CN101568371B - 选择性催化还原车辆废气中的氮氧化物的方法 - Google Patents
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Abstract
本发明描述了在车辆废气中用氨选择性催化还原氮氧化物的方法,其中将任选地与尿素和/或氨和/或铵盐组合的具有40至850g/kg氨形成潜力的胍盐溶液,在由选自二氧化钛、氧化铝、二氧化硅或者它们的混合物的氧化物以及完全或部分经金属交换的水热稳定的沸石构成的催化活性、非氧化活性的涂层的存在下催化分解。借助本发明提出的胍盐可将氮氧化物还原约90%。此外,用该胍盐可在同等的抗冻性(冻点低于-25℃)下,使氨形成潜力从相应于现有技术的0.2kg提高到直至0.4kg氨/升胍盐。最后,本发明所使用的胍盐溶液的腐蚀风险相比含有甲酸铵的溶液也显著降低。
Description
技术领域
本发明涉及借助胍盐溶液选择性催化还原车辆废气中的氮氧化物的方法,其中由相应的胍盐通过蒸发和催化分解产生氨,并将其作为还原剂用于随后的氮氧化物的选择性催化还原。
背景技术
根据现有技术,氨(NH3)在选择性催化还原含氧的车辆废气中的氮氧化物时用作还原剂,其在特殊的SCR-催化剂上游或在整合于消声器中的一组可平行穿流过的SCR-催化剂模块上游被引入到燃烧装置和内燃发动机的排气管中,尤其是车辆的内燃发动机的排气管中,并在SCR-催化剂中引发在废气中所含有的氮氧化物的还原。SCR的意思是氮氧化物(NOx)在氧存在下的选择性催化还原。
为了产生氨,尤其是在车辆中,迄今为止已知有各种液态和固态的氨前体物质,这些物质在下文中详述。
在多用途车辆(Nutzfahrzeugen)中,已有使用水性、低共熔的尿素在水中的溶液(AdBlueTM)作为氨前体物质,该溶液具有32.5重量%的尿素含量,-11℃的冻点和0.2kg/kg的氨形成潜力。为了在低至-30℃,即低至在抗冻质量下柴油燃料的冷滤点(CFPP,运行温度的下限)的温度下运行SCR-装置,需要相对昂贵且易于出运行故障的、用于在冬季寒冷气候下的AdBlue-使用和AdBlue-供料的储罐、管道和阀门的附加加热装置。
对于催化还原NOx所需的氨在尿素热分解中形成。为此涉及到以下反应:尿素在加热下不蒸发,而是根据方程式[1]基本上分解成异氰酸(HNCO)和氨(NH3)。
(H2N2)CO→HNCO+NH3 [1]
异氰酸可容易地聚合成非挥发性物质,如氰尿酸。在这种情况下,可能在阀门上、在喷嘴上和在排气管中产生造成运行故障的沉积物。
使异氰酸(HNCO)在水(H2O)的存在下根据方程式[2]水解生成氨(NH3)和二氧化碳(CO2)。
HNCO+H2O→NH2+CO2 [2]
反应[2]在气相下非常缓慢地进行。相反,该反应在金属氧化物催化剂和/或沸石催化剂上非常快地进行,在由于其WO3-含量而呈强酸性的金属氧化物催化剂,如基于由氧化钒、氧化钨和氧化钛构成的混合氧化物的SCR-催化剂上则较慢一些进行。
在与机动车相关的尿素-SCR-催化体系的已知应用中,通常在将发动机废气的热函充分用于根据反应[1]的尿素分解的情况下利用发动机废气。原则上反应[1]可在SCR-催化剂上游即已进行,而必须将反应[2]催化加速。原则上反应[1]和[2]也可在SCR-催化剂上进行,由此降低其SCR-活性。
对于处于寒冷气候的国家来说有利的是,能够使用更防冻的氨前体物质。通过向尿素在水中的溶液中添加甲酸铵可以使冻点显著降低。由此使附加加热成为多余并在制备费用和供料成本方面获得巨大的节约。26.2%的甲酸铵和20.1%的尿素在水中的溶液具有-30℃的冻点,并以商品名Denoxium-30可商购获得,且可有利地在寒冷的季节中代替AdBlueTM(SAE technical papers 2005-01-1856)。
通过向尿素在水中的溶液中添加甲酸铵,可在35%的甲酸铵和30%的尿素在水中的溶液中,将氨形成潜力从0.2kg/kg提高到0.3kg/kg。由此,使具有氨前体物质填充的车辆的作用距离(Reichweite)提高了三分之一,并且在轿车的情况下一般提高了检查间隔之间的持久填充的可能性。这些措施的缺点是使所述溶液的冻点升高到-11至-15℃的范围内(Denoxium January 2005,www.kemira.com)
在EP 487 886 A1中提出一种通过在160至550℃的温度范围内水解生成氨(NH3)和二氧化碳(CO2)而定量分解尿素在水中的水溶液的方法,其中结果是使不期望的异氰酸及其固态副产物的形成得以避免。在该已知的方法中,首先将尿素溶液借助喷嘴喷射到位于废气之中或废气之外的蒸发器/催化剂上。为了后处理,引导在此产生的气体产物经过水解催化剂,以便定量地形成氨。
由EP 555 746 A1已知一种方法,其中蒸发器由于其构造而如此均匀地分散尿素溶液,使得液滴与分解催化剂的通道壁的接触得以保证。通过均匀的分散,避免了在催化剂上的沉积并减少了过量的还原剂的滑动(Schlupf)。应仅在从160℃起的废气温度下开始(aktivieren)计量添加尿素,因为在低于该温度的情况下会形成不期望的沉积物。
