CN108722393A - 一种催化材料涂层与堇青石蜂窝陶瓷载体间结合强度的控制方法 - Google Patents
一种催化材料涂层与堇青石蜂窝陶瓷载体间结合强度的控制方法 Download PDFInfo
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
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Abstract
本发明公开了一种催化材料涂层与堇青石蜂窝陶瓷载体间结合强度的控制方法,保障催化剂中催化涂层与堇青石蜂窝陶瓷载体间具有优良的结合强度,减少或避免催化涂层脱落,保证催化剂性能。控制技术方法:1)对物料颗粒粒径较大的催化涂层材料浆料,通过增大堇青石蜂窝陶瓷载体网格壁的微孔孔径来提高催化剂中催化涂层与载体间的结合强度。2)对网格壁内微孔孔径较小的堇青石蜂窝陶瓷载体,通过减小涂层浆料内物料颗粒的粒径来提高催化剂涂层与载体间的结合强度。通过上述控制技术,可使堇青石蜂窝陶瓷载体催化剂的催化涂层与载体间具有优异的结合强度,涂层脱落率≤0.25%。
Description
技术领域
本发明涉及汽车尾气催化净化技术领域,特别是涉及柴油发动机尾气净化器中SCR 催化剂的催化涂层(无机非金属材料涂层)与堇青石蜂窝陶瓷载体(陶瓷衬底)间的结合强度控制技术。
背景技术
随着国家环境保护法规对汽车尾气的排放要求越来越严,发动机或整车厂商对汽车尾气净化器的净化性能要求越来越高。尾气净化器中的催化剂(催化涂层材料涂覆在堇青石蜂窝陶瓷载体网格壁上)是整个催化净化单元的核心。对于催化剂而言,其性能主要受到以下因素影响:1)催化涂层材料本身的性能;2)催化材料涂层与蜂窝陶瓷载体间的结合强度。当催化涂层与载体间的结合强度差时,汽车尾气气流通过催化剂将导致催化涂层容易脱落(涂层脱落率越大,涂层与载体间结合强度越差,催化涂层材料减少量越大),进而影响催化剂的催化净化效果,即使选择再好的催化涂层材料,也无法获得满足性能要求的催化剂。当前,我国市场上提供或在用的柴油车SCR催化剂都存在不同程度的催化涂层脱落现象,这将降低催化剂在使用过程中的催化净化性能及使用寿命,同时,也使得汽车尾气污染物的排放量没有得到预期的减少。(完成制备未使用的蜂窝陶瓷载体催化剂涂层脱落率≥2%,则催化剂不合格;使用过程催化涂层持续脱落则催化剂亦不合格)
从当前可查阅到的文献看,仍未发现有关柴油车尾气净化器中SCR催化剂的催化涂层(无机非金属材料涂层)与堇青石蜂窝陶瓷载体(陶瓷衬底)间的结合强度控制技术内容。因此本发明重点研究催化涂层与堇青石蜂窝陶瓷载体间的匹配问题,发明调控催化材料涂层与载体间结合强度的技术和方法,解决涂层与载体应如何匹配问题,进而减少或避免涂催化涂层的脱落现象,保障汽车尾气净化器的性能。
发明内容
为克服上述蜂窝陶瓷载体SCR催化剂的催化涂层与载体间结合强度差的不足和弥补现有控制技术空白,本发明提供了一种催化材料涂层与堇青石蜂窝陶瓷载体(网格壁)间结合强度的控制方法,保障涂层与载体间具有优良的结合强度。
本发明所采用的技术方案是:堇青石蜂窝陶瓷载体的微孔孔径大小及分布特征必须与涂层材料浆料内物料颗粒粒径大小及分布相匹配,调控方法为:1)调整及改变蜂窝陶瓷载体网格壁的微孔孔径大小及分布特征来匹配既定浆料;2)调整及改变催化涂层材料浆料内物料颗粒粒径大小及分布特征来匹配既定载体。
