CN113275009A - 一种燃气机尾气全污染物净化催化剂及其制备方法 - Google Patents
一种燃气机尾气全污染物净化催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种燃气机尾气全污染物净化催化剂及其制备方法，属于燃气机尾气净化催化剂技术领域。包括载体和活性组分，载体为锆基多孔材料，活性组分为贵金属的改性前驱体，载体与贵金属的质量比为1:0.001～0.03，其制备方法为：先将贵金属的原液分散于去离子水中，得到浓度为0.05%～12%的贵金属稀释溶液，经水热处理、离心、再分散后制得贵金属的改性前驱体；再将载体材料分散于去离子水中，加入贵金属改性前驱体，经搅拌、调pH、干燥、焙烧、制浆、涂覆制得所述催化剂。本发明载体采用锆基材料，由于具有更多的氧空位，可支撑贵金属高效、全面净化HC、CO、NOx和NH3。
Description
技术领域
本发明属于燃气机尾气净化催化剂技术领域，具体涉及一种燃气机尾气全污染物净化催化剂及其制备方法。
背景技术
随着排放标准的趋严，燃气机发动机的燃烧方式从稀燃升级到理论燃烧，相应地，后处理催化剂从氧化型催化剂变更为三效催化剂TWC。TWC在当量燃烧条件下，能将尾气中的HC(包括CH4和NMHC)、CO、和NOx转化为N2、CO2和H2O，但同时会产生副产物NH3。而NH3也是国六新排放法规的限值排放的污染物。
为使燃气机尾气排放满足国六法规，必须开发一种后处理催化剂，可同时将尾气中的HC、CO、NOx、和NH3净化到国六限值内。
发明内容
本发明所要解决的技术问题是：提供一种燃气机尾气全污染物净化催化剂及其制备方法，载体采用锆基材料，由于具有更多的氧空位，可支撑贵金属高效、全面净化HC、CO、NOx和NH3。
本发明所采取的技术方案是：
一种燃气机尾气全污染物净化催化剂及其制备方法，包括载体和活性组分，所述载体为锆基多孔材料，所述活性组分为贵金属的改性前驱体，所述载体与贵金属的质量比为1:0.001～0.03。
进一步的，所述贵金属为Pd、Rh、Pt、Ru、Os、Ir、Au、Ag中的至少一种，所述锆基多孔材料为纯锆、锆基稀土改性、锆基铝改性、锆基硅改性、锆基钒钛钨改性中的中的至少一种。
进一步的，所述贵金属为Pd、Rh、Pt，所述锆基多孔材料为锆基稀土改性、锆基铝改性多孔材料。
进一步的，所述锆基稀土改性、锆基铝改性多孔材料中氧化锆的质量分数为70%～100%。
进一步的，所述氧化锆的质量分数为90%～95%。
进一步的，所述贵金属的改性前驱体为金属氯化物、金属硝酸盐、金属氢氧化物、金属水合氧化物、金属有机分散液中的至少一种。
一种燃气机尾气全污染物净化催化剂的制备方法，包括如下步骤：
步骤一、将贵金属的原液分散于去离子水中，得到浓度为0.05%～12%的贵金属稀释溶液，经水热处理、离心、再分散后制得贵金属的改性前驱体；
步骤二、将载体材料分散于去离子水中，再加入步骤一得到的贵金属改性前驱体，经搅拌、调pH、干燥、焙烧、制浆、涂覆，即得到所述催化剂。
进一步的，所述步骤一中的水热处理温度为60～250℃，水热处理时间为4～48h，再分散所用溶剂为醇、有机酸、醚；
进一步的，所述步骤二中的pH范围为2～14，其pH调节剂为无机碱、有机碱，所述干燥的温度为60～250℃，干燥时间为4～48h，所述焙烧的温度为400～600℃，焙烧时间为2～12h。
本发明的有益效果是：本发明中载体为锆基稀土改性、锆基铝改性多孔材料，活性组分采用贵金属的改性前驱体，一方面，由于改性贵金属降低了无机离子含量，且具有一定的微观尺度，可有效解决贵金属在制备和反应过程的中发生颗粒团聚而导致活性降低的问题，从而起到防止烧结、分散贵金属的作用，同时，锆基材料由于具有更多的氧空位，可以支撑贵金属高效、全面净化HC、CO、NOx、和NH3。
具体实施方式
下面结合实施例对本发明的具体实施方式进行详细说明。
实施例1：
一种燃气机尾气全污染物净化催化剂，包括载体和活性组分，所述载体为锆基稀土改性、锆基铝改性多孔材料，所述活性组分为贵金属Pd、Rh、Pt的改性前驱体，其原液为Pt含量为15％的硝酸铂水溶液，Pd含量为15％的硝酸钯水溶液，Rh含量为10％的硝酸铑水溶液，且载体、Pd、Rh、Pt的质量比为0.991:0.004: 0.004:0.001。
