CN112844381B - 镁铝尖晶石改性的Pt基汽车尾气催化剂及制备方法和应用 - Google Patents
镁铝尖晶石改性的Pt基汽车尾气催化剂及制备方法和应用 Download PDFInfo
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Abstract
本发明提供的一种镁铝尖晶石改性的Pt基汽车尾气催化剂及制备方法和应用,将Pt负载在MgAl2O4载体上,再与CeZrO2载体高能球磨。本发明通过利用Pt与MgAl2O4晶面外延匹配与强相互作用,有效控制Pt的价态和尺寸;MgAl2O4尖晶石辅助改性制备的三效催化剂能够提高CO、HC、NO活性和抗高温老化性能。
Description
技术领域
本发明属于多相催化剂制备技术领域,尤其属于机动车尾气处理催化剂制备技术领域,特别涉及一种镁铝尖晶石改性的Pt基汽车尾气催化剂及制备方法和应用。
背景技术
机动车尾气是大气污染物的主要来源之一,主要污染物包括:一氧化碳(CO)、碳氢化合物(HC)、氮氧化合物(NOx)和颗粒物(PMs);不仅造成严重的环境污染,而且对人类身体健康危害极大。汽油车因其燃油经济性、高热效率,已得到广泛使用。三效催化剂(TWCs)是净化汽油车尾气气态污染物最有效的技术手段,能在理论空燃比(A/F=14.6)附近将HC、CO、NOx同时转化为H2O、CO2、N2。目前三效催化剂,主要以Pt、Pd、Rh等作为活性组分,以高比表面、高热稳定的Al2O3基材料,以及具有优异储放氧性能的CeO2基材料为三效催化剂的载体。然而,随着排放法规的日益严苛,更高的排放标准给三效催化剂的发展带来了新的挑战和机遇。
汽油车国Ⅵ-b阶段排放标准将于2023年全面实施,相比国Ⅵ-a,CO严格了30%(0.5→0.35g/km),HC、NOx严格了60%(0.1→0.032g/km、0.06→0.02g/km),耐久性里程提高到20万公里;未来准零排放标准对三效催化剂的低温活性和高温耐久性要求更高。经研究发现,初始分散较好的贵金属颗粒,在高温下聚集或晶粒长大,导致表面活性位减少,催化活性和稳定性降低。同时,载体的高温烧结也会引起孔结构坍塌,活性位点减少,也会导致活性降低。然而,无论汽油车是GDI发动机还是PFI发动机,都会面临短暂的高负荷排气条件,其尾气温度能达到1000℃以上,必然会造成三效催化剂活性组分Pt、Pd、Rh等或/和载体材料烧结,导致三效催化剂活性、稳定性下降。
因此,开发一种同时具有低温活性和高温稳定性的三效催化剂制备技术,对于满足国Ⅵ-b甚至更高排放标准的汽油车尾气净化系统的开发具有重要意义。
发明内容
本发明公开了一种镁铝尖晶石辅助改性的高稳定性Pt基三效催化剂及其制备方法。本发明的目的是提供一种同时具有低温活性和高温稳定性的整体式汽油车三效催化剂及其制备方法。
本发明通过以下技术方案实现:
镁铝尖晶石改性的Pt基汽车尾气催化剂的制备方法,将Pt负载在MgAl2O4载体上,再与CeZrO2载体高能球磨。
MgAl2O4在载体中的质量百分比含量是10~30wt%。
Pt总负载量0.5~3wt%。
具体的制备方法,包括以下步骤:
(1)采用液相还原浸渍法制备Pt/MgAl2O4粉末,按计量比称取10~30wt%的MgAl2O4,倒入还原后的Pt胶体溶液,水浴60~80℃搅拌1~2h干燥;
(2)将步骤(1)得到的混合物置于干燥箱中在60~120℃干燥6~12h,最后在焙烧炉中于450~550℃焙烧3h,得到Pt/MgAl2O4粉末材料;
