CN116870904A - 一种促进汽车尾气净化的催化剂 - Google Patents
一种促进汽车尾气净化的催化剂 Download PDFInfo
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- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
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Abstract
本发明提供一种促进汽车尾气净化的催化剂,催化剂包括载体及涂覆于载体上的涂层,涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段包括贵金属Pd,Pd负载于La2O3‑Al2O3上;上涂层包括Mn,Mn负载于二氧化钛和铈锆固溶体上。本发明的促进汽车尾气净化的催化剂,通过优化涂层组成及贵金属分布来增强尾气净化性能,下涂层Rh负载于CeAl固溶体可以避免Rh被过度老化造成Rh还原性能下降,Pd负载于后段La2O3‑Al2O3提高Pd的抗劣化性能;上涂层Mn负载于TiO2和铈锆固溶体促进不同工况下对NOx的转化。
Description
技术领域
本发明涉及催化剂技术领域,尤其涉及一种促进汽车尾气净化的催化剂。
背景技术
汽油车三元催化剂是指将汽车尾气原排中的一氧化碳(CO)、碳氢化合物(HC)和氮氧化合物(NOx)通过催化反应转化为无害的二氧化碳(CO2)、水(H2O)和氮气(N2)的车用催化剂;随着社会的发展,全球机动车的保有量不断增加,汽车尾气的污染物已成为城市空气污染的主要来源之一,不仅危害着人类健康,同时也对生态环境有着巨大的破坏;因此,各国都在制定越来越严苛的汽车尾气排放法规,来限制气态污染物的排放,随着“国六”法规的实施,人们对三元催化剂的性能也提出了更高的要求。
提高汽车尾气净化催化剂的性能对我国汽车产业的升级和大气污染的防治都具有非常重要的意义。
发明内容
本发明的目的是在于克服、补充现有技术中存在的不足,提供一种促进汽车尾气净化的催化剂,通过优化涂层组成及贵金属分布来增强尾气净化性能。
本发明采用的技术方案是:
一种促进汽车尾气净化的催化剂,其中:催化剂包括载体及涂覆于所述载体上的涂层,所述涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,所述下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段包括贵金属Pd,Pd负载于La2O3~Al2O3上;上涂层包括Mn,Mn负载于二氧化钛和铈锆固溶体上。
优选的是,所述的促进汽车尾气净化的催化剂,其中:CeAl固溶体中包括以下组分:20wt%~80wt%的CeO2和80wt%~20wt%的Al2O3。
优选的是,所述的促进汽车尾气净化的催化剂,其中:La2O3~Al2O3中包括以下组分:1wt%~10wt%的La2O3和90wt%~99wt%的Al2O3。
优选的是,所述的促进汽车尾气净化的催化剂,其中:铈锆固溶体包括ZrO2和CeO2,其中CeO2的含量为50wt%~95wt%。
优选的是,所述的促进汽车尾气净化的催化剂,其中:所述铈锆固溶体还包括La2O3、Y2O3、Pr6O11、Nd2O3中的一种或几种,其含量为1wt%~10wt%。
优选的是,所述的促进汽车尾气净化的催化剂,其中:所述Mn的来源为醋酸锰、硝酸锰、氯化锰中的一种或几种。
优选的是,所述的促进汽车尾气净化的催化剂,其中:所述进气段的涂覆量为50~300g/L,所述出气段的涂覆量为50~150g/L。
优选的是,所述的促进汽车尾气净化的催化剂,其中:所述上涂层的涂覆量为50~130g/L。
优选的是,所述的促进汽车尾气净化的催化剂,其中:所述进气段中Rh的含量为0.1~10g/ft3,所述出气段中Pd的含量为1~150g/ft3,所述上涂层Mn的含量为0.05~10g/ft3。
优选的是,所述的促进汽车尾气净化的催化剂,其中:所述二氧化钛和铈锆固溶体的质量比为1:10~10:1。
本发明的优点:
(1)本发明的促进汽车尾气净化的催化剂,通过优化涂层组成及贵金属分布来增强尾气净化性能,下涂层Rh负载于CeAl固溶体可以避免Rh被过度老化造成Rh还原性能下降,Pd负载于后段La2O3-Al2O3提高Pd的抗劣化性能;上涂层Mn负载于TiO2和铈锆固溶体促进不同工况下对NOx的转化。