本发明的有益效果是通过调控及匹配,所制备的SCR催化剂催化涂层与堇青石蜂窝陶瓷载体的网格壁间结合强度优良,催化涂层无脱落或仅微量脱落。涂层材料浆料与载体间参数匹配及效果见下表1。从表1可看出:1)对粒径D50=1.39μm,D90=35.01μm的浆料(S-4),载体的微孔孔径分布中,大孔增多时,所制得催化剂的催化涂层脱落率降低,涂层与载体间的结合强度增大(脱落率从4.79%降至0.19%)。数据结果表明,对于粒径较大的浆料,通过增大堇青石蜂窝陶瓷载体网格壁的微孔孔径,可以提高催化剂中催化涂层与载体间的结合强度。2)对于微孔较小、分布一定的载体(C-1#),通过减小涂层浆料内物料颗粒的粒径,可提高催化剂涂层与载体间的结合强度(脱落率从4.24%降至 0.20%)。3)对于微孔孔径D90与微孔孔容之积(μm·cm3/g)在1.823~6.083的堇青石蜂窝陶瓷载体,其涂覆上粒径D50=0.80~1.39μm,D90=1.54~35.01μm的涂层浆料,所制得催化剂催化涂层脱落率<1%,涂层与载体间的结合强度较强;其中微孔孔径较大的载体(C-3#、 C-4#),对不同粒径分布的催化涂层浆料的适应性更强,涂层与载体间有优异的结合强度(涂层脱落率≤0.25%)。
表1催化涂层浆料与堇青石蜂窝陶瓷载体匹配及效果(涂层脱落率情况)
附图说明
图1为:不同堇青石蜂窝陶瓷载体的微孔孔径大小及分布特征,
图2为:不同催化涂层浆料的物料粒径大小及分布特征。
具体实施方式
下面结合附图1-2对本发明进一步说明。
实施例一:
通过球磨,制备粒径D50=1.39μm,D90=35.01μm,分布曲线如图2中S-4所示的TiO2-WO3-V2O5-SiO2体系催化涂层材料浆料(去离子水+催化涂层各组分粉料或原料)。通过调整制备工艺,分别制备网格壁微孔孔径大小及分布如图1所示的堇青石蜂窝陶瓷载体C-1#、C-2#、C-3#、C-4#(规格Φ190*152.4mm·mm)。通过浸渍-真空抽吸的涂覆方式,将浆料S-4分别涂覆到载体C-1#、C-2#、C-3#、C-4#上,制备了催化涂层干料负载量在1161~1247g范围的汽车尾气催化剂样品1#-4、2#-4、3#-4、4#-4。分别通过压缩空气吹扫法测试样品1#-4、2#-4、3#-4、4#-4的催化涂层脱落率来评估催化涂层与载体间的结合强度情况。
实施例二:
通过球磨,分别制备粒径D50=0.80μm,D90=1.54μm;D50=0.87μm,D90=5.19μm;D50=1.05μm,D90=15.9μm,分布曲线如图2中S-1、S-2、S-3所示的TiO2-WO3-V2O5-SiO2体系催化涂层材料浆料(去离子水+催化涂层各组分粉料或原料)。通过浸渍-真空抽吸的涂覆方式,将浆料S-1、S-2、S-3分别涂覆到载体C-1#上,制备了催化涂层干料负载量在1161~1247g范围的汽车尾气催化剂样品1#-1、1#-2、1#-3。分别通过压缩空气吹扫法测试样品1#-1、1#-2、1#-3的催化涂层脱落率来评估催化涂层与载体间的结合强度情况。
实施例三:
通过球磨,分别制备粒径D50=0.80μm,D90=1.54μm;D50=0.87μm,D90=5.19μm;D50=1.05μm,D90=15.9μm,分布曲线如图2中S-1、S-2、S-3所示的TiO2-WO3-V2O5-SiO2体系催化涂层材料浆料(去离子水+催化涂层各组分粉料或原料)。通过浸渍-真空抽吸的涂覆方式,将浆料S-1、S-2、S-3分别涂覆到载体C-2#上,制备了催化涂层干料负载量在1161~1247g范围的汽车尾气催化剂样品2#-1、2#-2、2#-3。分别通过压缩空气吹扫法测试样品2#-1、2#-2、2#-3的催化涂层脱落率来评估催化涂层与载体间的结合强度情况。
实施例四:
通过球磨,分别制备粒径D50=0.80μm,D90=1.54μm,D50=0.87μm,D90=5.19μm;D50=1.05μm,D90=15.9μm,分布曲线如图2中S-1、S-2、S-3所示的TiO2-WO3-V2O5-SiO2体系催化涂层材料浆料(去离子水+催化涂层各组分粉料或原料)。通过浸渍-真空抽吸的涂覆方式,将浆料S-1、S-2、S-3分别涂覆到载体C-3#上,制备了催化涂层干料负载量在1161~1247g范围的汽车尾气催化剂样品3#-1、3#-2、3#-3。分别通过压缩空气吹扫法测试样品3#-1、3#-2、3#-3的催化涂层脱落率来评估催化涂层与载体间的结合强度情况。
