CN108380207A - 用于减少来自富燃废气的氨排放的催化剂 - Google Patents
用于减少来自富燃废气的氨排放的催化剂 Download PDFInfo
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- CN108380207A CN108380207A CN201810181205.2A CN201810181205A CN108380207A CN 108380207 A CN108380207 A CN 108380207A CN 201810181205 A CN201810181205 A CN 201810181205A CN 108380207 A CN108380207 A CN 108380207A
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- catalyst
- molecular sieve
- transition metal
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- 239000002808 molecular sieve Substances 0.000 claims abstract description 98
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Classifications
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
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- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
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Abstract
减少氨(NH3)排放的***包括(a)包含含有三效催化剂的第一基底的第一组件,其中第一组件位于包含含有氨氧化催化剂的第二基底的第二组件上游,其中所述氨氧化催化剂包含负载至少一种过渡金属的小孔分子筛;和(b)位于这些组件之间的含氧气体入口。例如,可以使用CHA骨架型小孔分子筛。减少NH3排放的方法包括将含氧气体引入气流中以产生充氧气流;和使该充氧气流暴露在NH3氧化催化剂下以将至少一部分NH3选择性氧化成N2。该方法可进一步包括使富燃废气暴露在三效催化剂下以产生包含NH3的气流的步骤。
Description
本申请是原始中国专利申请号201280024430.6,申请日2012年1月23日,发明名称“用于减少来自富燃废气的氨排放的催化剂”的分案申请。
发明领域
本发明涉及小孔分子筛负载的过渡金属催化剂。本发明还涉及使用小孔分子筛负载的过渡金属催化剂减少来自富燃废气的氨(NH3)的***。
发明背景
典型发动机废气是含有气体排放物如一氧化碳(CO)、未燃或部分燃烧的烃或其氧化物(HC)和氮氧化物(NOx)等成分的不均匀混合物。通常,在发动机排气***中提供催化剂组合物和该组合物所处的基底以将某些或所有这些废气组分转化成无害组分。例如,已知在固定式富燃发动机中合适地使用三效(TWC)催化剂以减少氮氧化物(NOx)、烃(HC)和一氧化碳(CO)的排放。由于这些发动机在富燃条件(其中空燃比具有大于化学计量的燃料量(即空燃比低于化学计量比)条件)下运行,相当大部分的发动机输出的NOx在三效催化剂上转化成氨(NH3)并因此作为二次排放排出。对于配有TWC催化剂的典型富燃发动机,尾管NH3可以为大约400ppm。
适用于在稀燃废气条件下的固定源的确证NOx减除技术是选择性催化还原(SCR)。在这种方法中,在通常由贱金属构成的催化剂上用还原剂如氨(NH3)将NOx还原成氮气(N2)。SCR提供NOx的有效转化,只要废气温度在该催化剂的活性温度范围内。使用NH3将NOx物类还原成N2有助于达到稀燃发动机中的NOx排放目标。使用NH3作为还原剂的后果在于,在不完全转化或废气温度上升的条件下,NH3会从车辆废气中逃逸。为避免NH3逃逸,可以将亚化学计算量的NH3注射到废气流中,但NOx转化率降低。或者,可以将NH3超剂量送入该***以提高NOx转化率,但废气随后需要进一步处理以除去过量或逸出的NH3。即使在NH3的亚化学计量的剂量下,废气温度的提高也可能释放储存在NOx减除催化剂上的氨,以致NH3逃逸。传统的贵金属基氧化催化剂如负载在氧化铝上的铂在225℃以上对除氨非常有效,但它们产生相当多的N2O和NOx作为不想要的副产物而非所需N2产物。通常,柴油机催化剂用于汽油机、固定式柴油或天然气发动机会导致生成NH3排放,因为该催化剂非常活泼。
