CN102725486A - 柴油机的排气净化装置以及排气净化方法 - Google Patents

柴油机的排气净化装置以及排气净化方法 Download PDF

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CN102725486A
CN102725486A CN2011800070390A CN201180007039A CN102725486A CN 102725486 A CN102725486 A CN 102725486A CN 2011800070390 A CN2011800070390 A CN 2011800070390A CN 201180007039 A CN201180007039 A CN 201180007039A CN 102725486 A CN102725486 A CN 102725486A
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oxidation catalyst
exhaust gas
diesel engine
exhaust
urea
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CN102725486B (zh
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大角和生
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Isuzu Motors Ltd
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Abstract

本发明提供通过巧妙地配置各后处理单元即可有效地利用排气的热量且实现了小型化的柴油机的排气净化装置以及使用了该排气净化装置的排气净化方法。排气净化装置(17)具备：配置在柴油机(1)的排气通路(7)上且净化废气中的CO、HC的氧化催化剂(19)；配置在氧化催化剂(19)的下游且用于通过向废气中喷雾尿素水来生成氨的尿素喷射喷嘴(22)；配置在尿素喷射喷嘴(22)的下游且搅拌所喷雾的尿素水来促进尿素分解的涡轮增压器(9)的涡轮(13)；配置在涡轮(13)的下游且通过使废气中的NOx与氨发生还原反应来实现无害化的选择性还原型催化剂(23)；以及配置在选择性还原型催化剂(23)的下游且捕集废气中的PM的DPF(20)。

Description

柴油机的排气净化装置以及排气净化方法
技术领域
本发明涉及柴油机的排气净化装置以及排气净化方法。
背景技术
在搭载于货车、公共汽车等车辆中的柴油机的废气中存在颗粒物(PM)、氮氧化物(NOx)、一氧化碳(CO)、碳氢化合物(HC)等有害物质。
近年来，为了减少来自车辆的这些有害物质的排放量，采取了下列对策：通过改良柴油机的燃烧来减少有害物质的产生本身；以及通过在柴油机的排气通路中配置氧化催化剂(DOC：Diesel Oxidation Catalyst，柴油机氧化催化剂)、柴油颗粒过滤器(DPF：Diesel Particulate Filter)、尿素选择性还原型催化剂(尿素SCR：Urea-Selective Catalytic Reduction)或NOx吸藏还原型催化剂(LNT：Lean NOx Trap，稀油氮氧化物捕集器)等多个后处理单元来尽可能地从废气中除去上述有害物质(参见专利文献1、2)。
现有技术文献
专利文献
专利文献1：日本特开2009-264147号公报
专利文献2：日本特开2009-257226号公报
发明内容
发明要解决的技术问题
