CN110461470B - 选择性催化还原催化剂 - Google Patents

选择性催化还原催化剂 Download PDF

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CN110461470B
CN110461470B CN201880021400.7A CN201880021400A CN110461470B CN 110461470 B CN110461470 B CN 110461470B CN 201880021400 A CN201880021400 A CN 201880021400A CN 110461470 B CN110461470 B CN 110461470B
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catalyst
catalyst composition
component
metal
substrate
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CN110461470A (zh
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D·比斯库泊斯基
J·W·明奇
I·皮拉斯
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Johnson Matthey Catalysts Germany GmbH
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Abstract

用于应用含氮还原剂转化废气中氮氧化物(NOx)的选择性催化还原催化剂组合物，所述催化剂组合物包含第一组分和第二组分的混合物，其中所述第一组分为H型铝硅酸盐菱沸石(CHA)或H型铝硅酸盐丝光沸石(MOR)与H型铝硅酸盐菱沸石(CHA)的混合物；和所述第二组分为在金属氧化物载体上载带的钒氧化物，所述载体为二氧化钛、二氧化硅稳定的二氧化钛或二氧化钛与二氧化硅稳定的二氧化钛的混合物，其中第一组分与第二组分的重量比为10:90至25:75。

Description

选择性催化还原催化剂
本发明涉及用于应用含氮还原剂转化废气中氮氧化物(NOx)的选择性催化还原催化剂组合物。
本申请人的WO 2014/027207 A1公开了用于处理由燃烧过程获得的废气中氮氧化物的催化剂组合物，例如来自内燃机(移动或固定的)、燃气透平或燃煤或燃油电站的废气，所述催化剂包含第一组分和第二组分的掺混物，其中所述第一组分为铝硅酸盐或铁硅酸盐分子筛组分，和其中所述分子筛或者为H+型或者用一种或多种过渡金属进行了离子交换，和所述第二组分为在选自氧化铝、二氧化钛、氧化锆、二氧化铈、二氧化硅及其组合上载带的钒氧化物。
EP 255121A2公开了包含如下的催化剂：(A)’钛的氧化物、(B)’选自钨和钼的至少一种金属的氧化物、(C)’钒的氧化物和(D)’选自钇、镧、铈、钕、铜、钴、锰和铁的至少一种金属，组分(D)’沉积于沸石上，这种催化剂用于脱除固定产生源如燃烧炉或锅炉产生的含氮氧化物和砷化合物的废气中的氮氧化物。
US 4798813公开了用于脱除燃烧炉废气中氮氧化物的催化剂，所述废气包含可挥发性催化剂毒物如砷、硒和碲。所述催化剂包含表面积为20m2/g或更低的二氧化钛和在其上载带0.01-20wt％铜的沸石，所述沸石平均孔径为
Figure BDA0002216041580000011
或更小和二氧化硅/氧化铝的摩尔比为10或更大。
US 4735927A1公开了用于在氨的存在下选择性还原氮氧化物为氮的催化剂，其对于废气中包含的硫氧化物中毒具有耐受性，所述催化剂为由如下物质的混合物形成的复合体形式：锐钛矿(5-40wt％)、沸石(50-90％)、粘结材料(0-30％)和任选至少为0.1wt％的选自钒、钼和铜的氧化物的促进剂。
