CN103670615A - 用于内燃发动机的贫氮氧化物阱催化剂的活化涂层技术 - Google Patents
用于内燃发动机的贫氮氧化物阱催化剂的活化涂层技术 Download PDFInfo
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Abstract
本发明的实施例提供一种贫氮氧化物阱(281)的催化转换器,其包括涂覆有具有至少两个活性区域的活化涂层的催化剂基层,其中后部区域包括两种活性成分,氧化催化剂和吸附剂,和最小的氧储存能力(OSC),且其中紧位于后部区域之前的区域包括氧化催化剂、还原催化剂、吸附剂和氧储存能力(OSC)。
Description
技术领域
本公开涉及一种用于内燃发动机的贫氮氧化物阱的新的活化涂层技术,其用于增强氨产物。
背景技术
已知柴油发动机的排气后处理***可装备有贫氮氧化物阱(Lean NOxTrap,即LNT)和其它装置。
贫氮氧化物阱(LNT)被设置用于捕获包含在排气中的氮氧化物NOx且位于排气管线中。
LNT是包含PGM(铂族金属)催化剂和吸附剂(例如钡基元件)的催化装置,其提供适于结合包含在排气中的氮氧化物(NOx)的活化点用于将它们捕获在装置自身内。
贫氮氧化物阱(LNT)受到周期性再生处理,该再生处理通常被用于从LNT释放和减少捕获的氮氧化物(NOx)。
LNT被循环操作,例如通过将发动机从贫油燃烧操作切换至过量燃油可用的操作(也称为富油操作或再生阶段)。由于发动机的正常操作,NOx被储存在催化表面上。当发动机被切换至富油操作时,储存在吸附剂点上的NOx与排气中的还原剂反应且被解吸收和转换为氮气和氨,由此再生催化剂的吸附剂点。
本领域还存在已知的用于减排特别是来自柴油发动机排气的氮氧化物(NOx)和颗粒的排气后处理***。这些***设置有沿发动机的排气管线安装的后处理装置且通常包括柴油颗粒过滤器(DPF)用于控制颗粒,和选择性催化还原(SCR)***用于NOx控制。
在本领域中还已知,在一些排气***配置中,为了在柴油发动机的排气管中喷射反应剂(催化剂)以通过上述后处理装置降低排放。特别地,碳氢基反应剂,通常被表示为HC,如图用于给发动机供油的柴油一样,被喷射在排气管中以通过燃烧积蓄在其中的烟灰来促进柴油颗粒过滤器(DPF)的再生。而且,流体催化剂例如尿素、或氨或其组合(通常是水溶液)也被喷射至柴油发动机的排气管中,以促进选择性催化还原***(SCR)中的氮氧化物(NOx)的还原。
碳氢化合物(HC)和尿素催化剂通过安装在排气管中的两个喷射器而被喷射至发动机产生的排气中。
这种配置,由于部件的数量,且特别是用于在排气管中分配碳氢化合物和尿素所需的喷射器的数量,导致高***复杂性、高制造成本,且还导致排气处理***的安装柔性的降低。
这种复杂的排气***的可能的简化是组合上游贫氮氧化物阱(LNT)至NH3储存装置(SCR,选择性催化还原***或SCRF,包括选择性催化还原***的颗粒过滤器)。这种架构的一个大的可能是一方面后处理装置数量的减少另一方面是外部尿素/氨喷射器不再被需要,或至少外部尿素需求被大大降低。实际上,由于富油操作,储存在吸附剂点上的NOx与排气中的还原剂反应且被解吸收和转换为氮气和氨。
从LNT产生的氨可被有利地用于下游SCR/SCRF以去除过多的NOx,同时过滤器去除颗粒物质。这样,不需要尿素喷射器(见图3),由此允许较便宜的排气***架构,或在任意情况下降低了外部尿素需求。必须要说的是,氨的产生必须被小心地控制:量少不足于帮助进行没有外部催化剂喷射的完整的氮还原,而量多则导致氨滑至下游SCR或SCRF。这可通过改善控制策略获得,且本申请以就此主题或替代地催化剂技术提出专利申请。
由此,存在对于LNT的新技术的需求,其在富油阶段(即在LNT的再生处理过程中)优化氨的生成。