所述催化剂的制备方法依次包括以下步骤：
一、先将三种贵金属的原液分散于去离子水中，得到浓度为0.8%的贵金属稀释溶液，分别将之水热处理110℃/10h，离心去掉上清液，再用乙二醇分散沉积物，制得三种贵金属的有机改性前驱体；
二、将锆基铈改性多孔材料分散于去离子水中，再加入步骤一得到的贵金属改性前驱体，搅拌均匀后用氨水调pH至9，继续搅拌1h，而后100℃干燥24h、600℃焙烧5h、制浆、涂覆，即得到催化剂C1。该催化剂经封装、活化，进行台架测试。
实施例2：
配方和步骤与实施例1类似，不同点在于：
本实施例步骤一中的有机物为正丁醇，步骤二中的载体为锆基镧钕钇改性多孔材料，即得到催化剂C2。该催化剂经封装、活化，进行台架测试。
测试结果如下表所示：
| 污染物 | CO（mg/KW·h） | NOX（mg/KW·h） | CH4（mg/KW·h） | NH3（ppm） |
| 国六限值 | 4000 | 460 | 500 | 10 |
| 劣化限值 | 3077 | 400 | 357 | 10 |
| 催化剂C1 | 365 | 73 | 86 | 5.7 |
| 催化剂C2 | 427 | 186 | 74 | 5.1 |
本发明克服了现有技术中污染物，尤其是NH3净化效率低的问题，载体采用的锆基多孔材料由于具有更多的氧空位，可以支撑贵金属高效、全面净化燃气机尾气中的全污染物HC、CO、NOx、和NH3。而且本发明活性组分采用贵金属的改性前驱体，降低了无机离子含量，且具有一定的微观尺度，可有效解决贵金属在制备和反应过程的中发生颗粒团聚而导致活性降低的问题，从而起到防止烧结、分散贵金属的作用，降低了催化剂的制备成本。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明的范围内。本发明要求保护范围由所附的权利要求书及其等同物界定。
Claims (9)
1.一种燃气机尾气全污染物净化催化剂，其特征在于：包括载体和活性组分，所述载体为锆基多孔材料，所述活性组分为贵金属的改性前驱体，所述载体与贵金属的质量比为1:0.001～0.03。
2.如权利要求1所述的一种燃气机尾气全污染物净化催化剂，其特征在于：所述贵金属为Pd、Rh、Pt、Ru、Os、Ir、Au、Ag中的至少一种，所述锆基多孔材料为纯锆、锆基稀土改性、锆基铝改性、锆基硅改性、锆基钒钛钨改性中的中的至少一种。
3.如权利要求2所述的一种燃气机尾气全污染物净化催化剂，其特征在于：所述贵金属为Pd、Rh、Pt，所述锆基多孔材料为锆基稀土改性、锆基铝改性多孔材料。
4.如权利要求3所述的一种燃气机尾气全污染物净化催化剂，其特征在于：所述锆基稀土改性、锆基铝改性多孔材料中氧化锆的质量分数为70%～100%。
5.如权利要求4所述的一种燃气机尾气全污染物净化催化剂，其特征在于：所述氧化锆的质量分数为90%～95%。
6.如权利要求1所述的一种燃气机尾气全污染物净化催化剂，其特征在于：所述贵金属的改性前驱体为金属氯化物、金属硝酸盐、金属氢氧化物、金属水合氧化物、金属有机分散液中的至少一种。
7.一种如权利要求1所述的燃气机尾气全污染物净化催化剂的制备方法，其特征在于包括如下步骤：
步骤一、将贵金属的原液分散于去离子水中，得到浓度为0.05%～12%的贵金属稀释溶液，经水热处理、离心、再分散后制得贵金属的改性前驱体；
步骤二、将载体材料分散于去离子水中，再加入步骤一得到的贵金属改性前驱体，经搅拌、调pH、干燥、焙烧、制浆、涂覆，即得到所述催化剂。
8.如权利要求7所述的一种燃气机尾气全污染物净化催化剂的制备方法，其特征在于：所述步骤一中的水热处理温度为60～250℃，水热处理时间为4～48h，再分散所用溶剂为醇、有机酸、醚。
9.如权利要求7所述的一种燃气机尾气全污染物净化催化剂的制备方法，其特征在于：所述步骤二中的pH范围为2～14，其pH调节剂为无机碱、有机碱，所述干燥的温度为60～250℃，干燥时间为4～48h，所述焙烧的温度为400～600℃，焙烧时间为2～12h。
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