WO 88/02659公开了用于脱除电站或工业炉排出的烟气中的氮氧化物的催化剂，所述催化剂包含孔径为
Figure BDA0002216041580000021
和处于其酸形式(H型)的耐酸沸石。催化剂的组分可以包括作为附加试剂的少量过渡金属元素铁、钒、钼、钨、镍、钴、铜、铬和/或铀。另外，以催化剂的质量计，所述催化剂可以包含至多40wt％的氧化钛。
US 2002/0004446A1公开了用于在还原剂的存在下在400-750℃的温度下分解氮氧化物的催化剂体，所述催化剂体包含：包含氢离子交换的酸沸石和活性组分的活性材料，所述活性材料包含40-60wt％的所述沸石和40-60wt％的所述活性组分，所述活性组分包含70-95wt％的二氧化钛、2-30wt％的三氧化钨、0.1-10wt％的氧化铝和0.1-10wt％的二氧化硅。
WO 2008/089957 A1公开了用于还原柴油机废气中氮氧化物的催化剂组合物，所述催化剂包含选自V2O5、WO3、TiO2的至少两种氧化物和金属交换的不含贵金属的沸石。所述交换金属优选为Co、Cu、Fe或Ni，特别是Fe。催化剂组合物中金属交换的沸石的含量限制为小于10wt％，5-8wt％最为优选。
US 4663300A公开了用于还原烟气中氮氧化物为氮的催化剂组合物和方法。所述催化剂包含二氧化钛、丝光沸石和金属组分。优选的金属组分包括钒氧化物和钨氧化物。至少存在15wt％的丝光沸石，优选的是高二氧化硅H-丝光沸石。
EP 2614886 A1公开了一种NOx还原催化剂，其用于对燃烧高含硫煤、来自PowderRiver Basin(USA)的煤、生物质等的锅炉废气用氨进行氮氧化物的催化还原，废气中也包含催化剂毒物如砷、磷和钾。这种催化剂需要较低比率的SO2氧化，以避免SO3排放和形成所谓的“酸雨”，和要求氧化废气中存在汞的高活性。所述催化剂由催化剂组合物组成，其包含钛(Ti)、磷的氧化物、钼(Mo)和/或钨(W)、钒(V)的氧化物、和高二氧化硅沸石(其SiO2/Al2O3比不小于20)。
随着对WO 2014/027207 A1中公开的催化剂配制物的继续研究，本发明人发现H型铝硅酸盐菱沸石或H型铝硅酸盐菱沸石与H型铝硅酸盐丝光沸石的组合物作为第一组分与第二载带的钒氧化物组分的组合物(掺混物)具有更好的NOx转化率和更低或可对比的N2O选择性(即选择性地转化NOx为N2，而不是N2O)，特别是当作为新催化剂进行测试时，无论与US4663300A中公开的只包含H型丝光沸石的组合物相比还是与WO 2014/027207 A1中公开的只包含铁促进的铝硅酸盐MFI沸石的组合物相比都如此，特别是当温度至多400℃时。这种协同作用按所附权利要求和下文描述进行定义。
按照第一方面，本发明提供用于应用含氮还原剂转化废气中氮氧化物(NOx)的选择性催化还原催化剂组合物，所述催化剂组合物包含第一组分和第二组分的混合物，其中所述第一组分为H型铝硅酸盐菱沸石(CHA)或H型铝硅酸盐丝光沸石(MOR)与H型铝硅酸盐菱沸石(CHA)的混合物；和所述第二组分为在金属氧化物载体上载带的钒氧化物，所述载体为二氧化钛、二氧化硅稳定的二氧化钛或二氧化钛与二氧化硅稳定的二氧化钛的混合物，其中第一组分与第二组分的重量比为10:90至25:75。
下面将进一步描述本发明。在下文中，将更为详细地描述本发明的不同方面/实施方案。如果没有明显地相反说明，这样定义的每一方面/实施方案可以与任意的其它方面/实施方案组合。具体地，作为优选或有利指出的任何特征均可以与作为优选或有利指出的任何其它特征组合。打算的是与产品相关所公开的特征可以与方法相关所公开的那些特征组合，或者相反。
另外，这里所应用的术语“包含”可以与定义“主要包含…”或“由…组成”互换。术语“包含”用于指所提到的元素是主要的，但可以加入其它元素，和仍在权利要求范围内。“主要包含…”限制权利要求的范围至指定的材料或步骤及不实质影响所要求发明基础和新颖性特性的特征。术语“由…组成”封闭了权利要求，其包括除通常与之相关的杂质以外引述的那些不同的材料。