使用分级NOx处理-NH3处理构造的两级***是工业中已知的。但是,这些***所用的催化剂在400℃以上无法实现NH3转化成N2的高选择性,其中NH3过度氧化成NOx会导致该***超出NOx法规。另外,现有技术的***通常涉及在化学计量比以上运行的稀燃发动机。在这种稀燃条件下,大多数现有技术的***使用用于NOx的选择性催化还原(SCR)的催化剂。已经为许多稀燃用途开发出用含氮化合物如氨或脲进行NOx的SCR,包括用于处理工业固定式用途、热电厂、燃气轮机、火力发电厂、化学加工工业中的工厂和炼油厂加热炉和锅炉、熔炉、炼焦炉、市政垃圾处理厂和焚化炉,和许多车载(移动)用途,例如用于处理柴油机废气。但是,类似于已知的两级***,已知的SCR催化剂和***在400℃以上无法实现NH3转化成N2的高选择性,其中NH3过度氧化成NOx会导致该***超出NOx法规。
目前,对燃烧***废气的NH3排放没有调控,因为没有用于减少此类***中的NH3排放、同时还符合对NOx、HC和CO的严格排放法规的商业上可得的技术。因此找出可以在使NOx、HC和CO排放低于现有法规的同时将NH3排放减至最低(例如低于10ppm)的催化剂和使用该催化剂的方法是有用的。因此,减少在高温下运行的富燃发动机废气的氮氧化物(NOx)、烃(HC)和一氧化碳(CO)排放并提供NH3氧化功能以减少流出物中的NH3量的催化剂和***仍然非常合意。
发明概述
根据本发明的一个实施方案,使用小孔分子筛催化剂作为用于在高温下运行的富燃发动机用途的氨氧化催化剂(AOC)。我们已经发现,在这样的用途中使用包含负载至少一种过渡金属的小孔分子筛的催化剂以将NH3以极高选择性氧化成N2。此前在用NH3选择性催化还原(SCR)NOx的稀燃用途中已使用类似的催化剂。但是,使用这样的催化剂作为氧化催化剂以将NH3氧化形成N2和H2O是不典型的。但是,本发明人的发明人已经发现,可有利地使用包括负载至少一种过渡金属的小孔分子筛的NH3氧化催化剂(AOC),包括在高温下运行的富燃发动机中或用于处理容易逸出不合意的NH3量的其它废气。在本文中提供使用此类催化剂的新型***和方法。
根据本发明的一个实施方案,减少氨(NH3)排放的***包含:(a)包含第一基底和位于其上的三效催化剂的第一组件,其中第一组件位于包含第二基底和位于其上的氨氧化催化剂的第二组件上游并与其流体连通,其中所述氨氧化催化剂包含负载至少一种过渡金属的小孔分子筛;和(b)位于所述第一和第二组件之间的含氧气体入口。
在本发明的另一实施方案中,该***另外包括:(c)包含来自富燃燃烧过程的废气的第一气体进料流,其中所述进料流在第一组件上游并与其流体连通;和(d)位于第一和第二组件之间并与它们流体连通并且与所述含氧气体入口流体连通的导管。在至少一个实施方案中,用于NH3氧化的小孔分子筛是载铜的CHA骨架型小孔分子筛,如载铜的SAPO-34。
在本发明的再一实施方案中,该AOC催化剂包括第一催化剂层形式的负载过渡金属的小孔分子筛。在另一实施方案中,该AOC催化剂可包括包含铂族金属的第二催化剂层,其中第一催化剂层与第二催化剂层的相对位置使得废气在接触第二催化剂层之前接触第一催化剂层。铂族金属可以是例如钌(Ru)、铑(Rh)、钯(Pd)、铼(Re)、铱(Ir)和铂(Pt)及其混合物。在本发明的至少一个实施方案中,第一催化剂层中的负载过渡金属的小孔分子筛是载铜的CHA骨架型小孔分子筛,如载铜的SAPO-34,且第二催化剂层中的铂族金属是Pt。当第二基底具有入口端、出口端、在入口端与出口端之间延伸的长度、沿长度延伸的壁元件和由壁元件划定的多个通道例如流通型整料时,该AOC催化剂层可位于例如壁元件上。
在本发明的另一实施方案中,减少氨(NH3)排放的方法包括:将含氧气体引入具有NH3和<1的λ的废气中以提供充氧气流;和使该充氧气流暴露在包含至少一种负载至少一种过渡金属的小孔分子筛的NH3氧化催化剂下以将至少一部分NH3选择性氧化成N2。在该方法的再一实施方案中,该方法在引入含氧气体的步骤上游进一步包括步骤:使富燃废气暴露在用于转化氮氧化物(NOx)、烃(HC)和一氧化碳(CO)的三效催化剂下以产生具有NH3和<1的λ的气流。可以引入该含氧气体以产生具有至少大约1:1,优选大约2:1至大约1:1的O2:NH3比的充氧气流。在至少一个实施方案中,该含氧气体包含至少0.1%氧,如环境空气。该暴露步骤优选在富燃废气处于至少大约350摄氏度,优选大约400-650摄氏度的温度下时进行。
在本发明的再一实施方案中,催化剂制品包含:(a)催化剂组合物,其包含:(i)包含划定出孔隙并具有原子位点的骨架的小孔分子筛;和(ii)以原子形式位于至少一个所述原子位点和以氧化物形式自由存在于至少一个所述孔隙中的至少一种过渡金属;和(b)基底,所述催化剂位于其上,其中所述催化剂制品适合氧化富燃废气的催化转化生成的氨。在至少一个实施方案中,该小孔分子筛是具有占催化剂总重量的大约0.1至大约20.0重量%铜的载铜(Cu)小孔分子筛。在另一实施方案中,游离铜以足以防止该催化剂的氮氧化物转化的水热劣化的量存在。在至少一个实施方案中,该小孔分子筛是载铜的CHA骨架型小孔分子筛,如载铜的SAPO-34。