(2)本发明的促进汽车尾气净化的催化剂,包括载体及涂覆于载体上的涂层,涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段包括贵金属Pd,Pd负载于La2O3-Al2O3上;上涂层包括Mn,Mn负载于二氧化钛和铈锆固溶体上,上述组分通过协同作用增强了催化剂的尾气净化性能。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
实施例1
一种促进汽车尾气净化的催化剂,包括载体及涂覆于所述载体上的涂层,所述涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,所述下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段包括贵金属Pd,Pd负载于La2O3-Al2O3上;上涂层包括Mn,Mn负载于二氧化钛和铈锆固溶体上。
CeAl固溶体中包括以下组分:20wt%的CeO2和80wt%的Al2O3,La2O3-Al2O3中包括以下组分:2wt%的La2O3和98wt%的Al2O3,铈锆固溶体包括ZrO2、CeO2和Y2O3,其中CeO2的含量为50wt%,ZrO2的含量为45wt%,Y2O3的含量为5wt%。
上述促进汽车尾气净化的催化剂的制备方法包括以下步骤:
(1)下涂层进气段的涂覆:将500g CeAl固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加10g硝酸铑溶液(含10wt%Rh)制得下层进气段浆料,并以100g/L的涂覆量从进气段涂覆四分之一催化剂长度,快速烘干,烘干温度为100℃,烘干时间为8min;
(2)下涂层出气段的涂覆:将500gLa2O3-Al2O3加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加10g硝酸钯溶液(含10wt%Pd)制得下层进气段浆料,并以100g/L的涂覆量从出气段涂覆四分之三催化剂长度,快速烘干,烘干温度为180℃,烘干时间为8min,随后将烘干后的催化剂以10℃/min的升温速率程序升温至500℃,焙烧1h,得到催化剂半成品;
(3)上涂层的涂覆:将250g二氧化钛和250g铈锆固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加25g硝酸锰溶液(含10wt%Mn)制得上涂层浆料,并以80g/L的涂覆量从进气段涂覆至步骤(2)制得的催化剂半成品上,烘干温度为180℃,烘干时间为8min,烘干后以20℃/min的升温速率程序升温至500℃,焙烧2h,得到催化剂成品。
实施例2
一种促进汽车尾气净化的催化剂,包括载体及涂覆于所述载体上的涂层,所述涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,所述下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段包括贵金属Pd,Pd负载于La2O3-Al2O3上;上涂层包括Mn,Mn负载于二氧化钛和铈锆固溶体上。
CeAl固溶体中包括以下组分:50wt%的CeO2和50wt%的Al2O3,La2O3-Al2O3中包括以下组分:4wt%的La2O3和96wt%的Al2O3,铈锆固溶体包括ZrO2、CeO2和Nd2O3,其中CeO2的含量为60wt%,ZrO2的含量为35wt%,Nd2O3的含量为5wt%。
上述促进汽车尾气净化的催化剂的制备方法包括以下步骤:
(1)下涂层进气段的涂覆:将500g CeAl固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加5g硝酸铑溶液(含10wt%Rh)制得下层进气段浆料,并以100g/L的涂覆量从进气段涂覆二分之一催化剂长度,快速烘干,烘干温度为100℃,烘干时间为8min;
(2)下涂层出气段的涂覆:将500gLa2O3-Al2O3加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加10g硝酸钯溶液(含10wt%Pd)制得下层进气段浆料,并以100g/L的涂覆量从出气段涂覆二分之一催化剂长度,快速烘干,烘干温度为180℃,烘干时间为8min,随后将烘干后的催化剂以10℃/min的升温速率程序升温至500℃,焙烧1h,得到催化剂半成品;