(3)称取70~90wt%的CeZrO2,与步骤(2)制备的Pt/MgAl2O4粉末材料高能球磨8-10min;
(4)将步骤(3)中得到的混合物置于850-950℃焙烧3h得到催化剂粉末材料;
(5)将步骤(4)制备得到的催化剂粉末涂覆在堇青石上,经干燥、焙烧,制得整体式催化剂。
所述的MgAl2O4的比表面积为90-150m2/g,孔容为0.6-0.9cm3/g;CeZrO2的比表面积是50-70m2/g,孔容为0.5-0.8cm3/g。
所述载体MgAl2O4由沉淀法制备,包括以下方法:
(1)将Al(NO3)3·9H2O、Mg(NO3)2·6H2O溶解于去离子水中得到0.5mol/L的硝酸铝、硝酸镁混合溶液,同时配制NH3·H2O:(NH4)2CO3摩尔比为3:3的NH3·H2O和(NH4)2CO3混合溶液2.5L;
(2)将硝酸铝、硝酸镁混合溶液与NH3·H2O和(NH4)2CO3混合溶液在剧烈搅拌下并流加入沉淀反应器,控制pH值在8.0-9.0,沉淀在90℃陈化6h,然后过滤、洗涤,再于100℃干燥12h;
(3)将步骤(2)得到的粉末逐渐升温到900℃焙烧4h,得到MgAl2O4;MgO在载体中的质量百分比含量控制在25~35wt%。
所述载体CeZrO2由沉淀法制备,包括以下方法:
(1)将Ce(NO3)3·6H2O、Zr(NO3)4·5H2O溶解于去离子水中得到0.5mol/L的Ce(NO3)3与Zr(NO3)4混合溶液,同时配制NH3·H2O:(NH4)2CO3摩尔比为3:3的NH3·H2O和(NH4)2CO3混合溶液2.5L;
(2)将Ce(NO3)3与Zr(NO3)4混合溶液与NH3·H2O和(NH4)2CO3混合溶液在剧烈搅拌下并流加入沉淀反应器,控制pH值在8.0-9.0,沉淀在90℃陈化6h,然后过滤、洗涤,再于100℃干燥12h;
(3)将步骤(2)得到的粉末逐渐升温到900℃焙烧4h,得到CeZrO2;CeO2在载体中的质量百分比含量控制在25~35wt%。
本发明获得的镁铝尖晶石改性的Pt基汽车尾气催化剂,对CO、HC、NO转化效果,具有良好的催化活性和高温稳定性,用于汽车尾气处理。
本发明有益性是:本发明通过利用Pt与MgAl2O4晶面外延匹配与强相互作用,有效控制Pt的价态和尺寸;MgAl2O4尖晶石辅助改性制备的三效催化剂能够提高CO、HC、NO活性和抗高温老化性能。
附图说明
图1a为实施例2与比较例3的CO新鲜样变化;
图1b为实施例2与比较例3的NO新鲜样变化;
图1c为实施例2与比较例3的C3H8新鲜样变化;
图1d为实施例2与比较例3的C3H6新鲜样变化;
图2a为实施例2与比较例3的CO老化样变化;
图2b为实施例2与比较例3的NO老化样变化;
图2c为实施例2与比较例3的C3H8老化样变化;
图2d为实施例2与比较例3的C3H6老化样变化。
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。
实施例1
本实施例提供Pt/MgAl2O4-CeZrO2催化剂的制备方法,包括以下步骤:
(1)采用液相还原浸渍法制备Pt/MgAl2O4粉末,按计量比称取10wt%的MgAl2O4,倒入还原后的Pt胶体溶液,水浴60~80℃搅拌1~2h;
(2)将(1)得到的样品置于干燥箱中在60℃~120℃干燥6~12h,最后在焙烧炉中于450~550℃焙烧3h,得到Pt/MgAl2O4-10%粉末材料;
(3)称取90wt%的CeZrO2,与(2)制备的Pt/MgAl2O4-10%粉末材料高能球磨8-10min;