附图简述
为了更充分理解本发明,仅作为示例参考下列附图,其中
图1是根据本发明的一个实施方案的***构造;
图2是显示在550℃和600℃下来自三效催化剂(TWC)***、根据本发明的一个实施方案的三效催化剂和NH3氧化催化剂(TWC-AOC)***和根据本发明的另一实施方案的含有氨逃逸催化剂的三效催化剂和多层NH3氧化催化剂***(TWC-ASC)的氨(NH3)排放的柱形图。
图3是显示在550℃和600℃下来自图2的描述中提到的三种***的氮氧化物(NOx)排放的柱形图;
图4是显示在550℃和600℃下来自TWC***、根据本发明的一个实施方案具有2.5%的铜载量的TWC-AOC***和根据本发明的另一实施方案的具有4.2%的铜载量的TWC-AOC***的氨(NH3)排放的柱形图;
图5是显示在550℃和600℃下来自图4的描述中提到的三种***的氮氧化物(NOx)排放的柱形图;
图6是显示在450℃、500℃、550℃和600℃下来自TWC***和根据本发明的另一实施方案的使用铜载量为4.2%的Cu/SAPO-34作为AOC催化剂的TWC-AOC***的氨(NH3)排放的柱形图;
图7是显示在450℃、500℃、550℃和600℃下来自图6的描述中提到的三种***的氮氧化物(NOx)排放的柱形图。
发明详述
已经确认,小孔分子筛负载的过渡金属催化剂可用于将NH3选择性氧化成N2。这些催化剂暴露在富燃过程(如在汽油机中和在燃气轮机、火力发电厂等的高功率运转中遇到的那些富燃过程)的废气中存在的还原气氛下后保持良好的活性、优异的热稳定性和耐久性。但是,可能由于过渡金属迁移、烧结和/或降低的过渡金属分散的效应,中孔和大孔分子筛暴露在还原气氛下时不保持它们的稳定性和活性。本发明的方法被发现特别有效地减少高温下的富燃废气或具有NH3和过量净还原物类(例如λ<1)的其它废气的NH3排放。在某些实施方案中,转化的富燃废气的温度为至少大约350摄氏度,优选大约400-650摄氏度。
可通过使富燃废气经过三效(TWC)催化剂而生成NH3。本文所用的TWC催化剂能够同时减少发动机废气中存在的氮氧化物(NOx)、烃(HC)和一氧化碳(CO)的排放水平,例如将至少一部分这样的气体转化成N2、O2、H2O和CO2。TWC是指涂布整料或挤出形式的由负载在载体材料上的单层或多层活性催化剂材料(即铂族金属(PGM)或非PGM)构成的催化剂,其可以具有或没有附加添加剂以增强特定的催化剂活性(例如H2S抑制、NOx存储、HC存储)。在富燃条件(即其中燃烧前的空燃比具有大于化学计量的燃料量(即空燃比低于化学计量比)下运行的燃烧过程中,相当大部分的排出NOx在三效催化剂上转化成氨(NH3),其通常作为二次排放排出。本发明涉及NH3氧化催化剂,尤其是小孔分子筛负载的过渡金属催化剂用于将NH3选择性氧化成N2并由此降低NH3排放水平的用途。在使用NH3作为还原剂还原NOx的稀燃废气处理中已使用类似的催化剂。这些催化剂现在已被发现作为在高温下运行的富燃发动机的废气中的NH3氧化催化剂具有惊人的结果。在该综合***中,AOC催化剂选择性氧化漏过TWC催化剂或由TWC催化剂在正常富燃运行条件过程中生成的一些或所有NH3。
与稀燃条件相比,富燃条件对催化剂组分提出额外的要求。也就是说,除具有良好活性和优异的热稳定性外,该AOC催化剂需要在暴露在高温还原气氛中后仍耐用。
空燃比(AFR)是燃烧过程中存在的空气与燃料的质量比。如果提供刚好足以完全燃烧所有燃料的空气,该比率被称作化学计量比。Lambda(λ)是表示AFR的另一方式。对汽油燃料(理想地是纯辛烷)而言,化学计量空燃比为大约14.7(即空气的近似质量是燃料质量的14.7倍)。小于14.7:1的这种燃料的任何混合物被认为是富混合物,而大于14.7:1的任何混合物被认为是稀混合物。最实用的AFR装置实际测量废气中的残留氧(对稀混合物而言)或未燃烃(对富混合物而言)的量。Lambda(λ)是给定混合物的实际AFR与化学计量的比率并且衡量气体的净氧化物类与净还原物类的比率。1.0的λ处于化学计量,富混合物具有小于1.0的λ,稀混合物具有大于1.0的λ。
本文所用的还原气氛是净还原,例如λ值小于1的废气(例如由小于化学计量的空燃比得出)。与此相比,非还原气氛是净氧化,例如具有大于1的λ值(例如由大于化学计量的空燃比得出)。