无需特别的预处理,通过将水性溶液喷入到热废气中,通过简单的升华作用从作为氨前体物质的甲酸铵到氨的转化是可能的。不利的是,同时释放出极具腐蚀性的甲酸,并可能在低于250℃的废气温度下在SCR-催化剂的表面上逆向形成甲酸铵。SCR-催化剂的孔体系以受热可逆的方式(temperaturreversibel)被堵塞。
发明内容
因此,本发明的目的在于,发展选择性催化还原车辆废气中氮氧化物的方法,该方法不具有相应于现有技术的缺点,而是其中使技术上简单地产生用于根据SCR-法减少NOx的氨成为可能,且在分解时不形成不期望的副产物。
该目的根据本发明由此得以实现:将具有40至1000g/kg,尤其是至850g/kg氨形成潜力的胍盐溶液,在由选自二氧化钛、氧化铝、二氧化硅的氧化物以及水热稳定的金属沸石或者它们的混合物构成的催化活性、非氧化活性的涂层的存在下催化分解。根据本发明,优选将胍盐溶液任选与尿素和/或氨和/或铵盐组合地使用。
也就是说已经令人惊奇地显示,借助本发明的方法可将约90%的车辆废气中的氮氧化物还原。此外,借助用本发明提出的胍盐可在同等的抗冻性(冻点低于-25℃)下,使氨形成潜力从相应于现有技术的0.2kg提高到直至0.4kg氨/升胍盐。
为了用氨选择性催化还原任选含氧的车辆废气中的氮氧化物,使用本发明的胍盐,其具有40至1000g/kg,尤其是80至850g/kg和特别优选250至600g/kg的氨形成潜力。在此,通式(I)的胍盐被认为是特别优选的,
其中
R=H、NH2、C1-C12烷基,
Xθ=乙酸根、碳酸根、氰酸根、甲酸根、氢氧根、甲醇根(Methylat)和草酸根。
在本发明的范围内毫无问题地可以使用由两种或更多种不同的胍盐组成的混合物。根据本发明优选使用具有5至85重量%,尤其是30至80重量%且优选5至60重量%胍盐含量的胍盐溶液。根据一个优选的实施方案,将本发明所使用的胍盐与尿素和/或氨和/或铵盐组合。胍盐与尿素以及氨或者铵盐的混合比例可在宽范围内变化,但是已经证明特别有利的是:胍盐与尿素的混合物具有5至60重量%的胍盐含量和5至35重量%,尤其是10至30重量%的尿素含量。此外,具有5至60重量%的胍盐含量和5至40重量%,尤其是10至35重量%的氨或者铵盐含量的胍盐与氨或者铵盐的混合物被认为是优选的。
在此,作为铵盐尤其证明通式(II)的化合物是合适的
其中
R=H、NH2、C1-C12烷基,
Xθ=乙酸根、碳酸根、氰酸根、甲酸根、氢氧根、甲醇根和草酸根。
本发明所使用的胍盐以及任选地,由尿素或铵盐组成的其它组分以溶液的形式使用,其中作为溶剂尤其优选使用水和/或C1-C4醇。在此,水溶液和/或醇溶液具有优选5至85重量%,尤其是30至80重量%的固含量。
在此,胍盐或胍盐的任选还与尿素组合的混合物在水中的溶液具有优选0.2至0.5kg氨/升溶液,尤其是0.25至0.35kg氨/升溶液的氨形成潜力。
作为本发明必要的是,使胍盐以及任选的其它组分在优选150至350℃的温度范围内经受催化分解而生成氨,其中作为其它的组分形成二氧化碳以及可能的一氧化碳。该使胍盐分解生成氨的过程优选在由选自二氧化钛、氧化铝和二氧化硅及其混合物的氧化物,或/和完全或部分经金属交换的水热稳定的沸石,尤其是ZSM 5-型或BEA-型铁沸石构成的催化活性、非氧化活性的涂层的存在下进行。在此,作为金属尤其考虑副族元素并优选铁或铜。相应的Fe-沸石-材料按照公知的方法例如固态交换法,例如用FeCl2制得,随后以浆料的形式施加到基材上(例如堇青石-整料),将其干燥或者在较高温度(约500℃)下煅烧。
优选将金属氧化物如氧化钛、氧化铝以及二氧化硅以及它们的混合物施加到金属载体材料例如导热-合金(尤其是铬-铝-钢)上。
优选胍盐或者其余组分还可催化分解生成氨和二氧化碳和可能的一氧化碳,其中除了具有非氧化活性涂层的催化剂外,还使用具有由选自二氧化钛、氧化铝和二氧化硅及其混合物的氧化物,或/和完全或部分经金属交换的水热稳定的沸石构成的氧化活性涂层的催化剂,其中将该涂层用作为氧化活性组分的金和/或钯浸渍。具有作为活性组分的钯和/或金的相应催化剂优选具有0.001至2重量%的贵金属含量。借助这种氧化催化剂可在胍盐分解时在氨产生时就已经避免不期望地形成作为副产物的一氧化碳。
优选为了催化分解胍盐以及可能的其它的组分,使用含有钯或/和金作为活性组分的,具有0.001至2重量%,尤其是0.01至1重量%贵金属含量的催化涂层。
在本发明的范围内可能的是,使用由两部分组成的催化剂,其中第一部分含有非氧化活性涂层,且第二部分含有氧化活性涂层。优选催化剂的5至90体积%由非氧化活性涂层组成,且催化剂的10至95体积%由氧化活性涂层组成。另选地也可在两种相继设置的催化剂的存在下进行所述催化分解,其中第一催化剂含有非氧化活性涂层,且第二催化剂含有氧化活性涂层。