(4)将(3)中得到的催化剂置于850-950℃焙烧3h得到催化剂粉末材料;
(5)将(4)得到的催化剂粉末材料与2~5wt%的铝溶胶、2~5wt%的醋酸研磨制成催化剂浆料,并控制固含量为35~45%;
(6)将(5)所得催化剂浆料均匀地涂覆在堇青石蜂窝陶瓷基体上,控制催化剂的上载量140~160g/L;
(7)将涂覆后的基体由室温逐步升至60℃缓慢干燥,然后在550℃空气气氛中焙烧3h,得到整体式Pt/MgAl2O4-CeZrO2-10%催化剂,记作Pt/MA-CZ-1。
实施例2
(1)采用液相还原浸渍法制备Pt/MgAl2O4粉末,按计量比称取20wt%的MgAl2O4,倒入还原后的Pt胶体溶液,水浴60~80℃搅拌1~2h干燥、焙烧与实施例1的步骤(2)相同},得到Pt/MgAl2O4-20wt%粉末材料;
(2)按照实施例1步骤(3)相同方法,称取80wt%的CeZrO2,与步骤(1)制备的Pt/MgAl2O4-20wt%粉末材料高能球磨8-10min;
(3)按照实施例1中步骤(4),(5),(6)和(7)相同方法,制备得到整体式Pt/MgAl2O4-CeZrO2-20%催化剂,记作Pt/MA-CZ-2。
实施例3
(1)采用液相还原浸渍法制备Pt/MgAl2O4粉末,按计量比称取30wt%的MgAl2O4,倒入还原后的Pt胶体溶液,水浴60~80℃搅拌1~2h干燥、焙烧{与实施例1的步骤(2)相同},得到Pt/MgAl2O4-30wt%粉末材料;
(2)按照实施例1步骤(3)相同方法,称取70wt%的CeZrO2,与(1)制备的Pt/MgAl2O4-30wt%粉末材料高能球磨8-10min;
(3)按照实施例1中步骤(4),(5),(6)和(7)相同方法,制备得到整体式Pt/MgAl2O4-CeZrO2-30%催化剂,记作Pt/MA-CZ-3。
比较例1
(1)采用液相还原浸渍法制备Pt/LaAl2O3粉末,按计量比称取0wt%的LaAl2O3,倒入还原后的Pt胶体溶液,水浴60~80℃搅拌1~2h干燥、焙烧{与实施例1的步骤(2)相同},得到Pt/LaAl2O3-10wt%粉末材料;
(2)按照实施例1步骤(3)相同方法,称取90wt%的CeZrO2,与(1)制备的Pt/LaAl2O3-10wt%粉末材料高能球磨8-10min;
(3)按照实施例1中步骤(4),(5),(6)和(7)相同方法,制备得到整体式Pt/LaAl2O3-CeZrO2-10%催化剂,记作Pt/LA-CZ-1。
比较例2
(1)采用液相还原浸渍法制备Pt/LaAl2O3粉末,按计量比称取20wt%的LaAl2O3,倒入还原后的Pt胶体溶液,水浴60~80℃搅拌1~2h干燥、焙烧{与实施例1的步骤(2)相同},得到Pt/LaAl2O3-20wt%粉末材料;
(2)按照实施例1步骤(3)相同方法,称取80wt%的CeZrO2,与(1)制备的Pt/LaAl2O3-20wt%粉末材料高能球磨8-10min;
(3)按照实施例1中步骤(4),(5),(6)和(7)相同方法,制备得到整体式Pt/LaAl2O3-CeZrO2-20%催化剂,记作Pt/LA-CZ-2。
比较例3
(1)采用液相还原浸渍法制备Pt/LaAl2O3粉末,按计量比称取30wt%的LaAl2O3,倒入还原后的Pt胶体溶液,水浴60~80℃搅拌1~2h干燥、焙烧{与实施例1的步骤(2)相同},得到Pt/LaAl2O3-30wt%粉末材料;