(3)上涂层的涂覆:将100g二氧化钛和400g铈锆固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加25g氯化锰溶液(含10wt%Mn)制得上涂层浆料,并以80g/L的涂覆量从进气段涂覆至步骤(2)制得的催化剂半成品上,烘干温度为180℃,烘干时间为8min,烘干后以20℃/min的升温速率程序升温至500℃,焙烧2h,得到催化剂成品。
实施例3
一种促进汽车尾气净化的催化剂,包括载体及涂覆于所述载体上的涂层,所述涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,所述下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段包括贵金属Pd,Pd负载于La2O3-Al2O3上;上涂层包括Mn,Mn负载于二氧化钛和铈锆固溶体上。
CeAl固溶体中包括以下组分:80wt%的CeO2和20wt%的Al2O3,La2O3-Al2O3中包括以下组分:4wt%的La2O3和96wt%的Al2O3,铈锆固溶体包括ZrO2、CeO2和La2O3,其中CeO2的含量为70wt%,ZrO2的含量为25wt%,La2O3的含量为5wt%。
上述促进汽车尾气净化的催化剂的制备方法包括以下步骤:
(1)下涂层进气段的涂覆:将500g CeAl固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加10g硝酸铑溶液(含10wt%Rh)制得下层进气段浆料,并以100g/L的涂覆量从进气段涂覆四分之一催化剂长度,快速烘干,烘干温度为100℃,烘干时间为8min;
(2)下涂层出气段的涂覆:将500gLa2O3-Al2O3加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加15g硝酸钯溶液(含10wt%Pd)制得下层进气段浆料,并以100g/L的涂覆量从出气段涂覆四分之三催化剂长度,快速烘干,烘干温度为180℃,烘干时间为8min,随后将烘干后的催化剂以10℃/min的升温速率程序升温至500℃,焙烧1h,得到催化剂半成品;
(3)上涂层的涂覆:将400g二氧化钛和100g铈锆固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加25g醋酸锰溶液(含10wt%Mn)制得上涂层浆料,并以80g/L的涂覆量从进气段涂覆至步骤(2)制得的催化剂半成品上,烘干温度为180℃,烘干时间为8min,烘干后以20℃/min的升温速率程序升温至500℃,焙烧2h,得到催化剂成品。
对比例1
一种促进汽车尾气净化的催化剂,包括载体及涂覆于所述载体上的涂层,所述涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,所述下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段包括贵金属Pd,Pd负载于La2O3-Al2O3上;上涂层包括Mn,Mn负载于铈锆固溶体上。
CeAl固溶体中包括以下组分:20wt%的CeO2和80wt%的Al2O3,La2O3-Al2O3中包括以下组分:2wt%的La2O3和98wt%的Al2O3,铈锆固溶体包括ZrO2、CeO2和Y2O3,其中CeO2的含量为50wt%,ZrO2的含量为45wt%,Y2O3的含量为5wt%。
上述促进汽车尾气净化的催化剂的制备方法包括以下步骤:
(1)下涂层进气段的涂覆:将500g CeAl固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加10g硝酸铑溶液(含10wt%Rh)制得下层进气段浆料,并以100g/L的涂覆量从进气段涂覆四分之一催化剂长度,快速烘干,烘干温度为100℃,烘干时间为8min;
(2)下涂层出气段的涂覆:将500gLa2O3-Al2O3加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加10g硝酸钯溶液(含10wt%Pd)制得下层进气段浆料,并以100g/L的涂覆量从出气段涂覆四分之三催化剂长度,快速烘干,烘干温度为180℃,烘干时间为8min,随后将烘干后的催化剂以10℃/min的升温速率程序升温至500℃,焙烧1h,得到催化剂半成品;
(3)上涂层的涂覆:将500g铈锆固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加25g硝酸锰溶液(含10wt%Mn)制得上涂层浆料,并以80g/L的涂覆量从进气段涂覆至步骤(2)制得的催化剂半成品上,烘干温度为180℃,烘干时间为8min,烘干后以20℃/min的升温速率程序升温至500℃,焙烧2h,得到催化剂成品。