当两者都存在时，H型铝硅酸盐丝光沸石(MOR)与H型铝硅酸盐菱沸石(CHA)的重量比优选为5:3至3:5，最优选为1:1至3:5。这些参数的优点在下文的实施例中示出。
任选地，第一组分与第二组分的重量比为15:85至20:80。
当按本发明的第一方面的催化剂组合物为用于挤出为基质时，所述催化剂组合物优选包含一种或多种粘结剂组分，其中第一和第二组分的组合重量与一种或多种粘结剂组分的组合重量的重量比为80:20至95:5，优选为90:10至85:15。所述一种多种粘结剂组分可以为粘土如氧化铝和/或玻璃纤维。
CHA骨架型号(由国际沸石协会定义)指共有相同结构的一类天然或合成分子筛。CHA定义为具有八个四面体原子的最大孔开口，和具有该特征的分子筛在文献中称为“小孔”分子筛。铝硅酸盐分子筛通常称作沸石。优选的CHA骨架型号的铝硅酸盐沸石为SSZ-13。合成铝硅酸盐CHA是已知的，和已进行过广泛研究和表征。例如参见美国专利US 4544538、WO 2008/106519和WO 2008/132452。
MOR骨架型号丝光沸石最初被认为是天然矿物，但其随后被合成生产(参见Meier,W.M.的The crystal structure of mordenite(ptilolite)Z.Kristallogr.,115,439-450(1961)；和美国专利US 4503023)。类似地，CHA骨架型号最初被认为是天然矿物，但其随后被合成生产(参见D.S.Coombs等人的Can.Mineral.35(1997)1571-1606；和美国专利US4544538)。虽然在本发明中可以应用天然丝光沸石和/或菱沸石，但要采取合适步骤例如通过洗涤和氨离子交换脱除天然材料中存在的杂质和反离子如钙、镁、锶、钠和/或钾(例如参见DE102005010221)，我们倾向于应用合成的铝硅酸盐丝光沸石。向用于制备本发明产品的混合物中添加的丝光沸石(参见实施例1)可为预制的H型丝光沸石或氨型，后者在煅烧后从中脱除氨转化为H型。
合成的铝硅酸盐CHA中二氧化硅与氧化铝的比(SAR)优选为20-50。如果SAR太高，沸石的表面积减少，则存在太少的酸位来有效地存贮氨和/或提供NOx转化活性。如果SAR太低，沸石易于结构损坏和因此在应用中通过水热老化造成骨架和表面坍塌。天然菱沸石的SAR为2-8。
与上文针对CHA讨论的原因相同，用于本发明的合成铝硅酸盐丝光沸石的丝光沸石的SAR可以为10-30。天然丝光沸石的SAR通常为8-12。
合适的粘土包括富勒土、海泡石、锂蒙脱石、蒙脱石、高岭土及其任意两种或更多种的混合物，其中高岭土可选自亚膨润土、蠕陶土、埃洛石、高岭石、地开石、珍珠陶土及其任意两种或更多种的混合物；蒙脱石可选自蒙脱土、绿脱石、蛭石、皂石及其任何两种或更多种的混合物；富勒土可以是蒙脱土或坡缕石(绿坡缕石)。
无机纤维可以选自碳纤维、玻璃纤维、金属纤维、硼纤维、氧化铝纤维、二氧化硅纤维、二氧化硅-氧化铝纤维、碳化硅纤维、钛酸钾纤维、硼酸铝纤维和陶瓷纤维。无机纤维可以改进在优选的汽车用途中应用的煅烧产品的机械强度，和在汽车废气系统中应用的煅烧产品“罐封”期间的机械强度。
氧化铝优选为γ氧化铝。当应用氧化铝时，为了确保与氧化铝粘结，有利的是向氧化铝或氧化铝的前体物质中加入水溶性金属盐的水溶液，随后加入其它初始物质。替代地，可以应用任意的其它过渡氧化铝，即α氧化铝、β氧化铝、χ氧化铝、η氧化铝、ρ氧化铝、κ氧化铝、θ氧化铝、δ氧化铝、镧β氧化铝和这些过渡氧化铝中任意两种或更多种的混合物。也可以将氧化铝作为溶胶加入到可挤出混合物中，好处是所得的煅烧产品机械性更强。
优选地，为了改进催化剂的热稳定性和新鲜催化剂的NOx转化活性，第二组分的金属氧化物载体包含钨氧化物、钼氧化物、钨氧化物和钼氧化物两者，但更优选为钨氧化物。