在至少一个实施方案中,本发明的方法包括例如通过注射将含氧气体引入含有NH3的气流中以产生充氧NH3气流的步骤。该含氧气体优选以足以提供用于将NH3选择性氧化成N2以将NH3的量减少至所需水平的至少最低量的氧的速率引入。在至少一个实施方案中,引入含氧气体以产生具有至少大约1:1,优选大约2:1至大约1:1的O2:NH3比的充氧气流。在至少一个实施方案中,该含氧气体包含至少0.1%氧,优选至少0.5%氧。尽管该含氧气体可能含有在0.5%氧以上的任何量的氧,氧量可以为0.5%氧至21%氧(即环境空气)以致不必用额外的氧含量补充该含氧气体。可以使用其它含氧气体,如在惰性气体如氩气中的氧气。如本领域普通技术人员所理解,注氧可以将含有NH3的气流的λ值调节至例如稀燃(即大于1的λ值)。
该AOC催化剂包含负载至少一种过渡金属的小孔分子筛。分子筛通常如下通过几元环定义:大孔环是12元环或更大;中孔环是10元环;小孔环是8元环或更小。本发明的小孔分子筛优选具有8个四面体原子的最大环尺寸。本文所用的“分子筛”被理解为是指含有尺寸精确和一致的微小孔隙的亚稳材料。分子筛骨架可以如International Zeol iteAssociation骨架类型码(在http://www.iza-online.org/)公认的那样定义。下面更详细描述这些分子筛。
根据本发明的另一实施方案,减少来自富燃废气的NH3排放的***包含:包含用于转化来自发动机废气的氮氧化物(NOx)、烃(HC)和一氧化碳(CO)的三效催化剂(TWC)的第一基底;用于引入含氧气体的装置如注射器,其中在第一基底下游引入该气体;和在注射器下游的包含NH3氧化催化剂(AOC)的第二基底,其中NH3氧化催化剂包含至少一种含有负载至少一种过渡金属的小孔分子筛的催化剂。如本领域普通技术人员所理解,术语“注入”和“注射器”无意将本发明限于引入含氧气体的特定装置或方法。根据本发明可以使用用于引入含氧气体的任何已知装置或手段。
图1显示根据本发明的这一实施方案的***构造。图1中所示的***构造包括含有用于转化例如来自发动机10的废气中的NOx、HC和CO的TWC催化剂的第一基底12。设置注射器14以使其在TWC催化剂下游和含有AOC催化剂的第二基底18上游的点16引入含氧气体。注射器14将含氧气体如空气注入来自TWC催化剂的NH3气流中以产生充氧NH3气流。如本领域普通技术人员所理解,如果废气的状况不要求减少特定污染物如NOx、HC和CO的排放,含有TWC催化剂的第一基底12可能不是必要的。因此,在另一实施方案中,该***可能包含用于将含氧气体如空气注入含有NH3的气流中的注射器,其中该注射器位于含有AOC催化剂的第二基底上游。优选地,引入该***中的含氧气体不含或基本不含氨或其任何前体如脲。
在来自特定类型发动机的某些废气条件中,AOC催化剂可以仅由负载至少一种过渡金属的小孔分子筛构成。这种催化剂可用在例如TWC催化剂或固定式柴油机后的汽油机减排***构造中。在这一实施方案中,负载至少一种过渡金属的小孔分子筛可以是第一催化剂层形式。在来自其它类型发动机的其它废气条件中,AOC催化剂可进一步包括另一类型的催化剂。例如,在至少一个实施方案中,AOC催化剂可进一步包括包含铂族金属(PGM)的第二催化剂层,以使第一催化剂层相对于经过或穿过催化剂的废气流位于第二催化剂层上。在这种构造中,废气在接触第二催化剂层之前接触第一催化剂层。例如,这两种催化剂可以沿整料的长度延伸,第二催化剂层位于第一催化剂层下方。或者,这两种催化剂可以连续布置,第一催化剂层在第二催化剂层上游。在另一实施方案中,第一和第二催化剂层可重叠至少一层的长度的例如大约25%,大约50%或大约75%。
这种多层AOC催化剂可用在例如燃天然气的固定式发动机中。燃天然气的固定式发动机已知在富燃条件下运行,包含PGM的第二催化剂层可用于一氧化碳(CO)氧化而不将NH3氧化成NOx。这种多层催化剂常被称作氨逃逸催化剂(ASC),因为其具有PGM催化剂底层和用于选择性NH3氧化的催化剂作为顶层。在这种构造中,使用足量的顶层催化剂以将NH3选择性氧化成N2,以使容许量的NH3或没有NH3到达PGM催化剂底层以致过氧化形成NOx。在本发明的至少一个实施方案中,顶层催化剂与底层催化剂的比率为大约0.5:1至大约10:1,更优选大约2:1至大约7:1。
如本领域普通技术人员所理解,这种多层催化剂可具有其它构造并可以以许多方式使用。例如,当含有AOC催化剂的第二基底具有入口端、出口端、在入口端与出口端之间延伸的长度、沿长度延伸的壁元件和由壁元件划定的多个通道,该多层AOC催化剂可位于例如壁元件上。基底的实例包括流通型蜂窝整料和壁流蜂窝整料。铂族金属可以是例如钌(Ru)、铑(Rh)、钯(Pd)、铼(Re)、铱(Ir)和铂(Pt)及其混合物。可以使用典型的载体,例如氧化铝、氧化锆、二氧化铈等。