本发明的目的是要提供一种新的LNT催化剂,其使用新的活化涂层技术,其优化了氨的生成。
本发明的另一目的是一种排气架构,其合并上游贫氮氧化物阱(LNT)至SCR或SCRF。特别地,该优化涉及新的LNT技术,改善了氨的生成。
这些目的是通过设置有能控制燃料喷射器的电子控制单元且具有独立权利要求所述特征的产品、排气***、发动机和汽车***实现。
从属权利要求限定了优选的和/或特别有利的方面。
发明内容
本公开的实施例提供一种贫氮氧化物阱的催化转换器,其包括涂覆有具有至少两个活性区域的活化涂层的催化剂基层,其中后部区域包括两种活性成分,氧化催化剂和吸附剂,和最小的氧储存能力,且其中紧位于后部区域之前的区域包括氧化催化剂、还原催化剂、吸附剂和氧储存能力。
该实施例的优点是,其提供一种催化剂,该催化剂具有后部区域和紧在后部区域之前的区域,其具有“标准”LNT的活性成分且由此能通过在富油燃烧模式过程中通过NOx氧化产生氨,该后部区域能保存氨,因为低氧储存能力减少了NH3氧化且还原催化剂的缺少最小化了还原NOx中的竞争性NH3消耗反应。
根据本发明的一方面,后部区域的所述氧化催化剂包括钯,所述氧化催化剂包括钯。
该方面的优点是钯的存在便于CO和HC的氧化。
根据本发明的另一方面,所述氧化催化剂包括铂,但是仅在紧在所述后部区域之前的区域中。
该方面的优点是铂的存在便于NOx的氧化,由此在紧在后部区域之前的区域中产生氨。相反,铂在后部区域不是需要的,在那里不应产生氨,但是被保留,且这允许活化涂层的显著成本节省。
根据本发明的另一方面,所述还原催化剂包括铑,但是仅在紧在所述后部区域之前的区域中。
该方面的优点是铑的存在在富油燃烧模式下在再生过程中便于紧在后部区域之前的区域中的NOx的还原。相反,铑在后部区域中不是需要的,在那里氨应被保留,因为其缺乏最小化了还原NOx中的竞争性NH3消耗反应。在后部区域中避免铑还允许活化涂层的显著成本节省。
根据本发明的又一方面,所述吸附剂包括钡氧化物。
该方面的优点是吸附剂的存在在发动机正常操作状况下即在贫油燃烧模式中便于NOx的储存。
根据另一实施例,本发明提供一种用于捕获氮氧化物然后还原和释放氮的贫氮氧化物阱,包括催化转换器,其具有涂覆有具有两个活性区域(前部区域和后部区域)的活化涂层的催化剂基层,其中后部区域根据前述实施例的方面实现,且其中前部区域如根据前述实施例的方面的紧在后部区域之前的所述区域实现。
该实施例的优点是贫氮氧化物阱可利用前部区域执行其通常的功能,而后部区域主要用于增强和维护氨生成。
根据又一实施例,本发明提供一种内燃发动机的后处理***,其包括至少两个后处理装置,该后处理装置至少为根据前述实施例的贫氮氧化物阱,和选择性催化还原***或包括颗粒过滤器的选择性催化还原***。
该实施例的优点是后处理***被优化以通过平衡两个装置的性能和提供氨给SCR/SCRF而不需要任意外部氨或尿素供应来减少NOx排放。
本发明的另一实施例提供装备有根据前述实施例的后处理***的汽车***的内燃发动机。
本发明的再一方面提供一种汽车***,其包括配置为控制根据前述实施例的内燃发动机的后处理***的电子控制单元。
附图说明
现在通过实例各种实施例参考附图描述各个实施例,在附图中:
图1示出了汽车***;
图2是属于图1的汽车***的内燃发动机的截面;
图3是根据本发明的后处理***和发动机的示意图;
图4是根据本发明的后处理***的示意图;
图5是根据本发明的实施例的结合活化涂层的LNT催化剂的示意图;
附图标记
40 数据载体
100 汽车***
110 内燃发动机
120 发动机缸体
125 汽缸
130 汽缸盖
135 凸轮轴
140 活塞
145 曲轴
150 燃烧室
155 凸轮相位器
160 燃料喷射器
170 燃料轨道
180 燃料泵
190 燃料源
200 进气歧管