第二组分的钒氧化物可以包含铁钒酸盐，因为其可以提供某些优点，包括改进低温(180-350℃)活性和比钒氧化物更高的温度稳定性，正如WO 2011/127505中所公开。
以催化剂组合物整体的总重量计，包括任何粘结剂的催化剂组合物可以包含0.5-5.0wt％按V2O5计算的钒，优选为1.0-3.0wt％。这种计算方法也适用于当钒组分为铁钒酸盐(FeVO4)时。
按照第二方面，提供一种催化载体涂层，所述载体涂层包含本发明第一方面的催化剂组合物，其包含一种或多种填料、粘结剂、处理助剂、水和掺杂剂。处理助剂可以包括在这种方法中应用的流变改性剂，例如在WO 99/047260 A1、WO 2011/080525 A1、WO 2014/195685 A1或WO 2015/145122 A2的涂覆方法中所公开的。
按照第三方面，本发明提供一种催化剂制品，其包含用本发明第二方面的催化载体涂层涂覆的整块基质。所述基质可为金属流通式基质、陶瓷流通式基质、壁流式过滤器、烧结金属过滤器或部分过滤器。
按照第四方面，优选的催化剂制品包含为挤出基质形式、优选为蜂窝整块形式的本发明第一方面的催化剂组合物。在这种情况中，催化剂组合物优选包含钨酸盐而不是钼酸盐。
将会理解的是无论催化剂组合物作为惰性基质上涂覆的载体涂层存在或作为挤出基质存在，均可以获得本发明的好处，即改进的NOx转化活性和产生更少的N2O。
制备本发明第四方面的挤出催化剂制品的方法例如由WO 2014/027207 A1和WO2011/092521 A1或这里作为背景技术认可的那些文献的任意一个已知。可以添加合适的有机助剂如粘结剂、填料、孔改性剂、挤出润滑剂和增塑剂以促进混合，从而形成均匀的可挤出物。所述有机助剂可以包括纤维素、水溶性树脂如聚环氧乙烷或聚乙二醇，并在煅烧过程中从最终基质中烧掉。
本发明第三或第四方面的催化剂制品可以包含为载体涂层形式的第二催化剂组合物，用于应用含氮还原剂选择性还原NOx和/或用于氧化NH3，其中第二催化剂组合物为：(a)本发明第一方面的催化剂混合物；(b)过渡金属促进的分子筛；(c)在金属氧化物上载带的铂族金属；或(d)在二氧化钛上载带的包含钒氧化物的催化剂。将会理解的是选项(a)已经由本发明的第三方面所定义，和因此可以由从属于本发明第三方面的任何权利要求中删除。
本发明第三或第四方面的催化剂制品可以包含氨滑流催化剂(ASC)，其包含用于氧化氨的第一层(c)和包含本发明第一方面催化剂的第二层，其中第一层直接放置于基质上，而第二层覆盖第一层上。这种设置由于可以促进如下反应而有利。在第一层中：2NH3+1.5O2→N2+3H2O(+NO和/或NO2)；和在第二层中：NO+NH3+1/4O2→N2+3/2H2O；或NO+NO2+2NH3→2N2+3H2O；或NO2+4/3NH3→7/6N2+2H2O。在第二层的反应中NO和NO2源可以为废气本身和/或第一层中产生NO或NO2的副反应。在第二层的反应中氨源可以为废气本身和/或由废气吸附到第二层组分中的氨。
按照第五方面，提供用于处理废气的废气系统，包含位于氨滑流催化剂(ASC)上游的选择性催化还原(SCR)催化剂，其中SCR和ASC催化剂的至少一个包含本发明第一方面的催化剂。
本发明第五方面的废气系统可以包含氧化催化剂，所述氧化催化剂包含在整块基质上涂覆的在金属氧化物中载带的铂族金属，和放置于SCR催化剂组合物的上游。这会促进废气中存在的氮氧化物以接近4NO:NO2至约NO:3NO2的体积比氧化为二氧化氮。如此操作以比单独的NO或NO2在动力学上更快速地转化NOx(例如参见S.Kasaoka等人的Nippon KagakuKaishi,1978,No.6,pp.874-881)。