根据本发明的另一实施方案,减少氨(NH3)排放的方法包括:将含氧气体引入具有NH3和<1的λ的废气中以提供充氧气流;和使该充氧气流暴露在包含至少一种负载至少一种过渡金属的小孔分子筛的NH3氧化催化剂下以将至少一部分NH3选择性氧化成N2。在该方法的再一实施方案中,该方法在引入含氧气体的步骤上游进一步包括步骤:使富燃废气暴露在用于转化氮氧化物(NOx)、烃(HC)和一氧化碳(CO)的三效催化剂下以产生具有NH3和<1的λ的气流。可以引入该含氧气体以产生具有至少大约1:1,优选大约2:1至大约1:1的O2:NH3比的充氧气流。在至少一个实施方案中,该含氧气体包含至少0.1%氧,如环境空气。该暴露步骤优选在富燃废气处于至少大约350摄氏度,优选大约400-650摄氏度的温度下时进行。以足以提供用于将NH3选择性氧化成N2以将NH3的量减少至所需水平的至少最低量的氧的速率注入该含氧气体。因此,引入的氧量优选产生具有至少大约1:1,优选大约2:1至大约1:1的O2:NH3比和大于1的λ值的充氧气流。
要认识到,通过借助它们的骨架类型编码(FTC)定义分子筛,我们意在包括通过该FTC规定的“类型材料(Type Material)”和任何和所有同型骨架材料。(“类型材料”是最初用于确立该骨架类型的物类)。参考表1,其列举用于本发明的一系列示例性分子筛材料。为避免疑问,除非另行指明,在本文中通过名称,例如“菱沸石”提到分子筛是指该分子筛材料本身(在此实例中是天然存在的类型材料菱沸石)而非指各分子筛所属的骨架类型编码所指的任何其它材料,例如另一些同型骨架材料。
分子筛类型材料,如天然存在的(即矿物)菱沸石与相同骨架类型编码内的同种型之间的区别不是仅仅随意的,而是反映了材料之间的性质差别,这又可能造成在本发明的方法中的活性差别。例如从下表1中会认识到,通过“MeAPSO”和“MeAlPO”,我们是指被一种或多种金属取代的沸石类型(zeotypes)。合适的取代金属包括但不限于As、B、Be、Co、Fe、Ga、Ge、Li、Mg、Mn、Zn、Cu、Ti、Sn、In和Zr中的一种或多种。
在一个具体实施方案中,用于本发明的小孔分子筛催化剂可选自硅铝酸盐分子筛、金属取代的硅铝酸盐分子筛和铝磷酸盐分子筛。可用于本发明的铝磷酸盐分子筛包括铝磷酸盐(AlPO)分子筛、金属取代的(MeAlPO)分子筛、硅-铝磷酸盐(SAPO)分子筛和金属取代的硅-铝磷酸盐(MeAPSO)分子筛。
在一个实施方案中,该小孔分子筛选自下列骨架类型: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及其混合物和/或共生物。在另一实施方案中,含有8个四面体原子的最大环尺寸的小孔分子筛选自骨架类型CHA、LEV、ERI、AEI、UFI和DDR及其混合物和/或共生物。在再一实施方案中,该小孔分子筛包含CHA骨架类型。如下论述,在至少一个实施方案中,本发明的小孔分子筛负载至少一种过渡金属,如铜。用于本发明的优选的含铜三维小孔分子筛/铝磷酸盐分子筛由Cu/CHA,如Cu/SAPO-34构成。在如上所述的多层AOC催化剂中,优选的AOC催化剂包括载铜的CHA骨架类型小孔分子筛,如SAPO-34作为第一催化剂顶层中的负载至少一种过渡金属的小孔分子筛和包括Pt作为第二催化剂底层中的铂族金属。
用于本发明的分子筛可包括经过为改进水热稳定性而进行的处理的那些。改进水热稳定性的示例性方法包括:
(i)通过下述脱铝:蒸汽处理和使用酸或络合剂,例如(EDTA-乙二胺四乙酸)的酸萃取;用酸和/或络合剂处理;用SiCl4气流处理(用Si替代分子筛骨架中的Al);
(i i)阳离子交换-使用多价阳离子,如La;和
(i i i)使用含磷化合物(参见例如美国专利No.5,958,818)。
合适的小孔分子筛的示例性实例列在表1中。
表1:小孔分子筛
特别适用于NH3氧化的小孔分子筛列在表2中。
表2:优选的小孔分子筛
用于本申请的分子筛包括天然和合成分子筛,优选合成分子筛,因为该分子筛具有更均匀的硅铝比(SAR)、微晶尺寸、微晶形态并且不存在杂质(例如碱土金属)。小孔硅铝酸盐分子筛可具有2至300,任选4至200,优选8至150的硅铝比(SAR)。要认识到,可以选择任何SAR比以改进热稳定性,但这可能不利地影响过渡金属交换。
用于本发明的小孔分子筛可具有三维维数,即在所有三个结晶维度中互连的孔隙结构,或二维维数。在一个实施方案中,用于本发明的小孔分子筛由具有三维维数的分子筛构成。在另一实施方案中,用于本发明的小孔分子筛由具有二维维数的分子筛构成。
在某些实施方案中,该小孔分子筛包含、基本上由或由选自ABC-6、AEI/CHA、AEI/SAV、AEN/UEI、AFS/BPH、BEC/ISV、beta、fuajasite、ITE/RTH、KFI/SAV、lovdarite、蒙特索马石、MTT/TON、pentasils、SBS/SBT、SSF/STF、SSZ-33和ZSM-48的无序骨架构成。在一个优选实施方案中,一种或多种小孔分子筛可包含选自SAPO-34、AlPO-34、SAPO-47、ZYT-6、CAL-1、SAPO-40、SSZ-62或SSZ-13的CHA骨架类型和/或选自AlPO-18、SAPO-18、SIZ-8或SSZ-39的AEI骨架类型。在一个实施方案中,该混合相组合物是AEI/CHA-混合相组合物。该分子筛中各骨架类型的比率不受特别限制。例如,AEI/CHA比可以为大约5/95至大约95/5,优选大约60/40至40/60。在一个示例性实施方案中,AEI/CHA比可以为大约5/95至大约40/60。