205 空气进入管
210 进气口
215 阀
220 口
225 排气歧管
230 涡轮增压器
240 压缩机
245 涡轮增压器轴
250 涡轮
260 中冷器
270 排气***
275 排气管
280 后处理装置
281 贫氮氧化物阱
282 选择性催化还原(SCR)***
283 包括颗粒过滤器的选择性催化还原***(SCRF)
284 SCR/SCRF上游的NH3/NOx双传感器
285 SCR/SCRF下游的NH3/NOx双传感器
290 VGT促动器
300 废气再循环***
310 EGR冷却器
320 EGR阀
330 节流阀体
340 空气质量流量和温度传感器
350 歧管压力和温度传感器
360 燃烧压力传感器
380 冷却剂温度和水平传感器
385 润滑油温度和水平传感器
390 金属温度传感器
400 燃料轨压力传感器
410 凸轮位置传感器
420 曲轴位置传感器
430 排气压力和温度传感器
440 EGR温度传感器
445 加速器位置传感器
446 加速器踏板
450 ECU
具体实施方式
一些实施例可包括汽车***100,如图1和2所示,其包括具有发动机缸体120的内燃发动机(ICE)110,缸体限定至少一个汽缸125,该汽缸具有活塞140,该活塞被联接为旋转曲轴145。汽缸盖130与活塞140协作以限定燃烧室150。然后和空气混合物(未示出)被布置在燃烧室150中且被点火,导致热膨胀排气,其导致活塞140的往复运动。燃料由至少一个燃料喷射器160提供,且空气是穿过至少一个进气口210提供。燃料以高压从与高压燃料泵180流体联通的燃料轨170提供至燃料喷射器160,高压燃料泵180提高收容燃料的燃料源190的压力。每个气缸125具有至少两个阀215,阀215由与曲轴145正时旋转的凸轮轴135促动。阀215选择性地允许空气经由口210进入燃烧室150,并交替允许废气通过口220排出。在一些示例中,凸轮相位器155可选择性地改变凸轮轴135和曲轴145之间的正时。
空气可经过进气歧管200被分配至空气进气口(一个或多个)210。空气入口管道205可提供来自周围环境的空气至进气歧管200。在其他实施例中,可提供节流阀体330以调节进入歧管220的空气流。在其他的实施例中,可提供强制进气***,例如涡轮增压器230,其具有可转动地联接到涡轮250的压缩机240。压缩机240的旋转提高了管道205和歧管200中的空气压力和温度。置在管道205中的中冷器260可降低空气的温度。涡轮250通过接收来自排气歧管225的废气而旋转,排气歧管225引导废气在膨胀经过涡轮250之前从排气口220经过一系列叶片。废气从涡轮250出来并被引导进入排气***270。该示例示出了可变几何涡轮(VGT)250,其布置有VGT致动器290以移动叶片从而改变经过涡轮250的废气流动。在其他实施方式中,涡轮增压器230可以是固定几何形状和/或包括废气门。
排气***270可包括具有一个或多个废气后处理装置280的排气管275。后处理装置可以是配置成改变废气成分的任何装置。后处理装置280的一些示例包括但不局限于,催化转化器(二元和三元)、氧化催化剂281、稀油NOx捕集器、碳氢化合物吸附剂、选择性催化还原(SCR)***、颗粒过滤器(DPF)282、或者最后两种装置的组合,即,包括颗粒过滤器的选择性催化还原***(SCRF)。一些实施例可包括联接在排气歧管225和进气歧管200之间的废气再循环(EGR)***300。EGR***300可包括EGR冷却器310以降低EGR***300中废气的温度。EGR阀320调节EGR***300中废气的流动。
