CN109268110A - 用于净化来自内燃机的废气的方法和系统 - Google Patents

用于净化来自内燃机的废气的方法和系统 Download PDF

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CN109268110A
CN109268110A CN201810946299.8A CN201810946299A CN109268110A CN 109268110 A CN109268110 A CN 109268110A CN 201810946299 A CN201810946299 A CN 201810946299A CN 109268110 A CN109268110 A CN 109268110A
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exhaust gas
zeolite
catalyst
copper
micropore
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CN109268110B (zh
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M.M.马林
C.F.马蒂
A.E.P.吉梅诺
A.C.卡诺斯
P.N.R.文内斯特罗姆
玛丽·格里尔
A.库斯托夫
J.R.托格森
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Umicore AG and Co KG
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Abstract

本发明涉及用于净化来自内燃机的废气的方法和系统。本发明提供了用于纯化来自内燃机的废气的系统和方法，其包括过滤器和SCR催化剂。过滤器周期性地再生，增加废气的温度至850℃以及水蒸气含量至100％体积。SCR催化剂包括具有AEI类型骨架和由铜助催化的水热微孔稳定的沸石和/或类沸石。

Description

用于净化来自内燃机的废气的方法和系统
本申请是申请日为2012年4月27日，申请号为201280072731.6，发明名称为“用于净化来自内燃机的废气的方法和系统”的发明专利申请的分案申请。
本发明涉及在去除或减少有害的化合物方面对来自内燃机的废气的后处理。更具体是，本发明集中在对来自稀燃烧内燃机(并且尤其是柴油发动机)的发动机废气中颗粒物质的去除和氮氧化物的还原。
稀燃烧发动机公知是能量有效的，但具有形成颗粒物质和氮氧化物的缺点，这些必须在发动机废气中除去或至少减少。
为了防止环境污染以及满足一些政府需求，现代柴油机设有废气净化系统，其包括串联的用于挥发性有机化合物去除的氧化催化剂，用于颗粒物质的去除的颗粒过滤器以及在氮氧化物(NOx)的选择性还原中有活性的催化剂。
还公知的是将SCR催化剂集成到颗粒过滤器。
废气中的NOx的选择性催化还原通常通过与原样或作为其前体导入的氨起反应而实现，氨喷入SCR催化剂的废气上游，用于将主要为二氧化氮和一氧化二氮的氮氧化物(NOx)选择性还原为氮。
为此，在文献中公开了许多催化剂组合物。
近来，用铜或铁助催化的沸石引起了很大的关注，尤其是在汽车应用中使用。
包含用于NH3-SCR应用的沸石催化剂的铜显示在低温下高的活性。然而，在某些应用中，催化剂可能暴露于废气中很高的温度偏移。此外废气包含来自燃烧发动机的高浓度的水蒸汽，这可以降低沸石催化剂性能。水热稳定性对于铜基沸石催化剂通常是个问题，一种可能的催化剂失活机理为由对于水-热条件的不稳定性造成的沸石骨架降解，其由铜的存在而进一步增强。
在NH3-SCR应用中含铜沸石催化剂的失活典型地由因为对于水-热条件的不稳定性造成的沸石骨架降解所引起，这由铜的存在而进一步增强。然而，稳定性对其中催化剂将经历含水废气流中的高温度偏差的汽车应用尤其重要。
催化剂的失活在配备有颗粒过滤器的废气净化系统中尤其是个问题，为了防止载有烟灰的过滤器上的压力积累，其必须周期性地活性再生。
活性再生通过燃烧捕集的烟灰而执行。再生可以通过将燃料喷射进入氧化催化剂上游的废气或通过颗粒过滤器的电加热而开始。
在活性再生期间，取决于过滤器中捕集的烟灰的量，在10至15分钟的时间期间在过滤器出口的废气温度可以达到850℃以上并且水蒸汽的含量为15％以上，最多100％。
本发明的总体目标是提供一种用于除去稀燃内燃机的有害的化合物，例如通过颗粒过滤器去除颗粒物质以及通过与催化剂接触的氮氧化物选择性催化还原而去除氮氧化物，所述催化剂当在颗粒过滤器的活性再生期间暴露于高温和水蒸气浓度时为水热稳定的。
我们已经发现本发明的目标可以通过使用具有水热稳定的AEI类型骨架的沸石或类沸石实现，其中在水热老化条件下即使当铜在沸石或类沸石中存在时，该结构得以保持。
按照上述发现，本发明提供一种用于净化来自内燃机的废气的方法，其包括
通过使气体经过颗粒过滤器降低废气中烟灰的含量；
随后在氨或其前体存在下通过与在NH3-SCR中有活性的催化剂接触，降低氮氧化物的含量；
通过燃烧过滤器中捕集的烟灰并且由此将废气的温度增加至850℃并且将水蒸气含量增加至100％体积，周期性地再生过滤器；以及