在本发明的至少一个实施方案中,小孔分子筛是一种或多种过渡金属的载体。本文所述的所述至少一种过渡金属意在包括铬(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。所述一种或多种过渡金属优选是铬(Cr)、铈(Ce)、锰(Mn)、铁(Fe)、钴(Co),、镍(Ni)、和铜(Cu)及其混合物,最优选铜。如本领域普通技术人员已知,过渡金属如铜可以与小孔分子筛骨架内的氧化铝交换以制造小孔分子筛负载的过渡金属催化剂。
过渡金属载量已被发现改进根据本发明的实施方案的催化剂的性能。如本领域普通技术人员所理解,载体催化剂如分子筛可以以许多方式加载过渡金属。过渡金属可以例如与分子筛结构中的原子交换位点处的原子成分交换。另外或或者,该过渡金属可以作为盐形式的未交换的过渡金属存在于分子筛中,例如存在于分子筛的孔隙内。在煅烧时,未交换的过渡金属盐分解形成过渡金属氧化物,其可以被称作“游离金属”。当过渡金属载量超过原子交换位点的饱和限(即所有交换位点已交换)时,在分子筛中可能存在未交换的过渡金属。尽管在本发明的NH3氧化用途中可能使用这样高的过渡金属载量,但这样的载量不同于标准SCR用途,因为过渡金属的氧化效应会与还原反应竞争。例如,当使用铜作为过渡金属时,氧化铜可能作为“游离铜”存在于分子筛的孔隙中。这种游离铜活金属是活性和选择性的,并且现在也被发现在经受高温热老化的催化剂中提供更高稳定性。
如本领域普通技术人员所理解,分子筛中可包括的过渡金属的总量取决于许多因素,包括例如所用分子筛的类型和酸度。分子筛中可包括的过渡金属的总量最多为每个酸位点1个金属原子,通过本领域中已知的典型NH3吸收方法测得的优选的金属/酸位点比为大约0.02:1至大约1:1。过渡金属的量还取决于例如使用AOC作为单层催化剂还是作为多层催化剂,如当使用小孔分子筛负载的过渡金属催化剂作为铂族金属催化剂底层上的顶层时。可通过任何可行的方法在分子筛中加入铜。例如,其可以在合成分子筛后例如通过初湿含浸或交换法加入;或可以在分子筛合成过程中加入。
在本发明的再一实施方案中,催化剂制品包含:(a)催化剂组合物,其包含:(i)包含划定出孔隙并具有原子位点的骨架的小孔分子筛;和(i i)以原子形式位于至少一个所述原子位点和以氧化物形式自由存在于至少一个所述孔隙中的至少一种过渡金属;和(b)基底,所述催化剂位于其上,其中所述催化剂制品适合氧化富燃废气的催化转化生成的氨。在另一实施方案中,游离过渡金属如游离铜以足以防止该催化剂的氮氧化物转化的水热劣化的量存在。不受制于任何理论,据信,过渡金属在低载量(即低于某一饱和限)下与骨架中的原子位点交换。当添加在这一饱和限以上的量的过渡金属时,剩余过渡金属以游离过渡金属(即过渡金属氧化物)的形式存在于该催化剂中。
在本发明的至少一个实施方案中,该小孔分子筛是CHA骨架类型的小孔分子筛负载的铜催化剂。用于本发明的优选的含铜三维小孔分子筛/铝磷酸盐分子筛由Cu/CHA,如Cu/SAPO-34构成。当使用Cu/SAPO-34作为单层催化剂中的小孔分子筛负载的过渡金属催化剂时,铜金属的总量可以为催化剂总重量的0.01至20重量%,优选2至8重量%,最优选2.5至6重量%。当使用Cu/SAPO-34作为多层催化剂中的小孔分子筛负载的过渡金属催化剂时,铜的总量可以为催化剂总重量的0.01至20重量%,优选0.2至4重量%,最优选0.5至3重量%。在另一实施方案中,游离铜以足以防止该催化剂的氮氧化物转化的水热劣化的量存在。但是,如本领域普通技术人员所理解和如上所述,分子筛中可包括的过渡金属的总量取决于许多因素,包括例如所用分子筛的类型和酸度和催化剂层数。
用于本发明的催化剂(包括分子筛催化剂和PGM催化剂)可以涂布在合适的基底整料上或可作为挤出型催化剂成形。在一个实施方案中,在流通型整料基底(即具有轴向经过整个部件的许多小的平行通道的蜂窝整料催化剂载体)或壁流过滤器,如壁流过滤器上涂布该催化剂。用于本发明的催化剂可例如作为活性涂层(washcoat)组分涂布在合适的整料基底,如金属或陶瓷流通型整料基底或过滤基底,如壁流过滤器或烧结金属或部分过滤器上(如WO 01/80978或EP 1057519中所公开,后一文献描述了包含至少减慢碳烟经过其中的曲折流径的基底)。或者,用于本发明的催化剂可以直接合成到基底上。或者,本发明的催化剂可以成形成挤出型流通催化剂。这种挤出型催化剂可成形为催化剂筒。挤出的AOC催化剂筒可独自或与TWC催化剂筒结合成形为单层或多层AOC催化剂筒。其它形式,如丸粒、珠粒或其它成型催化剂是可行的。