本发明所使用的胍盐以及任选地其它组分催化分解生成氨的过程可在废气内在车辆废气的主流、支流或侧流中进行,或在废气外在自动且外加热的车辆废气的配置设备中进行。
借助本发明提出的胍盐可将在车辆废气中的氮氧化物还原约90%。最后,本发明所使用的胍盐溶液的腐蚀风险相比含有甲酸铵的溶液显著降低。
下文的实施例将更详尽地阐释本发明。
具体实施方式
实施例1
相应于根据图1的描述在自动氨发生器中使用40重量%的甲酸胍
水溶液,(GF)(Fp<-20℃)作为氨前体物质
轿车发动机1产生200Nm3/h的废气流,将该废气流通过中间管2经铂氧化催化剂3和颗粒过滤器4引到废气中间管6中。在中间管6中的用FTIR-气体分析仪5测得的废气组成:150ppm的氧化氮(NO);150ppm的二氧化氮(NO2);7%的二氧化碳(CO2);8%的水蒸气,10ppm的一氧化碳(CO)。
在储罐7中有GF-溶液8,其借助计量泵9经输送管10和喷嘴12喷入到反应器11中。反应器11由加热到250℃的、垂直设置的内径51mm的且由奥氏体不锈钢制成的管构成并具有加热套15。在反应器11中有催化剂13和14。所述催化剂为用Südchemie AG公司的二氧化钛,D-Heufeld涂覆的金属载体,直径50mm,长度200mm;该金属载体的制造商:Emitec GmbH,D-53797Lohmar。催化剂13基于粗格栅的载体型MX/PE 40cpsi,100mm长。在下游方向,催化剂14由细格栅的载体型MX/PE 200cpsi构成,100mm长。由喷嘴12借助压力计量泵9用GF-溶液8喷洒粗格栅的催化剂13的正面。喷嘴12在反应器11中轴向地且在粗格栅的催化剂13的上游设置。在催化剂13上将GF-溶液8的水分蒸发并在催化剂13和14上将GF以热水解的方式(thermohydrolytisch)分解,使得避免形成中间产物尿素和异氰酸(HNCO)。
将产生的由氨、二氧化碳、一氧化碳和水蒸气组成的混合物在300℃下经导管16引入到在SCR-催化剂18上游的废气中间管6中,引入到用催化剂3和过滤器4预处理过的轿车发动机1的废气(200Nm3/h)中。用压力计量泵9如此调整GF-溶液8的计量添加,使得用FTIR-气体分析仪17可测得270ppm的氨浓度。在此,由于GF-溶液8的甲酸盐成分的分解,CO浓度同时升高90至100ppm。由GF-溶液8的蒸发和分解造成的CO2含量和水蒸气含量的升高如期待的那样低并几乎不能测量到。GF的催化水解是完全的,因为用气体分析仪17不能探测到异氰酸(HNCO),且无法检测到尿素及其分解产物的沉积。
在SCR-催化剂18的下游,用FTIR-气体分析仪19测得NO和NO2的浓度减少了90%到达30ppm。在此,氨(NH3)与NO和NO2进行完全反应生成氮气(N2)。在SCR-催化剂19下游的氨浓度<2ppm。
FTIR-气体分析仪5、17和19使同时进行组分NO、NO2、CO、CO2、H2O、氨(NH3)和异氰酸(HNCO)的废气分析成为可能。
实施例2
类似于实施例1操作,但是二氧化钛催化剂14被氧化钯-二氧化钛催化剂代替,其中将二氧化钛用Pd(NO3)2水溶液浸渍,使得在干燥和煅烧(5小时在500℃下)后产生含有1重量%PdO(=约0.9重量%Pd)的催化剂,且其导致一氧化碳的部分氧化。在FTIR-气体分析仪17上可测得CO-浓度未升高。
实施例3
类似于实施例1操作,但是代替40重量%的甲酸胍溶液使用15重量%的二碳酸胍溶液。同样将反应器11在250℃下加热,催化剂13和14与实施例1的那些相同。
在FTIR-气体分析仪17上未探测到副产物(<1ppm),约40ppm的CO2升高与预期相符;在气体分析仪19中可检测得NO和NO2浓度减少了约92%到达25ppm。
实施例4
类似于实施例1操作,但是催化剂13和14由Al2O3构成,且反应器11在350℃温度下运行。
在气体分析仪17中作为副产物仅测得CO(80ppm)和HCN(<10ppm);在SCR-催化剂下游,在气体分析仪19上测得NO2和NO还原了85%到达45ppm而且无HCN。
Claims (19)
2.根据权利要求1的方法,其特征在于,使用由两种或更多种不同的胍盐组成的混合物。
3.根据权利要求1的方法,其特征在于,所述胍盐具有250至600g/kg的氨形成潜力。
4.根据权利要求1的方法,其特征在于,所述胍盐和尿素的混合物具有5至60重量%的胍盐含量和5至35重量%的尿素含量。
5.根据权利要求1的方法,其特征在于,所述胍盐和氨或铵盐的混合物具有5至60重量%的胍盐含量和5至40重量%的氨或铵盐含量。
7.根据权利要求1的方法,其特征在于,在由水和/或C1-C4醇组成的溶剂中使用所述胍盐以及任选地其它组分。
8.根据权利要求1的方法,其特征在于,所述水溶液和/或醇溶液具有5至85重量%的固含量。
9.根据权利要求1的方法,其特征在于,胍盐或胍盐的任选还与尿素混合的混合物在水中的溶液具有0.2至0.5kg氨/升溶液的氨形成潜力。
