CN116173943A - 一种提升汽车尾气净化催化剂老化性能的方法 - Google Patents
一种提升汽车尾气净化催化剂老化性能的方法 Download PDFInfo
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Abstract
本发明公开了一种提升汽车尾气净化催化剂老化性能的方法。汽车尾气净化催化剂是三元催化剂,由蜂窝载体和涂覆于载体表面的催化剂涂层制成;催化剂涂层由包括贵金属、储氧材料、氧化铝材料经球磨制浆后、涂覆于载体表面并干燥制成;催化剂涂层浆料中加入多聚化合物,多聚化合物是糖类、酯类、醚类中的一种或几种。本发明催化剂制备中,将多聚化合物,如糖类、酯类、醚类中的一种或几种,添加到涂层材料中,经过焙烧分解,在催化剂涂层中产生孔隙,改变原有催化剂涂层的孔隙率和孔径分布,形成的催化剂涂层有利于汽车尾气中的污染物和涂层活性中心之间的质量传递。宏观上催化剂对汽车尾气中污染物转化率的提升,降低汽车尾气排放超标的风险。
Description
技术领域
本发明属于汽车尾气后处理净化催化剂制备技术领域,涉及一种提升汽车尾气净化催化剂老化性能的方法。
背景技术
随着社会经济的发展,人们生活水平的提高,汽车的保有量逐年增加,对汽车尾气净化的要求也越来越高。现阶段,汽车尾气的净化大多采用三元催化剂。汽车尾气中的CO、HC以及NOx等主要气态污染物在三元催化剂处理后可转化为CO2、H2O、N2等危害较小甚至无害的物质。汽车在行驶过程中,包括启动、提速、降速和停止阶段;三元催化对污染物的转化率受温度、组分、空速以及使用时间的影响,在启动和提速阶段,尾气的空速会明显增大,随着空速的增大,污染物在催化剂网格通道的停留时间降低,反应时间下降,催化剂的性能明显的下降。并且随着使用时间的增长,催化剂老化受损,其净化效果也会明显的下降。如何提升高空速和老化条件下的转化率,是提升催化剂净化效率的一个难题。
林涛等人在“低浓度甲苯催化燃烧蜂窝陶瓷催化剂的制备”(山东化工,2018)一文中提出:研究表明在制作氧化铝涂层时添加造孔剂能够有效提高甲苯起燃性能,但是对甲苯的高温转化率并未表现出明显的提升。我们都知道:在汽车尾气净化处理体系中,三元催化剂载体多选用为蜂窝载体,具有多孔道的结构,汽车尾气流经催化剂转化为无害气体的本质为气固相催化反应。整个反应过程可以概括为七个步骤:1.污染物由气流主体向催化剂涂层外表面传递;2.污染物由涂层外表面向内部活性中心传递;3.污染物在活性中心吸附;4.在活性中心上发生化学反应;5.反应产物进行解吸脱附;6反应产物向涂层外表面传递;7反应组分从涂层外表面向气流主体传递。综合上述反应过程可见,催化剂涂层的孔隙率和孔道结构直接影响其活性。因此,在催化剂制备的工业过程中,提升催化剂涂层的孔隙率和孔容分布是提升催化剂对污染物处理能力的一种可行办法。
发明内容
本发明根据现有技术的不足公开了一种提升汽车尾气净化催化剂老化性能的方法。本发明目的是提供一种制备方法,通过在制浆过程中添加助剂,改变涂层的孔隙率和孔道结构,提升催化剂对汽车尾气中一种或多种气态污染物的转化率。
本发明通过以下技术方案实现:
一种提升汽车尾气净化催化剂老化性能的方法,所述汽车尾气净化催化剂是三元催化剂,由蜂窝载体和涂覆于载体表面的催化剂涂层制成;催化剂涂层由包括贵金属、储氧材料、氧化铝材料经球磨制浆后、涂覆于载体表面并干燥制成;所述催化剂涂层浆料中加入多聚化合物,所述多聚化合物是糖类、酯类、醚类中的一种或几种。
一种选择多聚化合物糖类是淀粉。
一种选择多聚化合物酯类是聚甲基丙烯酸甲酯。
一种选择多聚化合物醚类是羟丙基纤维素醚。
本发明催化剂涂层由以下质量份数的成分制成:铂族贵金属,包括Pt、Pd和/或Rh,1.0~5.0份,以金属离子计;储氧材料65~75份;氧化铝材料10~30份;多聚化合物3~10份。
具体提升汽车尾气净化催化剂老化性能的制备方法,包括以下步骤:
a)计算各物料所需用量;