用于涂布到基底上的含有本发明的小孔分子筛负载的过渡金属催化剂的活性涂层组合物可包含本领域普通技术人员已知的其它成分。例如,这样的活性涂层组合物可另外包含选自氧化铝、二氧化硅、(非分子筛)二氧化硅-氧化铝、天然存在的粘土、TiO2、ZrO2、CeO2,和SnO2及其混合物和组合的粘合剂。该催化剂组合物可首先作为浆料制备并作为活性涂层浆料组合物使用任何已知方法施加到基底上。
本发明的方法可以在来自燃烧过程,如来自内燃机(无论是移动还是固定的)、燃气轮机和燃煤、燃油或燃天然气的工厂或发动机的气体上进行。该方法也可用于处理来自工业工艺,如精炼、来自炼油厂加热炉和锅炉、熔炉、化学加工工业、炼焦炉、市政垃圾处理厂和焚化炉、咖啡烘焙工厂等的气体。在一个具体实施方案中,该方法用于处理来自在富燃条件下的车辆内燃机,如汽油机,或来自以液体石油气或天然气为动力的固定式发动机的废气。
本文中引用的任何和所有专利和参考资料的整个内容经此引用并入本文。
实施例
下列实施例例示而非限制本发明。
实施例1.
进行试验以测量来自对比***和本发明的***的氨(NH3)排放和氮氧化物(NOx)排放。将含有三效催化剂(TWC)的对比***与根据本发明的一个实施方案的包括三效催化剂和NH3氧化催化剂的***(TWC-AOC***)和根据本发明的另一实施方案的包括三效催化剂和含有氨逃逸催化剂的多层NH3氧化催化剂***的***(TWC-ASC)进行比较。该多层NH3氧化催化剂***包括小孔分子筛负载的过渡金属催化剂的第一层(即顶层)和铂族金属催化剂的第二层(底层)。具体而言,使用Cu/SAPO-34作为多层NH3氧化催化剂的顶层和使用铂作为底层。特别地,沿流通型基底的壁涂布催化剂层,首先在基底上涂布第二层并在第二层上涂布第一层。
气流的空间速度为在TWC催化剂处100,000hr-1和在NH3氧化催化剂处50,000hr-1。TWC催化剂入口处的废气如下构成:1410ppm C3H8作为C1,0.45%CO,0.15%H2,2700ppm NO,0.25%O2,10%CO2,10%H2O,余量包含N2。TWC催化剂处的废气的λ值经计算为0.9905,而在注入含氧气体后,NH3氧化催化剂处的气体的λ值经计算为大约1.022。作为含氧气体的一部分加入0.5%氧。使用载铂的涂布整料基底。
图2显示在550℃和600℃下来自三个***的NH3排放。类似地,图3显示在550℃和600°下来自三个***的NOx排放。如图2和3中所示,TWC-AOC***和TWC-ASC***都能将出口NH3显著降至30ppm以下,但只有TWC-AOC***的NH3氧化催化剂(即单层小孔分子筛负载的过渡金属催化剂)减少或保持出口NOx浓度。TWC-ASC***的多层NH3氧化催化剂(即顶层小孔分子筛负载的过渡金属催化剂和铂族金属催化剂底层)导致NOx增加200ppm。这是因为一些NH3到达铂族金属底层催化剂(即ASC催化剂)并在接触底层催化剂时被气体中存在的一些氧化剂氧化成NOx。通过交换的分子筛(例如顶层载量含有占催化剂总重量的大约0.1.至大约20.0重量%铜,优选大约0.1至大约10.0重量%铜和最优选0.1重量%至大约6.0重量%铜)的较高顶层载量使这种效应最小化。此外,该TWC-ASC***更适合氧化可能较低的气体。
实施例2
进行试验以比较过渡金属载量对小孔分子筛催化剂的减排能力的影响。使用铜作为过渡金属。将含有三效催化剂(TWC)的对比***与具有2.5%铜载量的包括三效催化剂和NH3氧化催化剂的本发明的***(TWC-AOC***)和具有4.2%铜载量的包括三效催化剂和NH3氧化催化剂的本发明的***(TWC-AOC***)进行比较。具体而言,使用Cu/SAPO-34作为NH3氧化催化剂。
气流的空间速度为在TWC催化剂处100,000hr-1和在NH3氧化催化剂处50,000hr-1。TWC催化剂入口处的废气如下构成:1410ppm C3H8作为C1,0.45%CO,0.15%H2,2700ppm NO,0.25%O2,10%CO2,10%H2O,余量包含N2。TWC催化剂处的废气的λ值经计算为0.9905,而在注入含氧气体后,NH3氧化催化剂处的气体的λ值经计算为大约1.022。作为含氧气体的一部分加入0.5%氧。使用载铂的涂布整料基底。
图4显示在550℃和600℃下来自这些***的NH3排放,而图5显示NOx排放。如图4和5中所示,与对比TWC***相比,较高铜载量带来改进的NH3氧化以及额外的NOx逃逸。经确定,过量游离铜会提高NOx逃逸。在一些***中,一定量的NOx逃逸是可容许的;在这些***中,本领域技术人员容易平衡附加的游离铜催化剂的益处(例如防止催化剂的氮氧化物转化的水热劣化)与提高但仍容许的NOx逃逸量。
实施例3
进行试验以比较温度对小孔分子筛催化剂的减排能力的影响。使用铜作为过渡金属。将含有三效催化剂(TWC)的对比***与具有4.2%铜载量的包括三效催化剂和NH3氧化催化剂的本发明的***(TWC-AOC***)进行比较。具体而言,使用Cu/SAPO-34作为NH3氧化催化剂。