但是，当改良柴油机的燃烧来减少有害物质的产生本身时，从发动机的排气口流出的废气的温度与以往(改良前)相比降低30~50℃或降低更多。
此外，当在排气通路中配设多个后处理单元时，由这些后处理单元构成的排气净化装置会大型化，其热容量会增大。热容量增大了的排气净化装置根据发动机的运转状况的不同有时很难确保催化剂活性温度。
此外，大型的排气净化装置由于设置空间的问题而被配置在远离发动机排气口的位置上，更加难以确保催化剂活性温度。其结果是，会削弱排气净化装置的各后处理单元中的有害物质的减少效果。
鉴于以上情况而完成的本发明的目的在于提供通过巧妙地配置各后处理单元即可有效地利用废气的热量并能实现小型化的柴油机的排气净化装置以及使用了该排气净化装置的排气净化方法。
用于解决技术问题的手段
为了实现上述目的，本发明的柴油机的排气净化装置具备：配置在柴油机的排气通路上、且净化废气中的CO、HC的氧化催化剂；配置在该氧化催化剂的下游的上述排气通路上、且用于通过向废气中喷雾尿素水来生成氨的尿素喷射喷嘴；配置在该尿素喷射喷嘴的下游的上述排气通路上、且搅拌所喷雾的尿素水来促进尿素分解的涡轮增压器的涡轮；配置在该涡轮的下游的上述排气通路上、且通过使废气中的NOx与氨发生还原反应来实现无害化的选择性还原型催化剂；以及配置在该选择性还原型催化剂的下游的上述排气通路上、且捕集废气中的颗粒物的柴油颗粒过滤器。
上述柴油颗粒过滤器可以是涂布有用于将捕集到的颗粒物氧化的氧化催化剂的柴油颗粒过滤器。
在上述柴油颗粒过滤器的下游的上述排气通路上，可以进一步配置用于将从上述柴油颗粒过滤器流出的氨进行氧化来实现无害化的后段氧化催化剂。
上述氧化催化剂可以具有配置在上述柴油机的排气岐管的各汽缸部分上的岐管氧化催化剂和配置在上述排气岐管的集合部分上的涡轮前氧化催化剂(pre-turbine oxidation catalyst)，上述岐管氧化催化剂在CO净化上优于上述涡轮前氧化催化剂，上述涡轮前氧化催化剂在HC净化上优于上述岐管氧化催化剂。
上述岐管氧化催化剂可以是包含具有氧吸藏材料的氧化物和氧化物半导体的催化剂，上述涡轮前氧化催化剂可以是金属催化剂。
上述具有氧吸藏材料的氧化物可以是含有Ce的氧化物，上述氧化物半导体可以是TiO2、ZnO或Y2O3。
在上述具有氧吸藏材料的氧化物上可以担载有贵金属。
使用了以上所述的柴油机的排气净化装置的排气净化方法的特征在于，由从上述尿素喷射喷嘴喷雾的尿素水生成的氨(NH3)与废气中的硫氧化物(Sox)反应而发生2NH3＋SO4→(NH4)2SO4，该(NH4)2SO4被上述选择性还原型催化剂捕捉并通过热解而生成氨(NH3)，该氨(NH3)被用于NOx的还原反应。
发明效果
根据本发明的柴油机的排气净化装置以及排气净化方法，通过巧妙地配置各后处理单元，即可有效地利用废气的热量并能够实现装置的小型化。
附图说明
图1是表示比较例(非本发明的实施方式)的柴油机的排气净化装置、以及SCR及DOC的温度与净化率的关系的说明图。
图2是表示本发明的一个实施方式的柴油机的排气净化装置、以及SCR及DOC的温度与净化率的关系的说明图。
具体实施方式
结合附图对本发明的一个实施方式进行说明。
<比较例>
首先，用图1来说明用以与本发明的实施方式进行对比的比较例。
如图1所示，在柴油机1的吸气岐管2上连接有吸气配管3，在排气岐管4上连接有排气配管5。吸气岐管2和吸气配管3构成吸气通路6，排气岐管4和排气配管5构成排气通路7。在吸气配管3和排气配管5上串联地连接有高压级涡轮增压器(高压级涡轮机)8和低压级涡轮增压器(低压级涡轮机)9。