本发明的SCR催化剂组合物可以用于处理来自静态来源的NOx排放的废气，如燃气透平或燃煤或燃油电站。在这种情况中，可以将所述催化剂组合物涂覆于所谓的波纹打孔金属片的板型基质上。用于这类用途的催化剂组合物优选包括钼酸盐而不是钨酸盐。但优选的和按照本发明的第六方面，本发明提供机动车辆的贫燃内燃机，其包含本发明第五方面的废气系统。
按照第七方面，本发明提供包含本发明第六方面的发动机的机动车辆。
按照第八方面，本发明提供一种处理废气的方法，其任选地包含约4:1至约1:3体积比的NO与NO2比，该比率例如可以通过合适设计的氧化催化剂被动地促进，所述方法包括如下步骤：使含NOx和NH3的废气物流与本发明第一方面的催化剂或本发明第三或第四方面的催化剂制品接触；和按上文针对第一层和第二层所述的反应，转化至少一部分NOx为N2和/或转化至少一部分NH3为N2、NO和NO2中的至少一种，其中所述第一层为(c)，即金属氧化物上载带的铂族金属。
为了可以更全面地理解本发明，通过描述方式提供如下实施例。
实施例
实施例1：制备挤出的蜂窝状基质
通过首先使商购的粉末状H型铝硅酸盐CHA、商购的粉末状H型铝硅酸盐丝光沸石或粉末状H型铝硅酸盐CHA和粉末状H型铝硅酸盐丝光沸石两者的混合物与2wt％的V2O5-10wt％WO3/TiO2以及余量的改变挤出物流变性和增加挤出物机械强度的无机助剂混合，以制备WO 2014/027207 A1的挤出蜂窝状基质催化剂。所有的沸石均为合成沸石，并在优选的SAR范围内选择。加入合适的有机助剂以利于混合从而形成均匀的可挤出物。将所述可挤出物挤出，以形成具有流通结构(即在两端均有开口的蜂窝)的1-英寸直径x 70mm长的圆柱状蜂窝体，其蜂窝密度为每平方英寸400个蜂窝和蜂窝壁厚为11/1000英寸(mil)。然后干燥和煅烧如此形成的挤出蜂窝基质，以形成最终产品。
选择沸石、V2O5-WO3/TiO2、无机助剂的合适比例，从而通过煅烧脱除有机助剂后，所述挤出基质具有如下表1所示的wt％组成。
表1
Figure BDA0002216041580000081
实施例2：挤出的蜂窝状基质老化
使实施例1获得的挤出催化剂蜂窝基质在加速老化步骤中热老化(不加入水)，所述热老化在烘箱中在大于600℃下在空气中将它们加热2小时(在这里称作“新鲜的”)，或者在650℃下加热100小时(在这里称作“老化的”)进行，以模拟按欧洲排放标准法规在汽车寿命终端时蜂窝基质预期暴露于机动车辆废气中。
实施例3：催化剂性能
将所述新鲜和老化的基质分别暴露于空速约120,000/h的模拟柴油发动机废气中。所述的模拟废气包含约9.3wt％的O2、约7.0wt％的H2O、约300ppm的NOx(仅NO)、约300ppm的NH3，余量为N2。在180、215、250、300和400℃的温度下确定新鲜和老化催化剂基质两者转化NOx的活性。在表2和表3中给出了以％NOx转化率数据表示的结果(数值越大越好)。
表2–新鲜催化剂基质样品的NOx转化率％
Figure BDA0002216041580000091
表3–老化的催化剂基质样品的NOx转化率％
Figure BDA0002216041580000101
在表4中给出了500℃下经过“老化”催化剂基质样品产生的N2O ppm值(数值越小越好)。
表4–由“老化的”催化剂基质在500℃产生的N2O ppm
Figure BDA0002216041580000102
由表2、3和4所示的数据可以看出，实施例1的新鲜NOx转化活性与两个对比例相当，而实施例2和3好于两个对比例。实施例1的老化NOx转化活性好于任何一个对比例，实施例3与对比例2的活性相当，而实施例2与对比例1相当。表4中的N2O滑流数据表明实施例1比对比例2有更少的N2O生成，而与对比例1的N2O生成相当。实施例2和3均比对比例产生适度更多的N2O。
总之，这些数据表明优选顺序为实施例1>>实施例3>实施例2。
通过解释和描述方式提供了前述详细描述，但不限制所附权利要求的范围。这里描述的优选实施方案的许多改变对本领域普通技术人员来说是很明显的，并且保留在所附权利要求及其等价物的范围内。