气流的空间速度为在TWC催化剂处100,000hr-1和在NH3氧化催化剂处50,000hr-1。TWC催化剂入口处的废气如下构成:1410ppm C3H8作为C1,0.45%CO,0.15%H2,2700ppm NO,0.25%O2,10%CO2,10%H2O,余量包含N2。TWC催化剂处的废气的λ值经计算为0.9905,而在注入含氧气体后,NH3氧化催化剂处的气体的λ值经计算为大约1.022。作为含氧气体的一部分加入0.5%氧。使用载铂的涂布整料基底。
图6显示在450℃、500℃、550℃和600℃下来自这些***的NH3排放,而图7显示NOx排放。如图6和7中所示,NH3氧化催化剂即使在较高温度下也能显著减少出口NH3,同时也减少NOx排放。
相应地,载有过渡金属的小孔分子筛(即小孔分子筛负载的过渡金属)耐受富燃应用所需的长期高温老化并在高温低氧条件下高度选择性地将NH3转化成N2。现有***和催化剂在富燃条件中通常造成显著的NH3逃逸并且在高温下不高效。
尽管在本文中已经显示和描述了本发明的优选实施方案,但要理解的是,仅作为实例提供这样的实施方案。本领域技术人员在不背离本发明精神的情况下会想到许多变动、修改和替代。因此,所附权利要求旨在涵盖落在本发明的精神和范围内的所有这样的变动。
Claims (9)
1.催化剂制品,包含:
(a)含有氨氧化催化剂的活性涂层,其中所述氨氧化催化剂包含负载有至少一种交换的过渡金属和游离过渡金属的小孔分子筛,其中交换的过渡金属与游离过渡金属相同或不同,其中氨氧化催化剂对氧化废气流中的氨有效;和
(b)基底,所述活性涂层涂覆于其上,
其中所述活性涂层是在基底上的单层。
2.根据权利要求1的催化剂制品,其中所述至少一种过渡金属选自铬(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。
3.根据权利要求1的催化剂制品,其中所述活性涂层进一步包含负载有选自铜和铁的金属的第二小孔分子筛。
4.根据权利要求1的催化剂制品,其中所述活性涂层进一步包含氧化铝、二氧化硅、TiO2、ZrO2、CeO2和SnO2中的至少一种。
5.权利要求1的催化剂制品,其中所述至少一种过渡金属选自铬(Cr)、铈(Ce)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)和铜(Cu)及其混合物。
6.用于处理废气中的NH3的***,包括:
(a)第一催化剂制品,包含:
i.氨氧化催化剂组合物,其包含负载有选自下组的过渡金属的小孔分子筛:Cu、Fe、Ce、Mn、Ni、Zn、Ga、Mo和Cr,其中氨氧化催化剂对氧化废气流中的氨有效;和
ii.所述氨氧化催化剂涂覆于其上的第一基底,其中所述氨氧化催化剂和所述基底不含铂族金属,
(b)第二催化剂制品,其包含:
i.a.铂族金属;和
ii.a.所述铂族金属涂覆于其上的第二基底,
其中第一催化剂制品位于第二催化剂制品的下游。
7.根据权利要求6的***,其中所述铂族金属位于在第二基底上的第一层中,并且所述第二基底进一步包含位于第二基底上的非铂族金属作为第二层。
8.根据权利要求6的***,其中第二催化剂制品对于以下的一种或多种有效:存储NOx、抑制H2S、存储HC。
9.根据权利要求6的***,其中所述第二催化剂制品是氨源。
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WO2012138405A1 (en) | 2012-10-11 |
US20110182791A1 (en) | 2011-07-28 |
KR20140032398A (ko) | 2014-03-14 |
US8101146B2 (en) | 2012-01-24 |
US9757719B2 (en) | 2017-09-12 |
JP6328046B2 (ja) | 2018-05-23 |
KR20190131130A (ko) | 2019-11-25 |
RU2593293C2 (ru) | 2016-08-10 |
CN103547358A (zh) | 2014-01-29 |
US20160101413A1 (en) | 2016-04-14 |
RU2013149864A (ru) | 2015-05-20 |
BR112013025988A2 (pt) | 2016-12-20 |
KR102047049B1 (ko) | 2019-11-20 |
JP2014515701A (ja) | 2014-07-03 |
JP2017080734A (ja) | 2017-05-18 |
EP2694193A1 (en) | 2014-02-12 |
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