CN105163852A - 复合型选择性还原催化剂 - Google Patents
复合型选择性还原催化剂 Download PDFInfo
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Abstract
本发明涉及一种在上层或下层设置有V2O5/TiO2层，且在下层或上层设置有含金属的沸石层的双层结构复合SCR催化剂或者将V2O5/TiO2及含金属的沸石混合形成的单层结构复合SCR催化剂。具体讲，本发明涉及一种能够通过改善氨的吸藏力而在柴油发动机加减速区间有效地将NOx转化为无害成分的SCR催化剂，及利用该催化剂改善柴油发动机尾气净化能力，特别是在低温条件下改善氮氧化合物净化能力的尾气排放装置。
Description
技术领域
本发明涉及一种复合型选择性还原催化剂。具体讲，就是涉及一种能够通过改善氨的吸藏力从而在发动机加减速区间有效地将NOx转化为无害成分的SCR催化剂及利用该催化剂改善柴油发动机尾气净化能力，特别是在不能注入还原剂的低温条件下改善氮氧化合物净化能力的尾气排放装置。
背景技术
柴油发动机因其固有的高热效率(即，优秀的燃料经济性)及低速状态下的高扭矩(torque)使其作为运输工具(vehicle)的动力装置具有优秀的实用性，柴油发动机在燃料稀薄的条件下在较高的A/F(空气对燃料)下进行驱动。基于这一原因，对于柴油发动机来说，虽然碳氢化合物及一氧化碳的转化率较高，但是柴油尾气中氮氧化合物(NOx)及颗粒状物质的排放比例比较高。氮氧化合物(NOx)及颗粒状物质属于很难将其转化(conversion)为无害成分的柴油尾气成分，由于其关系到环保问题，近期也在逐渐提高排放标准。特别是，为了清除氮氧化合物，研发人员正在探索多种技术方案。比较具有代表性的就是选择性催化还原方式(SCR，SelectiveCatalyticReduction)或氮氧化合物吸附(LeanNOxTrap，LNT)催化剂系统。但是，本发明涉及SCR技术，具体一点就是涉及SCR催化剂。
图1是概略显示SCR系统的示意图。SCR使用作为还原剂的氨或尿素通过下述反应机理将NOx还原为N2和H2O。
通常情况下，作为适用于SCR系统中的催化剂都是V2O5/TiO2催化剂或含金属的沸石系统的催化剂。特别是，V2O5/TiO2催化剂的工作温度区间为250-450℃，尤其当只存在NO时，无法确保其在低温条件下的性能。但是，如果尾气中NO2成分较多，就能提高其性能，并且扩大低温工作区间。因此，采用在SCR系统上游(upstream)设置氧化催化剂将NO氧化为NO2以提高NO2浓度的方法。相反，如果NO2/NO之比过高，反而会使其性能降低，所以最好保持NO2/NO＝1的标准。因此，通常SCR系统依次由以下几个部分构成：将由发动机产生的NOx中的NO成分转化为NO2的氧化催化剂、微粒过滤器、还原剂注入部及SCR催化剂(参照图2)。
发明内容
技术问题
虽然V2O5/TiO2催化剂被柴油车辆燃料中所含的硫引发中毒的特性要优于沸石系列催化剂从而适用于柴油发动机。但却有着由于还原剂即氨的贮存性较低，从而在不可能注入还原剂的低温范围内其活性就会降低的缺点。具体讲，柴油发动机车辆频繁的加速及减速(transient)运转会导致产生多种发动机负荷条件，尾气温度有时会降低到不能使还原剂前驱体即尿素喷射的200℃以下。在这种低温条件下，V2O5/TiO2催化剂不能工作，因此无法将NOx除去。因此，在尿素不喷射的情况下，就需要能够通过吸藏在催化剂内部的NH3保持NOx持续还原的补充结构。即，需要增强V2O5/TiO2催化剂结构的NH3吸藏能力。
技术方案
本发明的目的在于，提供一种低温活性及NOx转化率都优秀的SCR催化剂。本发明的另一个目的在于，提供一种采用低温活性及NOx转化率都优秀的SCR催化剂的柴油发动机尾气排放装置。