即，在排气配管5上配设有高压级涡轮机8的高压级涡轮12和低压级涡轮机9的低压级涡轮13，在吸气配管3上配设有高压级涡轮机8的高压级压缩机10和低压级涡轮机9的低压级压缩机11。在高压级压缩机10的下游的吸气配管3上配置有中间冷却器14。排气岐管4和吸气配管3由EGR配管15连接，在EGR配管15上配设有EGR阀16。另外，还可以在EGR配管15上设置EGR冷却器(未图示)。
在低压级涡轮13的下游的排气配管5上配设有净化废气中的有害物质(PM、NOx、CO、HC等)的排气净化装置17a。关于排气净化装置17a，将在后面进行描述。在排气净化装置17a的下游的排气配管5上连接有低压EGR配管18，该低压EGR配管18将流向未图示的消声器的废气的一部分导入吸气配管3(低压级压缩机11的上游、低压级压缩机11和高压级压缩机10之间、高压级压缩机10的上游中的任一部分)。在低压EGR配管18上设有低压EGR阀(未图示)，当然也可以设置EGR冷却器。
排气净化装置17a具有：内部收纳有氧化催化剂(DOC)19a的第1收纳箱21a；配置在该第1收纳箱21a下游的排气配管5上且向排气配管5内喷雾尿素水的尿素喷射喷嘴22a；以及配置在该尿素喷射喷嘴22a下游的排气配管5上且在内部收纳有尿素选择性还原型催化剂(尿素SCR)23a、柴油颗粒过滤器(DPF)20a和后段氧化催化剂(R-DOC：Rear Diesel OxidationCatalyst，后段柴油机氧化催化剂)24a的第2收纳箱25a。
DOC19a具有在将废气中的CO、HC氧化而净化的同时将NO氧化的功能。尿素喷射喷嘴22a具有通过喷雾到排气配管5内的尿素水发生水解、热解来生成氨(NH3)的功能。尿素SCR23a具有通过使废气中的NOx与氨发生还原反应来无害化成水和氮的功能，DPF20a具有捕集废气中的PM的功能，R-DOC24a具有将从尿素SCR23a流出的氨进行氧化来实现无害化的功能。
所述排气净化装置17a由于构成排气净化装置17a的后处理单元(DOC19a、尿素喷射喷嘴22a、SCR23a、DPF20a、R-DOC24a)全部配置在低压级涡轮13的下游侧，因此从柴油机1的排气口到排气净化装置17a的距离长。由此，从柴油机1的排气口流出的废气在通过排气配管5时会散热，在低压级涡轮13中膨胀后，到达排气净化装置17a。因此，根据柴油机1的运转状态，有时DOC19a、SCR23a、DPF20a、R-DOC24a的温度不会上升到催化剂活性温度。
例如当在被称为JE05模式的过渡模式(加减速模式)下使柴油机1运转时，DOC19a、SCR23a、DPF20a的平均入口温度是DOC19a为约150℃、SCR23a为约140℃、DPF20a为约125℃。如图1所示，在150℃时DOC19a的HC净化率为10%左右(CO净化率也相同)，在140℃时SCR23a的NOx净化率为40%左右。其结果是，HC、CO、NOx的JE05模式下的平均净化率均为50%以下。
另外，当在JE05模式下的试验中进行DPF20a的再生(捕集到的PM的燃烧)时，必须将DPF20a从140℃加热至400℃以上，若为此而进行后喷射(从喷射器向柴油机1的燃烧室内进行了通常的燃料喷射后喷出不以在柴油机1中燃烧为目的的燃料的喷射)，则燃料消耗量会增加5%左右并会导致HC的产生。
此外，为了使从尿素喷射喷嘴22a喷雾到排气配管5内的尿素水在到达SCR23a之前均匀地扩散并恰当地分解成氨，从尿素喷射喷嘴22a的尿素喷射位置到SCR23a的入口的距离必须为规定距离(由实验可知必须是25cm以上)。这会导致SCR23a的温度下降、排气净化装置17a的大型化。
<实施方式>
用图2来说明消除了上述比较例的缺点的本发明的一个实施方式。本实施方式具有与上述比较例共同的构成要素，因此对共同的构成要素赋予相同的符号并省略说明。另外，关于排气净化装置17，带有“a”的表示比较例，没有“a”的表示本实施方式。