10.根据权利要求1的方法,其特征在于,胍盐以及任选地其它组分在废气内在车辆废气的主流、支流或侧流中,或在废气外在自动且外加热的配置设备中通过催化分解转化生成氨。
11.根据权利要求1的方法,其特征在于,为了使胍盐以及任选地其它组分催化分解生成氨、二氧化碳和任选的一氧化碳,除了具有非氧化活性的涂层的催化剂外还使用具有氧化活性的涂层的催化剂。
12.根据权利要求11的方法,其特征在于,使用具有由选自二氧化钛、氧化铝和二氧化硅的氧化物、水热稳定的金属沸石及它们的混合物构成的氧化活性涂层的催化剂,且该涂层经用金和/或钯浸渍。
13.根据权利要求11的方法,其特征在于,使用具有氧化活性涂层的催化剂,该涂层由作为活性组分的钯和/或金构成并具有0.001至2重量%的贵金属含量。
14.根据权利要求1的方法,其特征在于,为了使胍盐催化分解,使用由两部分组成的催化剂,其中第一部分含有非氧化活性涂层,且第二部分含有氧化活性涂层。
15.根据权利要求14的方法,其特征在于,催化剂的5至90体积%由非氧化活性涂层组成,且催化剂的10至95体积%由氧化活性涂层组成。
16.根据权利要求1的方法,其特征在于,在两种相继设置的催化剂的存在下进行所述胍盐的催化分解,其中第一催化剂由非氧化活性涂层构成,且第二催化剂由氧化活性涂层构成。
17.根据权利要求1的方法,其特征在于,在150至350℃下进行胍盐溶液的催化分解。
18.根据权利要求8的方法,其特征在于,所述水溶液和/或醇溶液具有30至80重量%的固含量。
19.根据权利要求9的方法,其特征在于,胍盐或胍盐的任选还与尿素混合的混合物在水中的溶液具有0.25至0.35kg氨/升溶液的氨形成潜力。
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Families Citing this family (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012104205A1 (en) | 2011-02-04 | 2012-08-09 | Paul Scherrer Institut | Ammonia generator converting liquid ammonia precursor solutions to gaseous ammonia for denox-applications using selective catalytic reduction of nitrogen oxides |
CN102278177B (zh) * | 2011-04-27 | 2014-05-07 | 汪家琳 | 内燃机尾气高效利用装置与方法 |
US8940543B2 (en) * | 2011-05-11 | 2015-01-27 | Fuel Tech, Inc. | Diagnostic tool and process for assessing thermal urea gasification performance |
CN103748039B (zh) * | 2011-07-01 | 2016-07-06 | 澳泽化学股份公司 | 用于还原废气中的氮氧化物产生氨的氨气发生器 |
DE102011106237A1 (de) | 2011-07-01 | 2013-01-03 | Alzchem Ag | Ammoniakgasgenerator sowie Verfahren zur Erzeugung von Ammoniak zur Reduzierung von Stickoxiden in Abgasen |
DE102011106233A1 (de) | 2011-07-01 | 2013-01-03 | Alzchem Ag | Verfahren zur Erzeugung von Ammoniak aus einer Ammoniakvorläufersubstanz zur Reduzierung von Stickoxiden in Abgasen |
DE102011106243A1 (de) | 2011-07-01 | 2013-01-03 | Alzchem Ag | Ammoniakgasgenerator zur Erzeugung von Ammoniak zur Reduzierung von Stickoxiden in Abgasen |
JP5985492B2 (ja) * | 2011-10-12 | 2016-09-06 | 株式会社堀場製作所 | ガス分析装置 |
DE102012025113A1 (de) | 2012-12-21 | 2014-06-26 | Alzchem Ag | Ammoniakgasgenerator, Verfahren zur Herstellung von Ammoniak sowie Verwendung derselben zur Reduktion von Stickoxiden in Abgasen |