为了实现上述目的，本发明的选择性还原催化剂具有以下结构：在上层设置V2O5/TiO2层，在下层设置含金属的沸石层的双层结构；或者在上层设置含金属的沸石层，在下层设置V2O5/TiO2层的双层结构；或者V2O5/TiO2及含金属的沸石混合的混合结构。除此之外，本发明还具有以下其它特征，但并非仅限定于此。沸石可以是β沸石、ZSM5、沸石Y、βZeolite、丝光沸石、CHA，含金属的沸石可以是含Cu或Fe的沸石。
有益效果
本发明的复合型SCR催化剂与V2O5/TiO2单一催化剂相比其活性更强。特别是，不仅其低温活性得以改善，同时其耐硫性也得以增强。
附图说明
图1是普通SCR系统的概略图；
图2是概略显示普通柴油发动机排气系统的示意图；
图3是本发明一个实施例即双层选择性还原催化剂结构示意图；
图4是针对比较催化剂(V2O5/TiO2单一)及本发明的双层催化剂(V2O5/TiO2//含金属的沸石)在不同温度条件下对NOx转化率进行测定的曲线图；
图5是测定出氨吸附量随V2O5/TiO2催化剂及含Fe沸石(Fe-Zeolite)催化剂的含量的曲线图；
图6是针对比较催化剂(V2O5/TiO2单一)及本发明的双层催化剂(V2O5/TiO2//Fe-Zeolite)对NOx转化率进行测定的曲线图；
图7是针对比较催化剂(V2O5/TiO2单一)及本发明的双层催化剂(V2O5/TiO2//Fe-Zeolite)在加减速区间的NOx转化率进行测定的曲线图；
图8是针对被硫成分引发中毒的比较催化剂(V2O5/TiO2单一)及本发明的催化剂(V2O5/TiO2//Fe-Zeolite)对NOx转化率进行测定的曲线图。
具体实施方式
本发明复合型选择性还原催化剂的一个实施例，即具有双层结构的选择性还原催化剂概略结构如图3所示。本发明的催化剂(以下简称“复合SCR催化剂”或“混合体(Hybrid)”)在上层设置有V2O5/TiO2层，在下层设置有含金属的沸石层。在所述下层可以设置含Cu或Fe的沸石。为了改善各成分间的附着力，设置在上层或下层的SCR催化剂中还可以加入二氧化硅、氧化锆或氧化铝成分。
本发明的复合型SCR催化剂被涂覆于堇青石等陶瓷型或不锈钢等耐火性金属型载体(基层)上，从而构成SCR催化剂模块。典型的载体采用带有正面及背面并具备将正面及背面进行线性连接的多个微细通道的“溢流道(flow-through)”型载体。所述SCR催化剂模块包括喷射还原剂的设置在前端的公知喷射装置。例如，这种喷射装置包括对作为还原剂的尿素或氨进行喷雾的泵及喷嘴。
适用于本发明SCR催化剂模块的复合SCR催化剂制造方法如下。首先，制造出含有可商业化获取的Fe成分的沸石(Fe-Zeolite)料浆后，将其涂覆于堇青石或金属型载体上经干燥、焙烧后，再制造出含有同样可商业化获取的V2O5/TiO2成分的料浆，将其涂覆于所述沸石层上部，经干燥、焙烧，制造出双层结构的复合SCR催化剂。优选地，V2O5含量为2.5～5.0重量％，TiO2含量为80-200g/L，Fe-Zeolite含量为30-100g/L。可以采用相同的方法在下层适用含Cu的沸石(Cu-Zeolite)层。下面，将对该领域的技术人员熟悉的制造方法进行简单说明。通过普通方法制造出含有SCR还原催化剂成分的沸石或二氧化钛料浆，再通过分散或研磨加工使大约90％的微粒大小达到1-12um，将料浆涂覆到堇青石蜂窝内部，在110℃～140℃的条件下干燥约10分钟后，再在450℃～500℃的条件下焙烧约40分钟，从而制造出复合SCR催化剂。
下面，将对本发明的复合SCR催化剂(上层3.0％V2O5/TiO2(140g/L)及下层Fe-Zeolite(70g/L)的双层)及比较催化剂(3.0％V2O5/TiO2(140g/L)单一)的催化活性进行比较。
图4是针对各种不同的催化剂按照空间速度60K/hr注入NH3/NOx比例1的还原剂/NOx时，对随温度变化的NOx转化率进行测定的示意图。从图中可以看出，虽然本发明的复合型催化剂及比较催化剂在V2O5/TiO2工作温度条件下显示出相似的转化率，但是在V2O5/TiO2催化剂不能工作的低温即低于250℃的条件下，复合型催化剂的NOx转化率显著提高。因此，本发明将沸石系列的SCR催化剂设置在下层结构中，由此大大增强V2O5/TiO2催化剂结构的NH3吸藏能力，从而可以改善低温活性。