如图2所示，本实施方式的柴油机1的排气净化装置17具备：配置在柴油机1的排气通路7上且在将废气中的CO、HC净化的同时将NO氧化的前段的氧化催化剂(DOC)19；配置在DOC19的下游的排气通路7上且用于通过向废气中喷雾尿素水来生成氨的尿素喷射喷嘴22；配置在尿素喷射喷嘴22的下游的排气通路7上且搅拌所喷雾的尿素水来促进尿素分解的涡轮(低压级涡轮)13；配置在低压级涡轮13的下游的排气通路7上且通过使废气中的NOx与氨发生还原反应来实现无害化的选择性还原型催化剂(尿素SCR)23；以及配置在尿素SCR23的下游的排气通路7上且捕集废气中的颗粒物(PM)的柴油颗粒过滤器(DPF)20。另外，在DPF20的下游的排气通路7上配置有用于将从DPF20流出的氨进行氧化来实现无害化的后段氧化催化剂(R-DOC)24。
关于各后处理单元(DOC19、尿素喷射喷嘴22、SCR23、DPF20、R-DOC24)，将在后面进行详细描述。
本实施方式为将高压级涡轮机8和低压级涡轮机9串联地连接而成的两段式的涡轮增压器、在低压级涡轮13和高压级涡轮12之间配置有尿素喷射喷嘴22、在高压级涡轮12的上游侧配置有DOC19的构成，但也可以省略高压级涡轮机8而为一段式的涡轮增压器。此时，在唯一的涡轮增压器(图2中的低压级涡轮机9)的涡轮(图2中的低压级涡轮13)的上游侧配置尿素喷射喷嘴22，在该尿素喷射喷嘴22的上游侧配置DOC19。
在本实施方式的排气净化装置17中，由于在低压级涡轮13的上游侧配置有尿素喷射喷嘴22和DOC19，因此与包括尿素喷射喷嘴22和DOC19在内的全部后处理单元均配置在低压级涡轮13的下游侧的图1所示的比较例相比，能够使各后处理单元(DOC19、SCR23、DPF20、R-DOC24)的设置位置更靠近柴油机1的排气口。由此，能够有效地利用废气的热量，容易将各后处理单元的温度确保为催化剂活性温度。
例如当在JE05模式下使柴油机1运转时，DOC19、SCR23、DPF20的平均入口温度是DOC19为约200℃、SCR23为约175℃、DPF20为约170℃。如图2所示，在200℃时DOC19的HC净化率大致为100%(CO净化率也相同)，在175℃时SCR23的NOx净化率为约80%。如上所述那样，在本实施方式中HC、CO、NOx的净化率与比较例相比大幅提高。
另外，在本实施方式中，在低压级涡轮13的正下方隔着SCR23配置有DPF20，与图1所示的比较例那样在低压级涡轮13的下游隔着DOC19a、尿素喷射喷嘴22a以及SCR23a而配置DPF20a的构成相比，DPF20的设置位置更靠上游侧。由此，与比较例相比DPF20的温度升高，即使减少后喷射或根据运转状态而不进行后喷射，也能够使DPF20捕集的PM燃烧。因此，能够避免因后喷射引起的燃料消耗量的增加，并且能够抑制因后喷射引起的HC的产生。
此外，在本实施方式中，由于将尿素喷射喷嘴22配置在低压级涡轮13的上游侧，因此从尿素喷射喷嘴22喷雾的尿素水被低压级涡轮13搅拌，在低压级涡轮13的下游侧大致均匀地扩散。因此，尿素的水解、热解得到促进，即使从尿素喷射喷嘴22的尿素喷射位置到SCR23的入口的距离与比较例相比更近，也能够恰当地生成氨。如上所述那样，由于SCR23的设置位置与比较例相比更靠近低压级涡轮13，因此与比较例相比能够提高SCR23的温度，并且能使排气净化装置17更紧凑。
对各后处理单元进行详细描述。
[DOC]