DE102012025112A1 (de) | 2012-12-21 | 2014-06-26 | Alzchem Ag | Ammoniakgasgenerator sowie Verwendung desselben zur Reduktion von Stickoxiden in Abgasen |
EP2935105B1 (de) | 2012-12-21 | 2017-07-26 | AlzChem AG | Ammoniakgasgenerator sowie verwendung desselben zur reduktion von stickoxiden in abgasen |
US8997463B2 (en) * | 2013-04-17 | 2015-04-07 | Continental Automotive Systems, Inc. | Reductant delivery unit for automotive selective catalytic reduction with reducing agent heating |
KR101436936B1 (ko) | 2013-06-05 | 2014-09-03 | 한국기계연구원 | 고체 암모늄염 반응기, 그 제어방법 및 고체 암모늄염과 선택적 환원촉매를 이용한 질소산화물 정화시스템 |
US9689293B2 (en) * | 2014-08-19 | 2017-06-27 | Continental Automotive Systems, Inc. | Reductant delivery unit for automotive selective catalytic reduction with optimized fluid heating |
AT517862A1 (de) * | 2015-11-09 | 2017-05-15 | M A L Umwelttechnik - Gmbh | Verfahren zur selektiven Reduktion von Stickoxiden in heißen Gasen |
JP6705334B2 (ja) * | 2016-08-10 | 2020-06-03 | いすゞ自動車株式会社 | 内燃機関の尿素由来堆積物の除去装置及び除去方法 |
CN109641743A (zh) * | 2016-08-30 | 2019-04-16 | 全耐塑料高级创新研究公司 | 用于在车辆上增大水溶液的尿素浓度的系统和方法 |
WO2018128902A1 (en) * | 2017-01-05 | 2018-07-12 | Fuel Tech, Inc. | Controlled, compact, on-demand ammonia gas generation process and apparatus |
CN108468583B (zh) * | 2018-03-24 | 2020-03-27 | 张鑫印 | 一种汽车尾气处理用除氮器 |
US10767529B2 (en) | 2018-11-08 | 2020-09-08 | Faurecia Emissions Control Technologies, Usa, Llc | Automotive exhaust aftertreatment system having onboard ammonia reactor with heated doser |
US10876454B2 (en) | 2018-11-08 | 2020-12-29 | Faurecia Emissions Control Technologies, Usa, Llc | Automotive exhaust aftertreatment system with multi-reductant injection and doser controls |
US10683787B2 (en) | 2018-11-08 | 2020-06-16 | Faurecia Emissions Control Technologies, Usa, Llc | Automotive exhaust aftertreatment system having onboard ammonia reactor with hybrid heating |
US11193413B2 (en) | 2019-12-12 | 2021-12-07 | Faurecia Emissions Control Technologies, Usa, Llc | Exhaust aftertreatment system with virtual temperature determination and control |
