CN104994954B - NOx捕集阱组合物 - Google Patents

NOx捕集阱组合物 Download PDF

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CN104994954B
CN104994954B CN201480009068.4A CN201480009068A CN104994954B CN 104994954 B CN104994954 B CN 104994954B CN 201480009068 A CN201480009068 A CN 201480009068A CN 104994954 B CN104994954 B CN 104994954B
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F-M·麦肯纳
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Abstract

公开了生产NOx捕集阱组合物的方法，及其在NOx捕集阱和在用于内燃机的排气系统中的用途。通过在惰性气体和有机化合物存在下加热，以产生经还原性煅烧的铁/沸石，来生产NOx捕集阱组合物。然后将钯化合物添加到经还原性煅烧的铁/沸石，然后所得Pd‑Fe/沸石在含氧气体存在下在400‑600℃煅烧，以产生NOx捕集阱组合物。NOx捕集阱组合物显示了200℃以下的低温NO能力，以及在200‑250℃范围内的另外的NO储存温度窗口。

Description

NOx捕集阱组合物
发明领域
本发明涉及NOx捕集阱组合物，它在内燃机排气系统中的用途，和用于处理内燃机废气的方法。
发明背景
内燃机产生含有多种污染物的废气，污染物包括氮氧化物(“NOx”)、一氧化碳、和未燃烧的烃，它们是政府法规的目标。排放控制系统广泛使用来减少这些污染物排放到大气中的量，通常一旦排放控制系统达到它们的操作温度(通常为200℃和更高)，则获得非常高的效率。但是，这些系统在它们的操作温度以下(“冷起动”时期)相对无效。
随着甚至更严格的国家和地区法规降低可以从柴油机或汽油机排放的污染物的量，在冷起动期间减少排放正成为主要挑战。因此，持续开发出用于减少冷起动条件期间NOx和烃的排放水平的方法。
对于冷起动NOx控制，特别是在贫燃条件下，已经研究了NOx储存和释放催化剂。该催化剂在温车期间吸附NOx，在更高的废气温度热解吸NOx。下游催化剂，例如选择性催化还原(“SCR”)或NOx吸附剂催化剂(“NAC”)，有效地将解吸的NOx还原为氮。
通常，NOx吸附剂材料由无机氧化物例如氧化铝、二氧化硅、二氧化铈、氧化锆、二氧化钛或混合氧化物组成，其涂覆有至少一种铂族金属。PCT国际申请WO 2008/047170公开了一种系统，其中来自贫废气的NOx在200℃以下的温度被吸附，随后在200℃以上热解吸。教导了NOx吸附剂由钯和二氧化铈或含有铈和至少一种其他过渡金属的混合氧化物或复合氧化物组成。
PCT国际申请WO 2004/076829公开了一种废气净化系统，其包括布置在SCR催化剂上游的NOx储存催化剂。NOx储存催化剂包含至少一种碱金属、碱土金属、稀土金属，其用至少一种铂族金属(Pt、Pd、Rh或Ir)涂覆或活化。教导了特别优选的NOx储存催化剂包括涂覆有铂的二氧化铈，和在基于氧化铝的载体上作为氧化催化剂的另外的铂。EP 1027919公开了一种NOx吸附剂材料，其包含多孔载体材料，例如氧化铝、沸石、氧化锆、二氧化钛和/或氧化镧，和至少0.1wt％的贵金属(Pt、Pd和/或Rh)。例示了负载在氧化铝上的铂。
另外，US专利5,656,244和5,800,793描述了将NOx储存/释放催化剂与三效催化剂结合的系统。教导了NOx吸附剂包含铬、铜、镍、锰、钼或钴以及其他金属的氧化物，其负载在氧化铝、莫来石、堇青石或碳化硅上。PCT国际申请WO 03/056150描述了将低温NO2捕集阱材料和烟灰过滤器结合的系统。教导了低温NO2捕集阱材料包含用贱金属阳离子交换的沸石，并且该沸石选自ZSM-5、ETS-10、Y-沸石、β沸石、镁碱沸石、丝光沸石、硅酸钛和磷酸铝，该贱金属选自Mn、Cu、Fe、Co、W、Re、Sn、Ag、Zn、Mg、Li、Na、K、Cs、Nd和Pr。