在再生过滤器期间使来自过滤器的废气通过催化剂，其中催化剂包括具有AEI类型骨架并且骨架中结合了铜的水热稳定的沸石和/或类沸石。
“水热稳定”是指沸石和类沸石催化剂能够在暴露于至少600℃的温度和100％体积的水蒸气含量经13小时后，保持初始表面积的80至90％以及微孔体积的80至90％，并且在暴露于至少750℃的温度和100％体积的水蒸气含量经13小时后，保持初始表面积和微孔体积的至少30至40％。
优选地，具有AEI类型骨架的水热稳定沸石或类沸石的硅与铝原子比率对于沸石为5-50，或对于类沸石为0.02-0.5。
本发明中使用的最优选的沸石或类沸石催化剂是沸石SSZ-39和类沸石SAPO-18，两者都具有“AEI”骨架结构，其中通过浸渍、液体离子交换或固体离子交换而引入铜。
原子铜与铝的比率对于沸石优选为约0.01-约1。对于类沸石，优选的原子铜与硅的比率相应为0.01-约1。
通过本发明中采用的上述催化剂，在750度老化后，与对于Cu-CHA催化剂的20％相比，维持在250℃下初始NOx还原的80％。
因此，在本发明的实施方案中，在催化剂已经暴露在750℃的温度和废气中100％的水蒸气含量经13小时后，维持在250℃下氮氧化物初始还原的80％。
本发明另外提供了一种废气净化系统，其包括活性可再生颗粒过滤器和SCR催化剂，所述催化剂包括具有AEI类型骨架和用铜助催化的水热多微孔稳定的沸石和/或类沸石。
在根据本发明的废气净化系统的一个实施方案中，SCR催化剂集成到颗粒过滤器中。
在另一实施方案中，对于沸石，原子铜与铝的比率为约0.01-约1，对于类沸石，原子铜与硅的比率为0.01-约1。
在又一实施方案中，沸石SCR催化剂中硅与铝的原子比率对于沸石为5-50，对于类沸石为0.02-0.5。
在另一实施方案中，在催化剂已经暴露在750℃的温度和废气中100％的水蒸气含量经13小时后，SCR催化剂保持在250℃下氮氧化物初始还原的80％。
在另一实施方案中，SCR催化剂在600℃老化后保持初始微孔率的80％至90％，以及在750℃老化后保持初始微孔率的30至40％。
在又一实施方案中，SCR催化剂是硅酸铝沸石SSZ-39和/或磷酸硅铝SAPO-18。
在上述实施方案中，SCR催化剂可以沉积在整体式担载结构上。
当用类似的Si/Al比率比较时，Cu-SSZ-39催化剂系统显示与典型的“技术发展水平”的Cu-SSZ-13相比改进的性能。
实施例1：Cu-SSZ-39催化剂制备
具有骨架类型代码AEI的沸石SSZ-39以与美国专利5.958.370给出的使用1，1，3，5-四甲基哌啶鎓作为有机模板类似的方式来合成。凝胶具有以下组成：30Si：1.0 Al：0.51NaOH：5.1 OSDA：600H2O，在135℃压热7天，将产物过滤，用水清洗，在空气中干燥和煅烧。最终的SSZ-39由ICP-AES测量具有Si/Al＝9.1。
为了获得Cu-SSZ-39，煅烧的沸石用Cu(CH3COO)2离子交换，以获得在煅烧后具有Cu/Al＝0.52的最终催化剂。
煅烧后Cu-SSZ-39的粉末X射线衍射(PXRD)图案在图1A中示出。
实施例2：催化剂测试
在固定床反应器中测试用于NOx的选择性催化再生的样品的活性，使用300mL/min的总流率模拟发动机废气流，其由N2中500ppm NO、533ppm NH3、7％O2，5％H2O组成，在其中测试40毫克催化剂。
来自反应器的出口气体中存在的NOx被连续分析，并且转化率在图2示出。
实施例3：水热耐久性测试
为了测试沸石的水热稳定性，对样品进行蒸汽处理。它们在常规烤箱中在13小时期间暴露于600或750℃的水进料(2.2mL/min)，然后类似于实施例2进行测试。
催化剂结果也可以在图2中看到。取决于在水热处理期间使用的温度，经受水热处理的样品已经用600或700℃标记。
还对全部处理的样品执行另外的表征。水热处理后的PXRD图案如图1A所示，并且处理的样本的BET表面积，微孔面积和微孔体积在以下表1中进行了总结。
实施例4：利用Cu-CHA(Cu-SSZ-13)的比较实施例
Cu-CHA沸石由具有以下摩尔组成的凝胶制备：SiO2：0.033 Al2O3：0.50 OSDA：0.50HF：3H2O，其中OSDA是N，N，N-三甲基-1-金刚烷氢氧化铵。
凝胶在翻滚状态下在150℃热压3天，在冲洗、干燥和煅烧后给出具有Si/Al＝12.7的最终沸石产物。
为了获得Cu-CHA，煅烧的沸石与Cu(CH3COO)2离子交换以获得具有Cu/Al＝0.54的最终催化剂。
煅烧后的Cu-CHA的粉末X射线衍射(PXRD)图案在图1B中示出。
该催化剂还根据实施例2测试，并且类似实施例3进行水热耐久性评估。催化结果在附图的图2中概括。处理的CHA样品的PXRD图案在图1B中示出，并且在表1上总结了构造属性(BET表面积，微孔体积，以及微孔面积)。
表1
实施例5：Cu-SAPO-18
具有骨架类型代码AEI的磷酸硅铝SAPO-18根据[J.Chen，J.M.Thomas，P.A.Wright，R.P.Townsend，Catal.Lett.28(1994)[241-248]]合成并且用2重量％的Cu浸渍。最终的Cu-SAPO-18催化剂在750℃下在10％的H2O和10％的O2中水热处理并且在与实施例2给出的相同的条件下测试。结果在附图的图3中示出。