US11319853B2 (en) | 2020-03-31 | 2022-05-03 | Faurecia Emissions Control Technologies, Usa, Llc | Automotive exhaust aftertreatment system with doser |
US11022014B1 (en) | 2020-04-28 | 2021-06-01 | Faurecia Emissions Control Technologies, Usa, Llc | Exhaust aftertreatment system with heated flash-boiling doser |
US11092054B1 (en) | 2020-04-29 | 2021-08-17 | Faurecia Emissions Control Technologies, Usa, Llc | Flash-boiling doser with thermal transfer helix |
US11511239B2 (en) | 2020-04-29 | 2022-11-29 | Faurecia Emissions Control Technologies, Usa, Llc | Heated flash-boiling doser with integrated helix |
US11384667B2 (en) | 2020-05-29 | 2022-07-12 | Faurecia Emissions Control Technologies, Usa, Llc | Exhaust aftertreatment system with heated dosing control |
CN113929903B (zh) * | 2020-06-29 | 2022-10-28 | 中国科学技术大学 | 质子化氨基引发npca聚合制备端基高保真度聚多肽的方法 |
US11225894B1 (en) | 2020-06-30 | 2022-01-18 | Faurecia Emissions Control Technologies, Usa, Llc | Exhaust aftertreatment system with thermally controlled reagent doser |
CN112121812B (zh) * | 2020-09-16 | 2022-04-22 | 万华化学集团股份有限公司 | 一种制备丙二胺的催化剂及其制备方法,以及制备丙二胺的方法 |
CN112090277A (zh) * | 2020-09-30 | 2020-12-18 | 河南弘康环保科技有限公司 | 一种含纳米级催化剂的车用尿素的生产工艺 |
JP2022067434A (ja) * | 2020-10-20 | 2022-05-06 | 株式会社三井E&Sマシナリー | 高融点配管閉塞物質の生成抑制装置及び方法 |
CN114738084A (zh) * | 2021-01-07 | 2022-07-12 | 长城汽车股份有限公司 | 汽车后处理系统及汽车 |
FR3123382A1 (fr) * | 2021-05-31 | 2022-12-02 | Faurecia Systemes D'echappement | Dispositif et méthode pour injecter un fluide dans un conduit d'échappement , ligne d'échappement et véhicule associés |
CN117599604A (zh) * | 2023-10-24 | 2024-02-27 | 上海全熙环保科技股份有限公司 | 一种碱炉专用脱硝剂复合材料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4221451A1 (de) * | 1992-06-30 | 1994-01-05 | Metallgesellschaft Ag | Verfahren und Vorrichtung zur katalysierten Entstickung der Abgase von Dieselmotoren und Mager-Ottomotoren |
US6266955B1 (en) * | 1999-08-20 | 2001-07-31 | Caterpillar Inc. | Diagnostic system for an emissions control on an engine |
CN1419471A (zh) * | 2000-12-01 | 2003-05-21 | 燃料技术公司 | 通过支流尿素分解实现的NOx的选择催化还原 |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1987002023A1 (en) | 1985-10-04 | 1987-04-09 | Fuel Tech, Inc. | Reduction of nitrogen- and carbon-based pollutants |