(2)按照实施例1步骤(3)相同方法,称取70wt%的CeZrO2,与步骤(1)制备的Pt/LaAl2O3-30wt%粉末材料高能球磨8-10min;
(3)按照实施例1中步骤(4),(5),(6)和(7)相同方法,制备得到整体式Pt/LaAl2O3-CeZrO2-30%催化剂,记作Pt/LA-CZ-3。
比较例4
(1)采用液相还原浸渍法制备Pt/CeZrO2粉末,按计量比称取90wt%的CeZrO2,倒入还原后的Pt胶体溶液,水浴60~80℃搅拌1~2h;
(2)将(1)得到的样品置于干燥箱中在60℃~120℃干燥6~12h,最后在焙烧炉中于450~550℃焙烧3h,得到Pt/CeZrO2-90%粉末材料;
(3)称取10wt%的MgAl2O4,与(2)制备的Pt/CeZrO2-90%粉末材料高能球磨8-10min;
(4)按照实施例1中步骤(4),(5),(6)和(7)相同方法,制备得到整体式Pt/CeZrO2-MgAl2O4催化剂,记作Pt/CZ-MA-1。
比较例5
(1)采用液相还原浸渍法制备Pt/CeZrO2-MgAl2O4粉末,按计量比称取90wt%的CeZrO2和10%的MgAl2O4,混合高能球磨8-10min;倒入还原后的Pt胶体溶液,水浴60~80℃搅拌1~2h;
(2)将(1)得到的样品置于干燥箱中在60℃~120℃干燥6~12h,最后在焙烧炉中于450~550℃焙烧3h,得到Pt/CeZrO2(90%)-MgAl2O4(10%)粉末材料;
(3)按照实施例1中步骤(4),(5),(6)和(7)相同方法,制备得到整体式Pt/CeZrO2-MgAl2O4催化剂,记作Pt/CZ-MA-2。
活性评价实验:
催化剂的活性评价在多路固定连续流动的微型反应器中进行,模拟汽油车尾气组成为:NO1250 ppm、CO 4600ppm、C3H6 220ppm、C3H8110 ppm、H2 1533ppm、O2 10%、CO2 11%、N2作为载气,空速为50000h-1。所有催化剂样品在反应前均在反应气氛(模拟汽油车尾气)中550℃预处理2h。然后以5℃/min的升温速率进行活性测试。CO、NO、C3H6、C3H8的浓度采用傅立叶红外气体分析仪(Thermol Fisher Scientific)进行测试。老化处理:将催化剂在1000℃条件下水热老化5h,通空气的流量为2000mL/min,含水量10vol%。
老化前后催化剂活性评价结果如表1所示:
表1老化前后的催化活性
如图1a到图1d,为实施例2与比较例2新鲜催化剂CO、NO、HC的转化率随温度变化;其中,纵坐标表示转化率,单位%;横坐标表示温度,单位℃;曲线A和曲线B分别是实施例2与比较例2新鲜样变化。
如图2a到图2d,为实施例2与比较例2老化催化剂CO、NO、HC的转化率随温度变化;其中,纵坐标表示转化率,单位%;横坐标表示温度,单位℃;曲线A-a和曲线B-a分别是实施例2和实施例2老化样变化。
实施例1至实施例3催化剂老化前后的活性结果表明,本发明添加不同含量的MgAl2O4载体制备的Pt/MA-CZ-1三效催化剂的CO、HC和NO的活性及抗高温老化性能均优于Pt/LA-CZ-1,Pt/LA-CZ-2,Pt/LA-CZ-3(比较例1、2、3);Pt预先负载在MgAl2O4载体上,再与CeZrO2高能球磨,Pt/MA-CZ-1催化剂活性优于其它制备方式制备的催化剂Pt/CZ-MA-1,实施例1至实施例3催化剂老化活性明显高于比较例1、比较例2和比较例3催化剂。
Claims (8)
1.镁铝尖晶石改性的Pt基汽车尾气催化剂的制备方法,其特征在于:将Pt负载在MgAl2O4载体上,再与CeZrO2载体高能球磨;