为了通过实验确认提高了氨吸藏力，按照下述成分比例制造出比较及复合SCR催化剂后，以NH3流动率250ml/分通过实验测定吸藏能力。
【表1】
结果如图5所示，可以看出与比较催化剂相比，本发明的混合体SCR催化剂的氨吸藏能力更加优秀。特别是，确认了这种吸藏力的改善能够通过更多的沸石成分来实现。
另外，还可以对V2O5/TiO2催化剂及含Fe沸石(Fe-Zeolite)催化剂的多种排列结构进行设想。因此，制造出以下3种结构后对NOx转化率进行了测定。即，1)将两种成分均匀混合；2)将Fe-Zeolite叠加在V2O5/TiO2成分上部形成的双层结构；3)将Fe-BEA叠加在V2O5/TiO2成分下部形成的双层结构。下表针对上述三种情况分别列出了在230℃及250℃条件下的转化率。
【表2】
上述结果表明，上层设置有钒催化剂成分且下层叠加有沸石成分的复合型催化剂与单一催化剂相比，其NOx转化率更加优秀。特别是，上层设置有钒催化剂成分且下层叠加有沸石成分的结构是一种最佳的结构。
图6是针对比较催化剂(V2O5/TiO2单一)及双层催化剂(V2O5/TiO2//Fe-Zeolite，混合体4)在250℃条件下对行驶中的NOx转化率进行测定的曲线图。从图中可以看出，双层催化剂的氨吸藏量得以改善。因此，与比较催化剂相比，自行驶开始其NOx转化率就增加。特别是，在NH3喷射停止的情况下，NOx清除率尤其明显。
图7是针对比较催化剂(V2O5/TiO2单一)及本发明的双层催化剂(V2O5/TiO2//Fe-Zeolite)在加减速区间的NOx转化率进行测定的曲线图。如图所示，在加减速区间(没有氨喷射的区间)，本发明复合型SCR催化剂的NOx转化率与比较及单一SCR催化剂相比得以显著改善。
本申请人不仅确认了本发明的复合SCR催化剂通过增加氨吸藏力改善了NOx转化率，更令人吃惊的是，还增强了耐硫性。图8是针对被硫成分引发中毒的比较催化剂(V2O5/TiO2)及本发明的双层催化剂(V2O5/TiO2//Fe-Zeolite)对NOx转化率进行测定的曲线图。将两种催化剂暴露在硫成分4g/L的环境中，然后对NOx转化率进行测定。出人意料的是，具有在上层设置V2O5/TiO2层且在下层设置含金属的沸石层的双层结构的选择性还原催化剂与比较催化剂(V2O5/TiO2)相比，对硫的耐毒性显著提高。
Claims (5)
1.一种复合SCR催化剂，其特征在于：
其具有双层结构，在上层设置有V2O5/TiO2层，在下层设置有含金属的沸石层。
2.一种复合SCR催化剂，其特征在于：
其具有双层结构，在上层设置有含金属的沸石层，在下层设置有V2O5/TiO2层。
3.一种复合SCR催化剂，其特征在于：
其具有单层结构，且由V2O5/TiO2及含金属的沸石混合形成。
4.根据权利要求1至3中任一权利要求所述的复合SCR催化剂，其特征在于：
含金属的沸石为含Cu或Fe的沸石。
5.根据权利要求1至3中任一权利要求所述的复合SCR催化剂，其特征在于：
为了改善催化剂成分的附着力，进一步包含二氧化硅、氧化锆或氧化铝成分。
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| PCT/KR2014/003826 WO2014178636A1 (ko) | 2013-05-02 | 2014-04-30 | 복합형 선택적 환원 촉매 |
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| WO2017030249A1 (ko) * | 2015-08-18 | 2017-02-23 | 한국과학기술원 | 철-에틸렌디아민사아세트산을 이용한 질소화합물 포집용 전기분해장치 |
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| KR20140131401A (ko) | 2014-11-13 |
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