实施例五:
通过球磨,分别制备粒径D50=0.80μm,D90=1.54μm;D50=0.87μm,D90=5.19μm;D50=1.05μm,D90=15.9μm,分布曲线如图2中S-1、S-2、S-3所示的TiO2-WO3-V2O5-SiO2体系催化涂层材料浆料(去离子水+催化涂层各组分粉料或原料)。通过浸渍-真空抽吸的涂覆方式,将浆料S-1、S-2、S-3分别涂覆到载体C-4#上,制备了催化涂层干料负载量在1161~1247g范围的汽车尾气催化剂样品4#-1、4#-2、4#-3。分别通过压缩空气吹扫法测试样品4#-1、4#-2、4#-3的催化涂层脱落率来评估催化涂层与载体间的结合强度情况。
Claims (4)
1.一种催化材料涂层与堇青石蜂窝陶瓷载体间结合强度的控制方法,其特征在于:
1)对物料颗粒粒径较大的催化涂层材料浆料,通过增大堇青石蜂窝陶瓷载体网格壁的微孔孔径来提高催化剂中催化涂层与载体间的结合强度;
2)对网格壁内微孔孔径较小的堇青石蜂窝陶瓷载体,通过减小涂层浆料内物料颗粒的粒径来提高催化剂涂层与载体间的结合强度。
2.一种催化材料涂层与堇青石蜂窝陶瓷载体间结合强度的控制方法,其特征在于:
1)堇青石蜂窝陶瓷网格壁的微孔孔径D90与微孔孔容之积(μm·cm3/g)在1.183~6.083范围内;其中网格壁微孔孔径D50=1.99~3.67μm,D90=7.00~61.79μm;
2)催化涂层材料浆料内物料颗粒粒径D50=0.80~1.39μm,D90=1.54~35.01μm;
3)涂层与载体间结合强度优良的催化剂是由物料颗粒粒径D50=0.80~1.39μm,D90=1.54~35.01μm的催化涂层材料浆料匹配涂覆在网格壁微孔孔径D90与微孔孔容之积(μm·cm3/g)在1.823~6.083范围的堇青石蜂窝陶瓷载体上;
4)涂层与载体间结合强度优良的催化剂,其催化涂层浆料涂覆至堇青石蜂窝陶瓷载体的匹配条件是:涂层浆料内物料颗粒粒径D90≤载体微孔孔径D90。
3.一种催化材料涂层与堇青石蜂窝陶瓷载体间结合强度的控制方法,其特征在于含有以下步骤:
通过球磨,制备粒径D50=1.39μm,D90=35.01μm,TiO2-WO3-V2O5-SiO2体系催化涂层材料浆料即去离子水+催化涂层各组分粉料或原料;
通过调整制备工艺,分别制备堇青石蜂窝陶瓷载体C-1#、C-2#、C-3#、C-4#,通过浸渍-真空抽吸的涂覆方式,将浆料S-4分别涂覆到载体C-1#、C-2#、C-3#、C-4#上,制备了催化涂层干料负载量在1161~1247g范围的汽车尾气催化剂样品1#-4、2#-4、3#-4、4#-4;
分别通过压缩空气吹扫法测试样品1#-4、2#-4、3#-4、4#-4的催化涂层脱落率来评估催化涂层与载体间的结合强度情况。
4.一种催化材料涂层与堇青石蜂窝陶瓷载体间结合强度的控制方法,其特征在于含有以下步骤:
通过球磨,分别制备粒径D50=0.80μm,D90=1.54μm;D50=0.87μm,D90=5.19μm;D50=1.05μm,D90=15.9μm,分布曲线如图2中S-1、S-2、S-3所示的TiO2-WO3-V2O5-SiO2体系催化涂层材料浆料,即去离子水+催化涂层各组分粉料或原料;
通过浸渍-真空抽吸的涂覆方式,将浆料S-1、S-2、S-3分别涂覆到载体C-1#上,制备了催化涂层干料负载量在1161~1247g范围的汽车尾气催化剂样品1#-1、1#-2、1#-3;
分别通过压缩空气吹扫法测试样品1#-1、1#-2、1#-3的催化涂层脱落率来评估催化涂层与载体间的结合强度情况。
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