b)根据计算值,对贵金属、储氧材料、氧化铝材料和去离子水进行称量;并放置球磨设备内进行球磨30~50min;检测浆料的粒度,若平均粒度在3~9um,合格,若大于9um,继续球磨,每隔5min检测一次粒度,直至平均粒度在3~9um;
c)称量所需多聚化合物,并加入球磨罐中与步骤b的浆料进行混合。
再次球磨5~10min;
d)取出步骤c制备完成的贵金属浆料;将涂覆至蜂窝陶瓷载体网格孔道内部,控制涂覆量在260~270g/L;
e)将涂覆后的样品进行干燥,干燥温度在100~150℃,时间15~25min;样品干燥完成后进行焙烧,焙烧温度在480~510℃,时间120~150min;得到制备的汽车尾气净化催化剂。
本发明有益性:本发明制备方法通过在制浆过程中添加助剂,改变涂层的孔隙率和孔道结构,提升催化剂对汽车尾气中各种气态污染物的转化率。制备中,将多聚化合物,如糖类、酯类、醚类中的一种或几种,添加到涂层材料中,经过焙烧分解,在催化剂涂层中产生孔隙,改变原有催化剂涂层的孔隙率和孔径分布,形成的催化剂涂层有利于汽车尾气中的污染物和涂层活性中心之间的质量传递。宏观上催化剂对汽车尾气中污染物转化率的提升,降低汽车尾气排放超标的风险。
附图说明
图1是本发明对比例与实施例催化剂老化后性能测试。
具体实施方式
下面结合具体实施方式对本发明进一步说明,具体实施方式是对本发明原理的进一步说明,不以任何方式限制本发明,与本发明相同或类似技术均没有超出本发明保护的范围。
对比例,常规浆料工艺制备催化剂方法:
a)计算实验各种物料所需求的用量;
b)根据计算值,对贵金属、储氧材料、氧化铝材料和去离子水进行称量。并放置球磨设备内进行球磨30~50min。检测浆料的粒度,若平均粒度在3~9um以内,表明浆料合格,若大于9um,则继续球磨,每隔5min检测一次粒度,直至平均粒度在3~9um;
c)取出步骤b制备完成的贵金属浆料。将涂覆至蜂窝陶瓷载体网格孔道内部,控制涂覆量在260~270g/L;
d)将涂覆后的样品进行干燥,干燥温度在100~150℃,时间15~25min。样品干燥完成后进行焙烧,焙烧温度在480~510℃,时间120~150min;
e)将成品催化剂在800℃温度下老化20h;
f)利用汽车台架设备对催化剂的性能进行测试。
实施例1:
a)计算实验各种物料所需求的用量;
b)根据计算值,对贵金属、储氧材料、氧化铝材料和去离子水进行称量。并放置球磨设备内进行球磨30~50min。检测浆料的粒度,若平均粒度在3~9um以内,表明浆料合格,若大于9um,则继续球磨,每隔5min检测一次粒度,直至平均粒度在3~9um;
c)称量所需要淀粉的多聚化合物质量,并加入球磨罐中与步骤b的浆料进行混合。再次球磨5~10min。
d)取出步骤c制备完成的贵金属浆料。将涂覆至蜂窝陶瓷载体网格孔道内部,控制涂覆量在260~270g/L;
e)将涂覆后的样品进行干燥,干燥温度在100~150℃,时间15~25min。样品干燥完成后进行焙烧,焙烧温度在480~510℃,时间120~150min;
f)将成品催化剂在800℃温度下老化20h;
g)利用汽车台架设备对催化剂的性能进行测试。
实施例2:
a)计算实验各种物料所需求的用量;
b)根据计算值,对贵金属、储氧材料、氧化铝材料和去离子水进行称量。并放置球磨设备内进行球磨30~50min。检测浆料的粒度,若平均粒度在3~9um以内,表明浆料合格,若大于9um,则继续球磨,每隔5min检测一次粒度,直至平均粒度在3~9um;
c)称量所需要聚甲基丙烯酸甲酯的多聚化合物,并加入球磨罐中与步骤b的浆料进行混合。再次球磨5~10min。
d)取出步骤c制备完成的贵金属浆料。将涂覆至蜂窝陶瓷载体网格孔道内部,控制涂覆量在260~270g/L;
e)将涂覆后的样品进行干燥,干燥温度在100~150℃,时间15~25min。样品干燥完成后进行焙烧,焙烧温度在480~510℃,时间120~150min;
f)将成品催化剂在800℃温度下老化20h;
g)利用汽车台架设备对催化剂的性能进行测试。
实施例3:
a)计算实验各种物料所需求的用量;
