)的方法,该方法包括使含PM的废气与具有本文所述的催化剂的过滤器制品接触。
该方法可以对源自燃烧过程的气体进行,例如源自内燃机(移动式或固定式)、燃气轮机和燃煤或燃油发电厂。该方法还可以用于处理来自工业过程的气体,如炼制、来自炼油厂加热器和锅炉、熔炉、化学加工工业、炼焦炉、城市垃圾厂和焚烧炉等。在具体的实施方案中,该方法用于处理来自车辆贫燃内燃机的废气,如柴油发动机、贫燃汽油发动机或由液化石油气或天然气供能的发动机。
根据另一个方面,本发明提供一种用于车辆贫燃内燃机的排气系统,该系统包括:用于运送流动废气的导管,含氮还原剂源,如本文所述的催化剂过滤器制品。该系统可以包括控制器,用于只在确定SCR催化剂能够如在高于100℃、高于150℃或高于175℃,以等于或高于所需的效率催化NOx还原时,才将含氮还原剂计量加入流动废气。确定控制装置可以由一个或多个指示发动机条件的合适的传感器输入来辅助,该发动机条件选自由以下组成的组:废气温度、催化床温度、油门位置、系统中废气的质量流量、歧管真空度、点火时机、发动机速度、废气的λ值,注入发动机的燃料量、废气再循环(EGR)阀的位置和由此EGR的量以及增压。
在具体的实施方案中,根据废气中氮氧化物的量来控制计量,氮氧化物的量例如使用存储在控制装置中的预关联的查询表或图来直接(用合适的NOx传感器)或间接确定,该查询表或图将任一个或多个指示发动机条件的上述输入与废气的预计NOx含量相关联。含氮还原剂的计量可以经布置以使得60%至200%的理论上的氨存在于进入SCR催化剂的废气中,按1∶1NH3/NO和4∶3NH3/NO2计算。控制装置可以包括预编程的处理器,如电子控制单元(ECU)。
在另一个实施方案中,用于将废气中的一氧化氮氧化成二氧化氮的氧化催化剂可以位于将含氮还原剂计量加入废气中的位置的上游。在一个实施方案中,氧化催化剂经调整以使进入SCR沸石催化剂的气流例如在氧化催化剂入口处在250℃至450℃的废气温度具有约4∶1至约1∶3的NO与NO2的体积比。氧化催化剂可以包含至少一种铂族金属(或它们的组合)如铂、钯或铑,其涂覆在流通式整体基底上。在一个实施方案中,该至少一种铂族金属是铂、钯或铂和钯的组合。铂族金属可以负载在高表面积的活化涂层组分上,如氧化铝、沸石如铝硅酸盐沸石、二氧化硅、非沸石二氧化硅-氧化铝、氧化铈、氧化锆、氧化钛或同时含有氧化铈和氧化锆的混合氧化物或复合氧化物。
在另一个方面中,提供了一种车辆用贫燃发动机,其包括根据本发明的排气系统。车辆用贫燃内燃机可以是柴油发动机、贫燃汽油发动机或由液化石油气或天然气供能的发动机。
尽管本发明参照具体的实施方案进行了说明和描述,但是本发明并不限于所示的细节。相反,可以对权利要求书的等同范围和界限之内的细节进行各种变化,而不背离本发明。
Claims (9)
1.一种过滤器制品,其包括:
a.未钝化的陶瓷壁流式过滤器,其包括具有入口面和出口面的多孔基底;和
b.SCR催化剂组合物,其涂覆在该多孔基底入口面、出口面和所述入口面和出口面之间中的至少之一上,其中该催化剂组合物包含过渡金属助催化的分子筛晶体,和其中:
i.所述晶体具有0.5至15μm的平均晶粒尺寸,
ii.所述晶体作为单个晶体、具有小于15μm的平均粒度的聚集体或者所述单个晶体和所述聚集体的组合存在于所述组合物中;
iii.所述晶体是具有八个四面体原子的最大环尺寸的骨架类型的铝硅酸盐或硅-铝磷酸盐;和
iv.所述SCR催化剂组合物基本上不含羧酸,
其中活化涂层直接涂覆在该多孔基底上,没有中间的非催化涂层,并且沸石晶体和聚集体是未碾磨的,以及
经活化涂覆的陶瓷壁流式过滤器具有空的微裂纹。
2.根据权利要求1所述的过滤器制品,其中所述晶体具有CHA、AEI、AFT或AFX骨架类型,且所述过渡金属选自Cu和Fe中的至少一种。
3.根据权利要求2所述的过滤器制品,其中该晶体是铝硅酸盐,并具有15至50的二氧化硅与氧化铝之比。
4.根据权利要求1所述的过滤器制品,其中该平均晶粒尺寸为1.5μm至5μm。
5.根据权利要求1所述的过滤器制品,其中该多孔基底具有平均孔隙尺寸,其中平均孔隙尺寸与平均晶粒尺寸之比为3:1至20:1。
6.根据权利要求1所述的过滤器制品,其中该陶瓷壁流式过滤器包括不含催化剂的亚微米的热膨胀结点。
7.根据权利要求6所述的过滤器制品,其中该过滤器制品未经过在350℃以上的温度进行用来除去或碳化钝化层的热处理。
8.根据权利要求1所述的过滤器制品,其中所述多孔基底是具有钛酸铝作为占优势结晶相的陶瓷壁流式整料。
9.一种用于处理废气的系统,其包括:
a.未钝化的催化壁流式过滤器,该催化壁流式过滤器包括
i.具有入口面和出口面的多孔基底;和
ii.SCR催化剂组合物,其涂覆在该多孔基底入口面、出口面和所述入口面和出口面之间中的至少之一上,其中该催化剂组合物包含过渡金属助催化的分子筛晶体,其中:所述晶体具有0.5μm至15μm的平均晶粒尺寸,所述晶体作为单个晶体、具有小于15μm的平均粒度的聚集体或者所述单个晶体和所述聚集体的组合存在于所述组合物中,
其中所述分子筛是具有八个四面体原子的最大环尺寸的骨架类型的铝硅酸盐或硅-铝磷酸盐,和
所述SCR催化剂组合物基本上不含羧酸;
其中活化涂层直接涂覆在该多孔基底上,没有中间的非催化涂层,并且沸石晶体和聚集体是未碾磨的,以及
经活化涂覆的陶瓷壁流式过滤器具有空的微裂纹,
b.导管,其将壁流式过滤器与含有颗粒物质和NOx的贫燃废气的源连接,以及
c.用于将还原剂引入贫燃废气的还原剂供给系统,其中该还原剂供给系统与该催化壁流式过滤器流体连通,并位于该催化壁流式过滤器相对于经过该过滤器的气流的上游。
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KR102037224B1 (ko) | 2019-10-28 |
KR20140095524A (ko) | 2014-08-01 |
CN104023843A (zh) | 2014-09-03 |
RU2014122106A (ru) | 2015-12-10 |
JP6781210B2 (ja) | 2020-11-04 |
BR112014010538B1 (pt) | 2020-12-15 |
WO2013064887A3 (en) | 2013-07-04 |
JP6395607B2 (ja) | 2018-09-26 |
BR112014010538A2 (pt) | 2017-04-25 |
JP2019010642A (ja) | 2019-01-24 |
WO2013064887A2 (en) | 2013-05-10 |
JP2015504353A (ja) | 2015-02-12 |
US20120258032A1 (en) | 2012-10-11 |
RU2649005C2 (ru) | 2018-03-29 |
EP2773457A2 (en) | 2014-09-10 |
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