FR2602507B1 (fr) * | 1986-08-08 | 1989-06-09 | Sanofi Pharma | Procede de preparation de diamino-2,4 benzyl-5 pyrimidines |
JPS6445A (en) * | 1987-06-23 | 1989-01-05 | Mitsui Toatsu Chem Inc | Production of 2-chloropropionaldehyde |
AT390208B (de) | 1988-05-09 | 1990-04-10 | Waagner Biro Ag | Verfahren zur entfernung von stickoxiden |
DE3815807A1 (de) | 1988-05-09 | 1989-11-23 | Sueddeutsche Kalkstickstoff | Verfahren zur selektiven nichtkatalytischen entfernung von stickoxiden aus abgasen |
US6051040A (en) * | 1988-12-28 | 2000-04-18 | Clean Diesel Technologies, Inc. | Method for reducing emissions of NOx and particulates from a diesel engine |
US4961917A (en) * | 1989-04-20 | 1990-10-09 | Engelhard Corporation | Method for reduction of nitrogen oxides with ammonia using promoted zeolite catalysts |
US5120695A (en) * | 1989-07-28 | 1992-06-09 | Degusaa Aktiengesellschaft (Degussa Ag) | Catalyst for purifying exhaust gases from internal combustion engines and gas turbines operated at above the stoichiometric ratio |
DE4315278A1 (de) * | 1993-05-07 | 1994-11-10 | Siemens Ag | Verfahren und Einrichtung zur Dosierung eines Reduktionsmittels in ein stickoxidhaltiges Abgas |
JPH09500164A (ja) * | 1993-07-12 | 1997-01-07 | プラチナム プラス インコーポレーテッド | ディーゼルエンジンからのNOx及び微粒子の排出を減少させる方法 |
WO1995004211A1 (en) | 1993-07-29 | 1995-02-09 | Platinum Plus, Inc. | METHOD FOR REDUCING NOx EMISSIONS FROM DIESEL ENGINES |
DE4417238C2 (de) * | 1994-05-17 | 2003-03-27 | Siemens Ag | Einrichtung zur Minderung der Stickoxide im Abgas eines mit Luftüberschuß betriebenen Verbrennungsmotors |
JP3604042B2 (ja) * | 1994-09-22 | 2004-12-22 | 株式会社リコー | 熱現像型ジアゾ複写材料 |
US5809775A (en) * | 1997-04-02 | 1998-09-22 | Clean Diesel Technologies, Inc. | Reducing NOx emissions from an engine by selective catalytic reduction utilizing solid reagents |
US6399034B1 (en) * | 1997-05-14 | 2002-06-04 | Hjs Fahrzeugtechnik Gmbh & Co. | Process for reducing nitrogen oxides on SCR catalyst |
GB9808876D0 (en) * | 1998-04-28 | 1998-06-24 | Johnson Matthey Plc | Combatting air pollution |