遗憾的是，这种系统的NOx吸附能力不够高，特别是在高NOx储存效率方面。U.S专利申请公布2012/0308439公开了一种改进的冷起动催化剂，其包含沸石催化剂，该沸石催化剂包含贱金属例如铁、贵金属和沸石，以及负载型铂族金属催化剂，该铂族金属催化剂包含一种或多种铂族金属和一种或多种无机氧化物载体。
对于任何汽车系统和过程，仍需要在废气处理系统进一步的改进，特别是在冷起动条件下。已经发现了新的NOx捕集阱组合物，其提供增强的对内燃机废气的清洁。
发明概述
本发明是制造NOx捕集阱组合物的方法，该NOx捕集阱组合物包含负载在沸石上的钯和铁。该方法包括在惰性气体和有机化合物存在 下加热含铁沸石，以产生经还原性煅烧的铁/沸石。然后将钯化合物添加到经还原性煅烧的铁/沸石，然后将所得Pd-Fe/沸石在含氧气体存在下在400-600℃煅烧，以产生NOx捕集阱组合物。本发明还包括由该方法制造的NOx捕集阱组合物，包含负载在载体上的NOx捕集阱组合物的NOx捕集阱，和它在排气系统中的用途。NOx捕集阱组合物显示了200℃以下的低温NO能力，以及在200-250℃范围的另外的NO储存温度窗口，使它在冷起动应用中非常有用。
发明详述
本发明的方法在惰性气体和有机化合物存在下加热含铁沸石，以产生经还原性煅烧的铁/沸石。
含铁沸石可以通过任何已知手段制备。优选地，含铁沸石通过将铁化合物添加到沸石以形成含铁沸石来制造。在用于本发明的方法中之前，含铁沸石优选在含氧气体存在下在400-600℃煅烧。适合的铁化合物包括铁的硝酸盐、硫酸盐、卤化物(例如氯化物、溴化物)和羧酸盐(例如乙酸盐)。
铁化合物可以通过任何已知手段添加到沸石，添加方式不认为是特别关键的。例如，铁化合物(例如硝酸铁)可以通过浸渍、吸附、离子交换、初始润湿、沉淀等负载在沸石上。
沸石可以是任何天然的或合成的沸石，包括分子筛，并且优选包含铝、硅和/或磷。沸石通常具有SiO4、AlO4,和/或PO4的三维排列，其通过共享氧原子而结合。沸石骨架通常是阴离子型，其电荷补偿阳离子(通常是碱金属和碱土金属元素(例如Na、K、Mg、Ca、Sr和Ba))还有质子来平衡。
沸石优选是β沸石、八面沸石(例如X-沸石或Y-沸石，包括NaY和USY)、L-沸石、ZSM沸石(例如ZSM-5、ZSM-48)、SSZ-沸石(例如SSZ-13、SSZ-41、SSZ-33)、丝光沸石、菱沸石、硅铝钾沸石、毛沸石、斜发沸石、硅质岩、磷酸铝沸石(包括金属铝磷酸盐，例如SAPO-34)、中孔沸石(例如MCM-41、MCM-49、SBA-15)、金属掺入 的沸石或者其混合物；更优选地，沸石是β沸石、ZSM-5沸石或SSZ-33或Y-沸石。沸石最优选是β沸石。
在将铁化合物添加到沸石之后，所得铁-沸石物质优选在含氧气体(例如空气)存在下在400-600℃煅烧。煅烧优选进行大于1小时。
含铁沸石在惰性气体和有机化合物存在下加热以产生经还原性煅烧的铁/沸石。惰性气体是基本上不含氧(小于1vol％氧，优选小于0.1vol％氧)的任何气体，更优选不含氧。优选地，惰性气体是氮气、氩气、氖气、氦气、二氧化碳等及其混合物。
有机化合物优选是有机聚合物和/或生物聚合物。适合的有机聚合物包括聚乙烯、聚丙烯和聚二醇例如聚环氧乙烷和聚环氧丙烷。适合的生物聚合物包括多糖、纤维素和聚葡糖胺和脂质。最优选地，有机化合物是聚环氧乙烷。有机化合物在较高温度分解，将氧排放到气态分解产物，这然后有助于烃气氛。使用还原性烃气氛来制造含铁SCR活性沸石催化剂公开于美国专利申请公布2012/0208692中，其教导在此引入以供参考。
通常，含铁沸石和有机化合物在加热之前混合，以使有机化合物:含铁沸石的重量比是0.05-2，更优选0.05-0.5。加热优选在300-700℃、更优选400-650℃的温度进行。