包括以下步骤:
(1)采用液相还原浸渍法制备Pt/MgAl2O4粉末,按载体的质量百分比计量,称取10~30wt%的MgAl2O4,倒入还原后的Pt胶体溶液,水浴60~80 ℃搅拌1~2 h干燥;
(2)将步骤(1)得到的混合物置于干燥箱中在60~120 ℃干燥6~12 h,最后在焙烧炉中于450~550 ℃焙烧3 h,得到Pt/MgAl2O4粉末材料;
(3)按载体的质量百分比计量,称取70~90 wt%的CeZrO2,与步骤(2)制备的Pt/MgAl2O4粉末材料高能球磨8-10 min;
(4)将步骤(3)中得到的混合物置于850-950 ℃焙烧3 h得到催化剂粉末材料;
(5)将步骤(4)制备得到的催化剂粉末涂覆在堇青石上,经干燥、焙烧,制得整体式催化剂。
2.根据权利要求1所述的镁铝尖晶石改性的Pt基汽车尾气催化剂的制备方法,其特征在于:MgAl2O4在载体中的质量百分比含量是10~30 wt%。
3.根据权利要求1所述的镁铝尖晶石改性的Pt基汽车尾气催化剂的制备方法,其特征在于: Pt总负载量0.5~3 wt%。
4.根据权利要求1所述的镁铝尖晶石改性的Pt基汽车尾气催化剂的制备方法,其特征在于:所述的MgAl2O4的比表面积为90-150 m2/g,孔容为0.6-0.9 cm3/g;CeZrO2的比表面积是50-70 m2/g,孔容为0.5-0.8 cm3/g。
5.根据权利要求4所述的镁铝尖晶石改性的Pt基汽车尾气催化剂的制备方法,其特征在于:所述载体MgAl2O4由沉淀法制备,包括以下方法:
(1)将Al(NO3)3·9H2O、Mg(NO3)2·6H2O溶解于去离子水中得到0.5 mol/L的硝酸铝、硝酸镁混合溶液,同时配制NH3·H2O:(NH4)2CO3摩尔比为3:3的NH3·H2O和(NH4)2CO3混合溶液2.5 L;
(2)将硝酸铝、硝酸镁混合溶液与NH3·H2O和(NH4)2CO3混合溶液在剧烈搅拌下并流加入沉淀反应器,控制pH值在8.0-9.0,沉淀在90 ℃陈化6 h,然后过滤、洗涤,再于100 ℃干燥12 h;
(3)将步骤(2)得到的粉末逐渐升温到900 ℃焙烧4 h,得到MgAl2O4;MgO在载体中的质量百分比含量控制在25~35 wt%。
6.根据权利要求4所述的镁铝尖晶石改性的Pt基汽车尾气催化剂的制备方法,其特征在于:所述载体CeZrO2由沉淀法制备,包括以下方法:
(1)将Ce(NO3)3·6H2O、Zr(NO3)4·5H2O溶解于去离子水中得到0.5 mol/L的Ce(NO3)3与Zr(NO3)4混合溶液,同时配制NH3·H2O:(NH4)2CO3摩尔比为3:3的NH3·H2O和(NH4)2CO3混合溶液2.5 L;
(2)将Ce(NO3)3与Zr(NO3)4混合溶液与NH3·H2O和(NH4)2CO3混合溶液在剧烈搅拌下并流加入沉淀反应器,控制pH值在8.0-9.0,沉淀在90 ℃陈化6 h,然后过滤、洗涤,再于100 ℃干燥12 h;
(3)将步骤(2)得到的粉末逐渐升温到900 ℃焙烧4 h,得到CeZrO2;CeO2在载体中的质量百分比含量控制在25~35 wt%。
7.镁铝尖晶石改性的Pt基汽车尾气催化剂,其特征在于,根据权利要求1到6任一项制备方法所得。
8.镁铝尖晶石改性的Pt基汽车尾气催化剂的应用,其特征在于,权利要求7所述的催化剂用于汽车尾气处理。
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