为避免怀疑，已知现有技术的全部内容在这里作为参考引入。

Claims (20)

1.用于应用含氮还原剂转化废气中氮氧化物NOx的选择性催化还原催化剂组合物，所述催化剂组合物包含第一组分和第二组分的混合物，其中所述第一组分为SAR为20-50的H型合成铝硅酸盐菱沸石CHA或者SAR为10-30的H型合成铝硅酸盐丝光沸石MOR与SAR为20-50的H型合成铝硅酸盐菱沸石CHA的混合物；和所述第二组分为在金属氧化物载体上载带的钒氧化物，所述载体为二氧化钛、二氧化硅稳定的二氧化钛、二氧化钛与二氧化硅稳定的二氧化钛的混合物或WO3/TiO2，其中第一组分与第二组分的重量比为10:90至25:75。
2.权利要求1的催化剂组合物，其中H型合成铝硅酸盐丝光沸石MOR与H型合成铝硅酸盐菱沸石CHA的重量比为5:3-3:5。
3.权利要求2的催化剂组合物，其中H型合成铝硅酸盐丝光沸石MOR与H型合成铝硅酸盐菱沸石CHA的重量比为1:1-3:5。
4.权利要求1-3任一项的催化剂组合物，其中第一组分与第二组分的重量比为15:85-20:80。
5.权利要求1-3任一项的催化剂组合物，包含一种或多种粘结剂组分，其中第一和第二组分的组合重量与一种或多种粘结剂组分的组合重量的重量比为80:20-95:5。
6.权利要求5的催化剂组合物，其中第一和第二组分的组合重量与一种或多种粘结剂组分的组合重量的重量比为90:10-85:15。
7.权利要求5的催化剂组合物，其中所述一种或多种粘结剂组分为粘土、氧化铝和/或玻璃纤维。
8.权利要求1-3任一项的催化剂组合物，其中第二组分的金属氧化物载体为WO3/TiO2。
9.权利要求1-3任一项的催化剂组合物，其中以催化剂组合物整体的总重量计，所述混合物包含0.5-5.0wt％按V2O5计算的钒。
10.权利要求9的催化剂组合物，其中以催化剂组合物整体的总重量计，所述混合物包含1.0-3.0wt％按V2O5计算的钒。
11.包含权利要求1-10任一项的催化剂组合物的催化载体涂层，包含一种或多种填料、粘结剂、处理助剂、水和掺杂剂。
12.包含用权利要求11的催化载体涂层涂覆的整块基质的催化剂制品，其中所述基质为金属流通式基质、陶瓷流通式基质、壁流式过滤器、烧结金属过滤器或部分过滤器。
13.为挤出基质形式的权利要求12的催化剂制品，其为蜂窝状整块。
14.权利要求12或13的催化剂制品，包含用于应用含氮还原剂选择性还原NOx和/或氧化NH3的为载体涂层形式的第二催化剂组合物，所述第二催化剂组合物为：(a)过渡金属促进的分子筛；(b)在金属氧化物上载带的铂族金属；或(c)包含在二氧化钛上载带的钒氧化物的催化剂。
15.权利要求14的催化剂制品，其中所述基质包含氨滑流催化剂ASC，所述氨滑流催化剂包括用于氧化氨的第一层和包含权利要求1-10任一项的催化剂组合物的第二层，其中第一层直接放置于基质上，和第二层覆盖在第一层上。
16.用于处理废气的废气系统，包含放置于氨滑流催化剂ASC上游的选择性催化还原SCR催化剂，其中SCR和ASC催化剂中至少之一包含权利要求1-10任一项的催化剂组合物。
17.权利要求16的废气系统，其包含氧化催化剂，所述氧化催化剂包含在整块基质上涂覆的在金属氧化物上载带的铂族金属，并放置于SCR催化剂组合物的上游。
18.一种机动车辆贫燃内燃机，其包含权利要求16或17的废气系统。
19.包含权利要求18的内燃机的机动车辆。
20.一种处理废气的方法，所述废气任选包含4:1至1:3体积比的NO与NO2比，所述方法包括如下步骤：
(i)使含NOx和NH3的废气物流与权利要求1-10任一项的催化剂组合物或权利要求12-15任一项的催化剂制品接触；和
(ii)转化至少一部分NOx为N2和/或转化至少一部分NH3为N2和NO2中的至少一种。
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