b)根据计算值,对贵金属、储氧材料、氧化铝材料和去离子水进行称量。并放置球磨设备内进行球磨30~50min。检测浆料的粒度,若平均粒度在3~9um以内,表明浆料合格,若大于9um,则继续球磨,每隔5min检测一次粒度,直至平均粒度在3~9um;
c)称量所需要羟丙基纤维素醚的多聚化合物,并加入球磨罐中与步骤b的浆料进行混合。再次球磨5~10min。
d)取出步骤c制备完成的贵金属浆料。将涂覆至蜂窝陶瓷载体网格孔道内部,控制涂覆量在260~270g/L;
e)将涂覆后的样品进行干燥,干燥温度在100~150℃,时间15~25min。样品干燥完成后进行焙烧,焙烧温度在480~510℃,时间120~150min;
f)将成品催化剂在800℃温度下老化20h;
g)利用汽车台架设备对催化剂的性能进行测试。
检测:
测试采用汽车台架测试系统模拟真实汽车使用情况。发动机选取排放在7L左右。转速控制1500~1700转/min。负荷控制在70~75%,发动机燃料与进气空气的流量比控制在14~14.5。测试温度区间为400~540℃。其空速在55000~70000W/h。
催化剂进口和出口处气体通过红外气体分析仪进行分析。其中转化率通过下式计算:A=(1-NC/NJ)×100%;其中,A是催化剂对污染物的转化率,NC是催化剂出口污染物浓度,NJ是催化剂进口污染物浓度。测试计算结果见图1。
通过四个实施例的测试,得到图1的数据。数据表明,对比例催化剂老化后,在400~540℃的区域,对HC污染物的转换率有所下降,催化剂在老化受损,存在对气态污染物HC转化能力不足的问题;进一步,对比例催化剂转化率表现出随温度升高,转化率出现下降的情况,说明空速较高的使用条件下,同时存在对污染物HC转化能力不足的问题。通过测试数据对比,在400℃~540℃温度区间,使用实施例1、实施例2和实施例3制备的催化剂较对比例1可明显提升催化剂对气态污染物HC的转化率。说明,本发明通过制浆时糖类、酯类以及醚类一种或多种助剂,可有效提升催化剂老化后对汽车尾气中一种或多种气态污染物的转化率。
Claims (6)
1.一种提升汽车尾气净化催化剂老化性能的方法,所述汽车尾气净化催化剂是三元催化剂,由蜂窝载体和涂覆于载体表面的催化剂涂层制成;催化剂涂层由包括贵金属、储氧材料、氧化铝材料经球磨制浆后、涂覆于载体表面并干燥制成;其特征在于:所述催化剂涂层浆料中加入多聚化合物,所述多聚化合物是糖类、酯类、醚类中的一种或几种。
2.根据权利要求1所述的提升汽车尾气净化催化剂老化性能的方法,其特征在于:多聚化合物糖类是淀粉。
3.根据权利要求1所述的提升汽车尾气净化催化剂老化性能的方法,其特征在于:多聚化合物酯类是聚甲基丙烯酸甲酯。
4.根据权利要求1所述的提升汽车尾气净化催化剂老化性能的方法,其特征在于:多聚化合物醚类是羟丙基纤维素醚。
5.根据权利要求1至4任一项所述的提升汽车尾气净化催化剂老化性能的方法,其特征在于:催化剂涂层由以下质量份数的成分制成:铂族贵金属,包括Pt、Pd和/或Rh,1.0~5.0份;储氧材料65~75份;氧化铝材料10~30份;多聚化合物3~10份。
6.根据权利要求5所述的提升汽车尾气净化催化剂老化性能的方法,其特征在于包括以下步骤:
a)计算各物料所需用量;
b)根据计算值,对贵金属、储氧材料、氧化铝材料和去离子水进行称量;并放置球磨设备内进行球磨30~50min;检测浆料的粒度,若平均粒度在3~9um,合格,若大于9um,继续球磨,每隔5min检测一次粒度,直至平均粒度在3~9um;
c)称量所需多聚化合物,并加入球磨罐中与步骤b的浆料进行混合。再次球磨5~10min;
d)取出步骤c制备完成的贵金属浆料;将涂覆至蜂窝陶瓷载体网格孔道内部,控制涂覆量在260~270g/L;
e)将涂覆后的样品进行干燥,干燥温度在100~150℃,时间15~25min;样品干燥完成后进行焙烧,焙烧温度在480~510℃,时间120~150min;得到制备的汽车尾气净化催化剂。
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