DOC19具有配置在柴油机1的排气岐管4的各汽缸部分上的岐管氧化催化剂(M/F-DOC)19x和配置在排气岐管4的集合部分上的涡轮前氧化催化剂(P/T-DOC)19y。上游侧的M/F-DOC19x使用在CO净化上优于下游侧的P/T-DOC19y的氧化催化剂，下游侧的P/T-DOC19y使用在HC净化上优于上游侧的M/F-DOC19x的氧化催化剂。这是因为DOC通常具有如下性质：当废气中不存在CO时HC的吸附和净化良好，即使废气中存在HC，CO的吸附和净化也不会变差。
M/F-DOC19x由包含具有CO净化(CO吸附)优异的氧吸藏材料(OSC：Oxygen Storage Capacity，氧吸藏功能)的氧化物和氧化物半导体的催化剂构成，P/T-DOC19y由HC净化(HC吸附)优异的金属催化剂(Pt催化剂等)构成。通过如此构成DOC19，在能够得到低温活性优异的催化剂构成的同时，能够使DOC19整体小型化，并能够轻松地配置在高压级涡轮12的上游侧。
另外，M/F-DOC19x可以制成包含具有OSC的氧化物和氧化物半导体混合存在的催化剂的催化剂层，P/T-DOC19y可以使用贵金属催化剂(Pt催化剂等)和HC吸附材料混合存在的催化剂。此外，具有OSC的氧化物使用含有铈(Ce)的氧化物(氧化铈等)，在该氧化物中可以担载有贵金属(Pt等)。另外，氧化物半导体使用TiO2、ZnO或Y2O3。
在M/F-DOC19x和P/T-DOC19y之间的排气岐管4上连接有EGR配管15。由此，通过M/F-DOC19x使CO得到净化后的废气会通过EGR配管15回流至吸气配管3。因此，回流的废气中的未燃烧物质(SOF成分：solubleorganic fraction elements，可溶性有机成分)减少，能够抑制由SOF引起的EGR阀16和EGR冷却器(未图示)的污染、堵塞等不良影响。
[尿素喷射喷嘴]
尿素喷射喷嘴22配设在低压级涡轮13的上游的排气配管5上。因此，从尿素喷射喷嘴22喷雾的尿素水被低压级涡轮13搅拌，在低压级涡轮13的下游侧大致均匀地扩散，尿素的水解、热解得到促进。由此，能够使从尿素喷射喷嘴22的尿素喷射位置到SCR23的入口的距离与比较例相比更近，如上所述那样与比较例相比能够提高SCR23的温度，并能使排气净化装置17更紧凑。
虽然高EGR燃烧时会在废气中产生硫氧化物(SOx)，但由该SOx引起的排气配管5、低压级涡轮13的腐蚀能够利用以下的反应来抑制。
首先，从尿素喷射喷嘴22喷雾的尿素水水解、热解而生成的氨(NH3)与废气中的SO4等反应，发生2NH3＋SO4→(NH4)2SO4。由于生成的(NH4)2SO4是中和物，因此不会产生排气配管5、低压级涡轮13腐蚀的问题。
然后，该(NH4)2SO4被低压级涡轮13的正下方的SCR23捕捉，当达到规定温度(例如120℃)以上时热解而生成氨(NH3)，该氨(NH3)在SCR23中用于NOx的还原反应。
[SCR]
SCR23配设为位于低压级涡轮13的下游，其具有通过使废气中的NOx与氨(NH3)发生还原反应来无害化成水和氮的功能。
此外，SCR23采用了小型的SCR，该小型的SCR通过使用催化剂载体(整体式催化剂：monolith catalyst)等而使单位比体积的催化剂量增加并且使体积与以往相比减少了50%以上。
另外，在图2的实施方式中，SCR23、DPF20和R-DOC24被收纳于与低压级涡轮13的涡轮壳一体形成的收纳箱26内，但也可以将收纳箱26与涡轮壳制成离体，并用短的排气配管将它们之间连接。
[DPF]
DPF20配设在收纳箱26内并位于SCR23的下游，使用过滤器主体上涂布有用于将捕集到的PM燃烧(氧化)的氧化催化剂(贵金属催化剂)的DPF(带催化剂DPF)。但是，只要能够确保使DPF20捕集到的PM能自燃的废气温度，也可以使用未涂布氧化催化剂的DPF20。