Claims (12)

1.一种用于净化来自内燃机的废气的方法，其包括逐次地
通过使所述废气通过氧化催化剂除去废气中的挥发性有机组分；
通过使所述废气通过过滤器，降低废气中烟灰的含量；
随后在氨或其前驱体存在下与在NH3-SCR中有活性的催化剂接触，降低氮氧化物的含量；
通过燃烧所述过滤器中捕集的烟灰周期性地活性地再生所述过滤器；以及
在再生所述过滤器期间使来自所述过滤器的废气通过所述催化剂，其中所述催化剂由选自SSZ-39和SAPO-18的具有AEI类型骨架的水热微孔稳定的沸石组成，其中所述沸石用铜助催化。
2.权利要求1的方法，其中周期性地活性地再生所述过滤器通过燃烧所述过滤器中捕集的烟灰并且由此将所述废气的温度增加至最高达850℃并且将水蒸气含量增加到最高达100%体积来进行。
3.权利要求1或2的方法，其中具有AEI类型骨架的水热微孔稳定的沸石是用铜助催化的SSZ-39，并且具有5-50的硅与铝的原子比率。
4.权利要求1至3中任一项的方法，其中具有AEI类型骨架的水热微孔稳定的沸石是用铜助催化的SSZ-39，其中原子铜与铝的比率为约0.01-1之间。
5.权利要求1至4中任一项的方法，其中在所述催化剂已经暴露在750℃的温度和所述废气中100%的水蒸气含量经13小时后，维持在250℃下氮氧化物初始还原的80%。
6.权利要求1至5中任一项的方法，其中在600℃老化后维持初始微孔率的至少80%至90%，并且在750℃老化后维持初始微孔率的至少30%至40%。
7.一种废气清洁系统，其包括串联的氧化催化剂、活性可再生颗粒过滤器和SCR催化剂，其特征在于所述SCR催化剂包括选自SSZ-39和SAPO-18的具有AEI类型骨架的水热微孔稳定的沸石，其中所述沸石用铜助催化。
8.根据权利要求7的废气清洁系统，其中具有AEI类型骨架的水热微孔稳定的沸石是用铜助催化的SSZ-39，并且具有5-50的硅与铝的原子比率。
9.根据权利要求7或8的废气清洁系统，其中具有AEI类型骨架的水热微孔稳定的沸石是用铜助催化的SSZ-39，其中原子铜与铝的比率为约0.01-1之间。
10.权利要求7至9中任一项的废气清洁系统，其中在所述SCR催化剂已经暴露在750℃的温度和所述废气中100%的水蒸气含量经13小时后，所述SCR催化剂维持在250℃下氮氧化物初始还原的80%。
11.权利要求7至10中任一项的废气清洁系统，其中所述SCR催化剂在600℃老化后维持初始微孔率的至少80%至90%，并且在750℃老化后维持初始微孔率的至少30%至40%。
12.权利要求7至11中任一项的废气清洁系统，其中所述SCR催化剂沉积在整体式担载结构上。
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