然后将钯化合物添加到经还原性煅烧的铁/沸石，以形成Pd-Fe/沸石。适合的钯化合物包括钯的硝酸盐、硫酸盐、卤化物(例如氯化物、溴化物)、羧酸盐(例如乙酸盐)和胺络合物。钯化合物可以通过任何已知手段添加到经还原性煅烧的铁/沸石，添加方式不认为是特别关键的。例如，钯化合物(例如硝酸钯)可以通过浸渍、吸附、离子交换、初始润湿、沉淀、喷雾干燥等添加到经还原性煅烧的铁/沸石。
在添加钯化合物之后，Pd-Fe/沸石在含氧气体(例如空气)存在下在400-600℃范围内的温度煅烧，以产生NOx捕集阱组合物。煅烧优选进行大于1小时。
本发明还包括根据上述方法制备的NOx捕集阱组合物，包含负载在金属或陶瓷基底上的该NOx捕集阱组合物的NOx捕集阱。
陶瓷基底可以由任何适合的难熔材料制成，例如氧化铝、二氧化硅、二氧化钛、二氧化铈、氧化锆、氧化镁、沸石、氮化硅、碳化硅、硅酸锆、硅酸镁、铝硅酸盐和金属铝硅酸盐(例如堇青石和锂辉石)或者其任意两种或更多种的混合物或混合氧化物。特别优选堇青石、铝硅酸镁和碳化硅。
金属基底可以由任何适合的金属制成，特别是耐热金属和金属合金例如钛和不锈钢以及含有铁、镍、铬和/或铝还有其他痕量金属的铁素体合金。
基底优选是流通式基底或过滤器基底。最优选地，基底是流通式基底。特别地，流通式基底是优选具有蜂窝体结构的流通式整料，具有许多小的、平行的薄壁通道，轴向穿过基底并在整个基底延伸。基底的通道截面可以是任何形状，但是优选方形、正弦曲线形、三角形、矩形、六边形、梯形、圆形或椭圆形。
优选地，NOx捕集阱通过使用活化涂覆(washcoat)程序将NOx捕集阱组合物沉积在基底上来制备。用于使用活化涂覆程序制备NOx捕集阱的代表性方法在下面阐述。将理解的是，以下方法可以根据本发明的不同实施方案而变化。
活化涂覆优选如下进行：首先在适合的溶剂(优选水)中使磨细的NOx捕集阱组合物颗粒制浆，以形成浆料。浆料优选含有5-70wt％的固体，更优选10-50wt％。优选地，将颗粒研磨或者使其经过另一粉碎过程，以确保在形成浆料之前，基本上全部的固体颗粒具有平均直径小于20微米的粒度。也可以在浆料中加入另外的组分，例如稳定剂或促进剂，作为水溶性或水分散性化合物或络合物的混合物。
基底然后可以用浆料涂覆一次或多次，以使所需负载量的NOx捕集阱组合物沉积在基底上。
还可以在基底上形成NOx捕集阱组合物，以产生NOx捕集阱。在这种程序中，如上所述将含铁沸石的浆料活化涂覆在基底上。在含铁沸石已经沉积在基底上之后，将基底在惰性气体和机化合物存在下加热，以在基底上产生经还原性煅烧的铁/沸石，如上所述。钯化合物然 后可以通过任何已知手段添加到基底，包括浸渍、吸附或离子交换，以在基底上形成Pd-Fe/沸石，其然后可以在含氧气体存在下在400-600℃煅烧，以产生NOx捕集阱。
优选地，基底的整个长度涂覆有NOx捕集阱组合物，从而NOx捕集阱组合物的活化涂层覆盖基底的整个表面。
在NOx捕集阱组合物沉积在基底上之后，NOx捕集阱通常通过在优选80-150℃的升高的温度加热来干燥，然后通过在升高的温度加热来煅烧。优选地，煅烧在400-600℃进行约1-8小时。
本发明还包括冷起动催化剂，其包含本发明的NOx捕集阱组合物和负载型铂族金属催化剂，该铂族金属催化剂包含一种或多种铂族金属和一种或多种无机氧化物载体。负载型铂族金属催化剂包含一种或多种铂族金属(“PGM”)和一种或多种无机氧化物载体。PGM可以是铂、钯、铑、铱或其组合，最优选是铂和/或钯。无机氧化物载体最通常包括第2、3、4、5、13和14族和镧系元素的氧化物。有用的无机氧化物载体优选具有10-700m2/g范围内的表面积，0.1-4mL/g范围内的孔体积，和约10-1000埃的孔径。无机氧化物载体优选是氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化铈、氧化铌、钽氧化物、钼氧化物、钨氧化物或者其任意两种或更多种的混合氧化物或复合氧化物，例如二氧化硅-氧化铝、二氧化铈-氧化锆或氧化铝-二氧化铈-氧化锆。特别优选氧化铝和二氧化铈。