另外，DPF20的过滤器主体通过实现气孔率、气孔径、壁厚的合理化，从而形成净化特性(PM的捕集特性)与现有产品等同并且压力损失小的结构。所用的DPF是通过这种改良使体积与现有产品相比小50%以上的小型的DPF。
[R-DOC]
R-DOC24配设在收纳箱26内并位于DPF20的下游，具有将没有被SCR23中的还原反应消耗而通过了DPF20的剩余的氨(NH3)氧化来实现无害化的功能。
另外，当DPF20为通常的带催化剂DPF时，由于没有被SCR23中的还原反应消耗而从SCR23流出的氨(NH3)在通过带催化剂的DPF20时会发生氧化而实现无害化，因此也可以省略R-DOC24。但是，即使在这种情况下，为确保氨(NH3)的无害化也可以设置R-DOC24。
此外，在根据柴油机1的运转状态来控制尿素水的喷雾量以使得由从尿素喷射喷嘴22喷雾的尿素水生成的氨(NH3)全部在SCR23中被消耗的情况下，也可以省略R-DOC24。
符号说明
1柴油机
4排气岐管
7排气通路
9涡轮增压器(低压级涡轮增压器)
13涡轮(低压级涡轮)
19氧化催化剂(DOC)
19x岐管氧化催化剂(M/F-DOC)
19y涡轮前氧化催化剂(P/T-DOC)
22尿素喷射喷嘴
20柴油颗粒过滤器(DPF)
23选择性还原型催化剂(SCR)
24后段氧化催化剂(R-DOC)

Claims (8)

1.一种柴油机的排气净化装置，其特征在于，具备：
配置在柴油机的排气通路上、且净化废气中的CO、HC的氧化催化剂；
配置在所述氧化催化剂的下游的所述排气通路上、且用于通过向废气中喷雾尿素水来生成氨的尿素喷射喷嘴；
配置在所述尿素喷射喷嘴的下游的所述排气通路上、且搅拌所喷雾的尿素水来促进尿素分解的涡轮增压器的涡轮；
配置在所述涡轮的下游的所述排气通路上、且通过使废气中的NOx与氨发生还原反应来实现无害化的选择性还原型催化剂；以及
配置在所述选择性还原型催化剂的下游的所述排气通路上、且捕集废气中的颗粒物的柴油颗粒过滤器。
2.根据权利要求1所述的柴油机的排气净化装置，其中，所述柴油颗粒过滤器是涂布有用于将捕集到的颗粒物氧化的氧化催化剂的柴油颗粒过滤器。
3.根据权利要求1或2所述的柴油机的排气净化装置，其中，在所述柴油颗粒过滤器的下游的所述排气通路上，进一步配置有用于将从所述柴油颗粒过滤器流出的氨进行氧化来实现无害化的后段氧化催化剂。
4.根据权利要求1~3中任一项所述的柴油机的排气净化装置，其中，
所述氧化催化剂具有配置在所述柴油机的排气岐管的各汽缸部分上的岐管氧化催化剂和配置在所述排气岐管的集合部分上的涡轮前氧化催化剂，
所述岐管氧化催化剂在CO净化上优于所述涡轮前氧化催化剂，
所述涡轮前氧化催化剂在HC净化上优于所述岐管氧化催化剂。
5.根据权利要求4所述的柴油机的排气净化装置，其中，所述岐管氧化催化剂是包含具有氧吸藏材料的氧化物和氧化物半导体的催化剂，所述涡轮前氧化催化剂是金属催化剂。
6.根据权利要求5所述的柴油机的排气净化装置，其中，所述具有氧吸藏材料的氧化物是含有Ce的氧化物，所述氧化物半导体是TiO2、ZnO或Y2O3。
7.根据权利要求5或6所述的柴油机的排气净化装置，其中，在所述具有氧吸藏材料的氧化物上担载有贵金属。
8.一种柴油机的排气净化方法，其特征在于，其是使用了权利要求1~7中任一项所述的柴油机的排气净化装置的排气净化方法，其中，
由从所述尿素喷射喷嘴喷雾的尿素水生成的氨NH3与废气中的硫氧化物SOx反应而发生2NH3+SO4→(NH4)2SO4，
该(NH4)2SO4被所述选择性还原型催化剂捕捉并通过热解而生成氨NH3，
该氨NH3被用于NOx的还原反应。
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