US6606856B1 (en) * | 2000-03-03 | 2003-08-19 | The Lubrizol Corporation | Process for reducing pollutants from the exhaust of a diesel engine |
US6415602B1 (en) * | 2000-10-16 | 2002-07-09 | Engelhard Corporation | Control system for mobile NOx SCR applications |
DE10103771A1 (de) * | 2001-01-27 | 2002-08-14 | Omg Ag & Co Kg | Verfahren zur Wiederherstellung der katalytischen Aktivität eines Katalysators, welcher im Abgastrakt eines Dieselmotors angeordnet ist und wenigstens eine Oxidationsfunktion aufweist |
DE10206028A1 (de) * | 2002-02-14 | 2003-08-28 | Man Nutzfahrzeuge Ag | Verfahren und Vorrichtung zur Erzeugung von Ammoniak |
US7229597B2 (en) * | 2003-08-05 | 2007-06-12 | Basfd Catalysts Llc | Catalyzed SCR filter and emission treatment system |
US7807110B2 (en) * | 2004-03-12 | 2010-10-05 | Cormetech Inc. | Catalyst systems |
NZ551021A (en) * | 2004-05-05 | 2009-11-27 | Vechten James Alden Van | Guanidine based composition and system for generating energy |
US7481983B2 (en) * | 2004-08-23 | 2009-01-27 | Basf Catalysts Llc | Zone coated catalyst to simultaneously reduce NOx and unreacted ammonia |
DE102004043632A1 (de) * | 2004-09-07 | 2006-03-09 | Basf Ag | Verfahren zur Herstellung heterocyclischer quartärer Ammonium- und/oder Guanidinium-Verbindungen |
JP2006110485A (ja) * | 2004-10-15 | 2006-04-27 | Johnson Matthey Japan Inc | 排気ガス触媒およびそれを用いた排気ガス処理装置 |
JP4599989B2 (ja) * | 2004-10-28 | 2010-12-15 | 日立造船株式会社 | アンモニアの製造方法および脱硝方法 |
EP2069049A2 (en) * | 2006-08-22 | 2009-06-17 | Babcock Power Inc. | Thermal decomposition of urea in a side stream of combustion flue gas using a regenerative heat exchanger |
-
2007
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4221451A1 (de) * | 1992-06-30 | 1994-01-05 | Metallgesellschaft Ag | Verfahren und Vorrichtung zur katalysierten Entstickung der Abgase von Dieselmotoren und Mager-Ottomotoren |
US6266955B1 (en) * | 1999-08-20 | 2001-07-31 | Caterpillar Inc. | Diagnostic system for an emissions control on an engine |
CN1419471A (zh) * | 2000-12-01 | 2003-05-21 | 燃料技术公司 | 通过支流尿素分解实现的NOx的选择催化还原 |
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