负载型铂族金属催化剂可以通过任何已知手段来制备。优选地，一种或多种铂族金属通过任何已知手段来加载到一种或多种无机氧化物上，以形成负载型PGM催化剂，添加方式不认为是特别关键的。例如，铂化合物(例如硝酸铂)可以通过浸渍、吸附、离子交换、初始润湿、沉淀等负载在无机氧化物上。也可以将其他金属添加到负载型PGM催化剂。
冷起动催化剂可以通过现有技术中公知的方法来制备。NOx捕集阱和负载型铂族金属催化剂可以物理混合以产生冷起动催化剂。优选地，冷起动催化剂进一步包含流通式基底或过滤器基底，从而NOx捕 集阱组合物和负载型铂族金属催化剂涂覆到流通式基底或过滤器基底上，优选使用活化涂覆程序沉积在流通式基底或过滤器基底上，以产生冷起动催化剂系统。
本发明还包括用于内燃机的排气系统，系包括本发明的NOx捕集阱。排气系统优选包括一个或多个另外的后处理装置，其能够在正常操作温度从内燃机废气中除去污染物。优选地，排气系统包括冷起动催化剂，和：(1)选择性催化还原系统；(2)微粒过滤器；(3)选择性催化还原过滤器系统；(4)NOx吸附剂催化剂；(5)三效催化剂系统；或者其任意组合。
这些后处理装置在本领域中是公知的。选择性催化还原(SCR)系统是通过与氮化合物(例如氨或尿素)或烃(贫NOx还原)反应将NOx还原为N2的装置。典型的SCR催化剂包含氧化钒-二氧化钛催化剂、氧化钒-氧化钨-二氧化钛催化剂或者金属/沸石催化剂例如铁/β沸石、铜/β沸石、铜/SSZ-13、铜/SAPO-34、Fe/ZSM-5或铜/ZSM-5。
微粒过滤器是从内燃机废气中减少微粒的装置。微粒过滤器包括催化型微粒过滤器和单纯(非催化型)微粒过滤器。催化型微粒过滤器(用于柴油和汽油应用)包含金属和金属氧化物组分(例如Pt、Pd、Fe、Mn、Cu和二氧化铈)，以氧化烃和一氧化碳，并且破坏被该过滤器捕集的烟灰。
选择性催化还原过滤器(SCRF)是结合了SCR和微粒过滤器的功能的单个基底装置。它们用来从内燃机减少NOx和微粒排放物。
NOx吸附剂催化剂(NAC)设计用来在贫废气条件下吸附NOx，在富条件下释放吸附的NOx，和将释放的NOx还原以形成N2。NAC通常包含NOx储存组分(例如Ba、Ca、Sr、Mg、K、Na、Li、Cs、La、Y、Pr和Nd)、氧化组分(优选Pt)和还原组分(优选Rh)。这些组分包含在一种或多种载体上。
三效催化剂系统(TWC)通常在化学计量条件下用于汽油机中，以在单个装置上将NOx转化为N2，将一氧化碳转化为CO2，和将烃转化为CO2和H2O。
本发明还包括处理内燃机废气，特别是处理机动车贫燃内燃机(例如柴油机、贫燃汽油机或由液化石油气或天然气提供动力的发动机)的废气。该方法包括使废气与本发明的NOx捕集阱接触。
以下实施例仅阐述本发明。本领域技术人员将认识到本发明主旨和权利要求书范围内的许多变化。
实施例1：制备催化剂
催化剂1A：催化剂1A通过以下来制备：将硝酸Fe湿浸渍到β沸石(Tosoh931)上，然后在空气中在500℃煅烧。所得粉末与8wt％聚环氧乙烷混合，在氮气存在下在600℃煅烧。然后将钯浸渍到Fe/β材料上至1wt％Pd的负载量，Pd-Fe/β产物然后在空气中在500℃煅烧，以产生催化剂1A(含有1wt％Pd和1wt％Fe)。
对比催化剂1B：对比催化剂1B根据催化剂1A的程序来制备，不过不进行还原性煅烧步骤(在聚环氧乙烷存在下)。对比催化剂1B含有1wt％Pd和1wt％Fe。
对比催化剂1C：对比催化剂1C根据对比催化剂1B的程序来制备，不过Pd-Fe/β产物在750℃煅烧，而非在500℃。对比催化剂1C含有1wt％Pd和1wt％Fe。
对比催化剂1D：对比催化剂1D通过以下来制备：将硝酸Fe湿浸渍到β沸石(Tosoh931)上，然后在空气中在500℃煅烧。随后在500℃在稀H2中进行直接还原处理2小时。然后将钯浸渍到Fe/β材料上至1wt％Pd的负载量，Pd-Fe/β产物然后在空气中在500℃煅烧，以产生对比催化剂1D(含有1wt％Pd和1wt％Fe)。