汽车***100可进一步包括电子控制单元(ECU)450,电子控制单元(ECU)450与一个或多个传感器和/或连接ICE110的装置相连通,并且装载有数据载体40。ECU450可接收来自不同传感器的输入信号,不同传感器配置为产生关于ICE110的与不同物理参数成比例的信号。传感器包括但是不局限于,空气质量流量和温度传感器340、歧管压力和温度传感器350、燃烧压力传感器360、冷却液和油温及液位传感器380、燃料轨压力传感器400、凸轮位置传感器410、曲轴位置传感器420、排气压力和温度传感器430、EGR温度传感器440、以及加速器踏板位置传感器445。此外,ECU450可产生针对不同控制装置的输出信号,布置不同的控制装置用于控制ICE110的运行,包括但不局限于,燃料喷射器160、节流阀体330、EGR阀320、VGT致动器290、以及凸轮相位器155。注意,虚线用于指示ECU450和不同传感器以及装置之间的连通,但是为了清楚省略了一些。
现在转向ECU450,该装置可包括与存储***以及接口总线相连接的数字中央处理单元(CPU)。CPU配置成执行作为程序被储存在存储***中的指令,并且向接口总线发送信号以及从接口总线接收信号。存储***可包括不同的存储器类型,包括光存贮器、固态存储器和其他非易失性存储器。接口总线可配置为向不同传感器和控制装置或者从不同传感器和控制装置发送、接收、以及调整模拟信号和/或数字信号。该程序可以包括此处揭示的方法,允许CPU执行该方法的步骤并控制ICE110。
转回至排气***270,提出的发明依赖于后处理***的优化,其特征在于两个NOx后处理装置的组合。组合的***包括以所有可能的紧联接和/或地板下配置定位的上游LNT281和下游SCR282或SCRF(DPF上的SCR)283。
优选地,第一催化剂可被尽可能靠近涡轮增压器定位以利用高温条件,其对于LNT和SCR/SCRF都是有利的。
LNT在贫油操作状况下高效地减少发动机排出的排气成分(CO和HC)且储存NOx。在富油操作状况下,NOx被释放和转化。
但是在富油操作状况下,当LNT催化剂被单独或与下游DPF一起使用时,NH3(氨)也被产生,虽然其通常不被监测。产生的氨的量依赖于富油燃烧状况的具体管理,例如空气/燃料比值,每单个DeNOx事件的时长和温度状况。
通常,如图4所示,在富油燃烧模式中LNT的氨生成可被布置在SCRF上游的特定传感器(即,NH3/NOx双传感器)监测。由此,可以独立于LNT技术量化到达SCRF的NH3的量。
第二特定传感器285,其布置在SCRF下游,监测滑过SCRF的NH3的量。由此,组合来自两个传感器的信息,可以监测储存至SCRF中的当前氨产物。
依赖于校准状态和各种知识和LNT活化涂层的特征,在富油燃烧模式中,当前氨产物可最终被预测和映射。由此,SCR/SCRF上游传感器284可被免除。
本发明的目的是要设计LNT上的新活化涂层技术。如已知的,LNT是基于包括催化剂基层或芯部的催化转换器,其该基层通常为具有蜂巢结构的陶瓷单体。该单体被涂覆有复杂物质,所谓的活化涂层(washcoat)。活化涂层是催化材料的载体且被用于在表面面积上分散材料。铝氧化物、钛氧化物、硅氧化物或硅土和矾土的混合物可被使用。催化材料(稀有金属,例如铂、钯和铑还有钡氧化物,在LNT特定情况下)在施加至芯部前被悬浮在活化涂层中。该新活化涂层的分区概念应是优选的实施例:实际上,除了“标准”LNT281功能,在预定的校准和控制操作下,该新活化涂层应增强NH3生成,以使得SCR/SCRF282、283正确地工作。更详细地,“标准”LNT的必要功能是:在富油燃烧模式中,转化碳氢化合物(HC)、碳氧化合物(CO)、捕获NOx、产生放热、转化NOx和释放硫化物。除了这些,新活化涂层技术的特征应为产生更多的氨。