实施例2：NOx储存测试程序
将催化剂(0.4g)在含NO气体中在90℃保持5分钟，然后以20℃/分钟的升温速率将温度提高到215℃，以获得200℃的床层温度，在这里将催化剂再保持5分钟，然后进一步升温到290℃，和275℃的床层温度保持另外5分钟。该吸附阶段之后是在TPD气体存在下的程序升温解吸(TPD)，直到床层温度达到约500℃，以清出催化剂中全部 储存的NOx用于进一步测试。
含NO气体包含10.5vol％O2、50ppm NO、6vol％CO2、1500ppm CO、100ppm烃和6.3vol％H2O。
TPD气体包含10.5vol％O2、6vol％CO2、1500ppm CO、100ppm烃和6.3vol％H2O。
NOx储存结果示于表1中。
储存测试结果显示，有两个NOx吸附在不同催化剂上的不同的温度窗口。在约90℃的较低温度窗口对冷起动性能是关键的。在该温度范围内较高的NOx储存表明用于冷起动应用的较大潜力。在200-250℃的较高温度窗口对避免高负荷操作期间的NOx漏失有用。表1的结果显示，仅催化剂1A和对比催化剂1C(经过高温750℃煅烧)展示出在低温(冷起动)窗口中良好的NOx吸收。但是，活化对比催化剂1C所需的高温处理是不希望的和昂贵的。另外，较高温度煅烧的对比催化剂1C材料没有展示出测试的高温(200-250℃)区域中的NOx吸收，因而具有总体上低的NOx吸收能力。
表1：NOx储存结果
*比较例。

Claims (17)

1.生产NOx捕集阱组合物的方法，其包括：
(a)在惰性气体和有机化合物存在下加热含铁沸石，以产生经还原性煅烧的铁/沸石；
(b)将钯化合物添加到经还原性煅烧的铁/沸石，以形成Pd-Fe/沸石；和
(c)在含氧气体存在下在400-600℃煅烧Pd-Fe/沸石，以产生NOx捕集阱组合物。
2.根据权利要求1所述的方法，其中沸石选自β沸石、八面沸石、L-沸石、ZSM沸石、SSZ-沸石、丝光沸石、菱沸石、硅铝钾沸石、毛沸石、斜发沸石、硅质岩、磷酸铝沸石、中孔沸石及其混合物。
3.根据权利要求1或2所述的方法，其中沸石是β沸石。
4.根据权利要求1或2所述的方法，其中惰性气体选自氮气、氩气、氖气、氦气、二氧化碳及其混合物。
5.根据权利要求1或2所述的方法，其中有机化合物是有机聚合物和/或生物聚合物。
6.根据权利要求1或2所述的方法，其中有机化合物选自聚乙烯、聚丙烯、聚二醇、多糖、纤维素、聚葡糖胺和脂质。
7.根据权利要求1或2所述的方法，其中有机化合物是聚环氧乙烷。
8.根据权利要求1或2所述的方法，其中钯化合物是钯的硝酸盐、硫酸盐、卤化物、羧酸盐或胺络合物。
9.根据权利要求1或2所述的方法，其中含铁沸石如下来制备：将铁化合物添加到沸石以形成铁-沸石物质，和在含氧气体存在下在400-600℃煅烧铁-沸石物质以产生含铁沸石。
10.根据权利要求9所述的方法，其中铁化合物是铁的硝酸盐、硫酸盐、卤化物或羧酸盐络合物。
11.NOx捕集阱组合物，其根据前述权利要求中任一项所述的方法制备或者能够获得。
12.NOx捕集阱，其包含负载在金属基底或陶瓷基底上的根据权利要求11所述的NOx捕集阱组合物。
13.根据权利要求12所述的NOx捕集阱，其中基底是流通式整料。
14.用于内燃机的排气系统，其包括根据权利要求12或13所述的NOx捕集阱。
15.根据权利要求14所述的排气系统，还包括：选择性催化还原催化剂系统；微粒过滤器；选择性催化还原过滤器系统；NOx吸附剂催化剂；三效催化剂系统；或其组合。
16.用于处理内燃机废气的方法，其包括使废气与根据权利要求12或13所述的NOx捕集阱接触。
17.冷起动催化剂，其包含根据权利要求11所述的NOx捕集阱组合物，和包含一种或多种铂族金属和一种或多种无机氧化物载体的负载型铂族金属催化剂。
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