用于LNT的已知活化涂层组合了三个活性成分:氧化催化剂,例如铂和钯(Pt-Pd),以增强CO、HC和NO(转化为NO2,以保持下游SCR/SCRF的优化的NO:NO2的比例)氧化反应;吸附剂,例如钡氧化剂(BaO),以储存发动机排出的NOx;和还原剂,例如铑(Rh),以在富油燃烧模式下再生过程中还原NOx。实际上,在富油模式中,从BaO点释放的NOx被转化为N2。而且,标准LNT活化涂层还包括氧储存能力(OSC),其提供用于氧化反应所需的氧。
还应注意,在富油燃烧模式下在DeNOx再生过程中,生成的N2,结合H2,将是产生NH3的反应剂。此外,释放的NOx可直接与HC或H2反应以生成NH3。由此,钡氧化物的量可被优化以增强两种类型的反应的NH3生成。
一旦生成,氨可被进一步氧化(由于可用的氧,其从OSC释放,且通过铂的存在而被增强),或被还原:铑的存在可改善带有必然的氨消耗的NOx(从催化剂滑动)至N2的反应。为了最小化这些进一步的反应,限定了新活化涂层概念。其特征在于分区涂层,其中至少紧在后部区域之前的区域被设计为做为标准LNT催化剂转化排放物。在图5中,这种分区涂层的实例被示出。其包括两个区域(但是在其它实施例中这些区域可多于两个)且紧在后部区域之前的区域,其在图5中的实例中是前部区域,被设计为做为标准LNT催化剂转化排放物。由此,其组合了三种活性成分:氧化催化剂(Pt-Pd)、吸附剂(BaO)和还原催化剂(Rh)。而且OSC可相当于标准LNT催化剂。
在后部区域中,活化涂层被设计为利用前部区域中产生的反应(和放热)。其包括仅两种活性成分:氧化催化剂和吸附剂(BaO)。氧化催化剂优选地应仅为钯,以改善CO和HC的氧化,同时铂的量可被降低至零,以降低用于NH3氧化的活性。还原催化剂(Rh)也可被减少至零,以最小化竞争性NH3消耗反应(从LNT滑动的NOx可被储存的NH3随后转化为N2,这是由于下游SCR/SCRF的存在)。OSC也必须被最小化以减少NH3氧化。
本新的活化涂层不影响LNT制造过程:实际上,这种贫氮氧化物阱的涂层可通过使用标准涂覆技术完成。
总之,获得更多氨(NH3)产物的催化特性是低氧储存能力(OSC)以减少NH3氧化,低或没有铑含量以最小化竞争性NH3消耗反应,以及分区涂层以控制和增强前部区域上的H2生成,减小后部区域上的OSC和控制NO至NO2氧化,保持用于下游SCR/SCRF的优化NO:NO2比。
LNT活化涂层设计的优化,车辆使用如图4中所示的后处理***,即LNT和SCR/SCRF,和适当的后处理控制,将具有下面的优点:
a)降低SCR/SCRF发动机管理***的硬件成本:实际上,当前/标准尿素注射***不再被需要:氨将就地以蒸气相产生;
b)降低了发动机排放气流中的NOx排放,这是由于通过LNT增强了低温NOx储存和通过下游SCR/SCRF去除了额外的NOx;
c)通过减少铑含量降低了LNT催化剂的成本,因为总的NOx转化效率可杠杆调节LNT和SCR/SCRF体积获得;
d)通过减少铂量降低了LNT催化剂的成本;
e)与地板下SCR相比,允许SCR/SCRF入口处的更高温度,且最终允许更好的NOx转化效率;
f)通过DeSOx再生过程中转化SCR/SCRF催化剂上的H2S的LNT副排放,降低了H2S排放(臭鸡蛋味);
g)降低了封装:与已知的紧联接DOC/DPF和地板下SCR类方案相比,这种方案提供了降低数量的基层和灌装盒;
h)降低了CO2排放和背压:这种更紧凑的封装也更轻;
i)通过反应来产生氨(NH3),进一步增强了碳氢化合物的转化。
至少一个示例性的实施例在前述的发明内容和具体实施方式中已经介绍,但应当认识到存在多种变型。还应当认识到示例性的实施方式仅仅是举例,且并非旨在以任何方式限制范围、适应性、或者构型。然而,前述的发明内容和具体实施方式将为本领域技术人员提供便利的手段图示以至少实现一个示例实施方式,应理解为可以对示例实施方式中所描述的元件功能和布置做出多种不同的变化,而不脱离在后附的权利要求以及其法定等同物中所设定的范围。
Claims (10)
1.一种贫氮氧化物阱(281)的催化转换器,其包括涂覆有具有至少两个活性区域的活化涂层的催化剂基层,其中后部区域包括两种活性成分,氧化催化剂和吸附剂,和最小化的氧储存能力(OSC),且其中紧位于后部区域之前的区域包括氧化催化剂、还原催化剂、吸附剂和氧储存能力(OSC)。
2.如权利要求1所述的催化转换器,其中后部区域的所述氧化催化剂包括钯(Pd)。
3.如权利要求1或2所述的催化转换器,其中所述氧化催化剂包括铂(Pt),但是仅在紧位于所述后部区域之前的区域中。
4.如前述权利要求任一项所述的催化转换器,其中所述还原催化剂包括铑(Rh),但是仅在紧位于所述后部区域之前的区域中。
5.如前述权利要求任一项所述的催化转换器,其中所述吸附剂包括钡氧化物(BaO)。
6.一种用于捕获氮氧化物然后还原和释放氮的贫氮氧化物阱(381),其包括催化转换器,该催化转换器包括涂覆有具有两个活性区域的活化涂层的催化剂基层,该两个区域为前部区域和后部区域,其中后部区域是根据权利要求1、2或5实现,且其中前部区域是根据权利要求1-5中任一项如所述紧位于后部区域之前的区域实现。
7.一种根据权利要求1-5中任一项的贫氮氧化物阱(281)的催化转换器的活化涂层。
8.一种内燃发动机(110)的后处理***,其包括至少两个后处理装置(280),该后处理装置至少为根据权利要求6的贫氮氧化物阱(281),和选择性催化还原***(282)或包括颗粒过滤器的选择性催化还原***(283)。
9.一种装备有根据权利要求8的后处理***的汽车***(100)的内燃发动机(110)。
10.一种汽车***(100),其包括配置为控制根据权利要求9的内燃发动机(110)的后处理***的电子控制单元(450)。
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US20040082470A1 (en) * | 2002-10-24 | 2004-04-29 | Gandhi Haren S. | Catalyst system for lean burn engines |
CN101230794A (zh) * | 2007-01-23 | 2008-07-30 | 通用汽车环球科技运作公司 | 催化转化器的优化 |
CN101749084A (zh) * | 2008-12-02 | 2010-06-23 | 福特环球技术公司 | 选择性催化还原反应(scr)排放控制*** |
CN101808714A (zh) * | 2007-07-26 | 2010-08-18 | 伊顿公司 | 用于柴油燃料重整装置的配置于废气流中的催化剂组合物和结构 |
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US20040082470A1 (en) * | 2002-10-24 | 2004-04-29 | Gandhi Haren S. | Catalyst system for lean burn engines |
CN101230794A (zh) * | 2007-01-23 | 2008-07-30 | 通用汽车环球科技运作公司 | 催化转化器的优化 |
CN101808714A (zh) * | 2007-07-26 | 2010-08-18 | 伊顿公司 | 用于柴油燃料重整装置的配置于废气流中的催化剂组合物和结构 |
CN101749084A (zh) * | 2008-12-02 | 2010-06-23 | 福特环球技术公司 | 选择性催化还原反应(scr)排放控制*** |
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