对比例2
一种促进汽车尾气净化的催化剂,包括载体及涂覆于所述载体上的涂层,所述涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,所述下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段包括贵金属Pd,Pd负载于La2O3-Al2O3上;上涂层包括Mn,Mn负载于二氧化钛和铈锆固溶体上。
La2O3-Al2O3中包括以下组分:4wt%的La2O3和96wt%的Al2O3,铈锆固溶体包括ZrO2和CeO2和Nd2O3,其中CeO2的含量为60wt%,ZrO2的含量为35wt%,Nd2O3的含量为5wt%。
上述促进汽车尾气净化的催化剂的制备方法包括以下步骤:
(1)下涂层进气段的涂覆:将500g铈锆固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加5g硝酸铑溶液(含10wt%Rh)制得下层进气段浆料,并以100g/L的涂覆量从进气段涂覆二分之一催化剂长度,快速烘干,烘干温度为100℃,烘干时间为8min;
(2)下涂层出气段的涂覆:将500gLa2O3-Al2O3加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加10g硝酸钯溶液(含10wt%Pd)Pd的可溶性溶液制得下层进气段浆料,并以100g/L的涂覆量从出气段涂覆二分之一催化剂长度,快速烘干,烘干温度为180℃,烘干时间为8min,随后将烘干后的催化剂以10℃/min的升温速率程序升温至500℃,焙烧1h,得到催化剂半成品;
(3)上涂层的涂覆:将100g二氧化钛和400g铈锆固溶体加入去离子水中搅拌30min,经过球磨控制颗粒度为15μm,滴加25g氯化锰溶液(含10wt%Mn)制得上涂层浆料,并以80g/L的涂覆量从进气段涂覆至步骤(2)制得的催化剂半成品上,烘干温度为180℃,烘干时间为8min,烘干后以20℃/min的升温速率程序升温至500℃,焙烧2h,得到催化剂成品。
将实施例1-3和对比例1-2制备的催化剂进行测试,测试方法包括以下步骤:
将实施例1-3、对比例1-2所得到的催化剂样品在1050℃的高温管式炉内同条件老化20h,氛围为N2,然后封装为净化器,按WLTCΙ型试验进行整车排放测试,实施例1-3和对比例1-2均为同一条件下测试,测试车辆的发动机排量为1.6L,排放测试结果如表1所示。
表1实施例1-3和对比例1-2得到的催化剂的催化性能比较
THC(mg/km) | CO(mg/km) | NOX(mg/km) | |
实施例1 | 19.5 | 162.1 | 30.3 |
实施例2 | 21.5 | 210.7 | 31.2 |
实施例3 | 22.7 | 220.4 | 33.8 |
对比例1 | 38.3 | 296.7 | 41.6 |
对比例2 | 41.5 | 310.6 | 44.9 |
注:表1中THC表示气体中含有碳氢化合物的总量的缩写。
如表1所示,催化剂性能评价的结果表明,与对比例1-2相比,本发明实施例1-3所制备的三元催化剂在各瞬态工况具有优异的尾气净化能力,其在CO、HC和NOx的转化方面均表现出较好的催化性能。
本发明的促进汽车尾气净化的催化剂,包括载体及涂覆于载体上的涂层,涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段为贵金属Pd,Pd负载于La2O3-Al2O3上;上涂层包括Mn,Mn负载于二氧化钛和铈锆固溶体上,本发明通过优化涂层组成及贵金属分布来增强尾气净化性能。
最后所应说明的是,以上具体实施方式仅用以说明本发明的技术方案而非限制,尽管参照实例对本发明进行了详细说明,本领域的技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (10)
1.一种促进汽车尾气净化的催化剂,其特征在于:催化剂包括载体及涂覆于所述载体上的涂层,所述涂层包括设置于载体上的下涂层和设置于下涂层上的上涂层,所述下涂层包括进气段和出气段,进气段包括贵金属Rh,贵金属Rh负载于CeAl固溶体上,出气段包括贵金属Pd,Pd负载于La2O3-Al2O3上;上涂层包括Mn,Mn负载于二氧化钛和铈锆固溶体上。
2.根据权利要求1所述的促进汽车尾气净化的催化剂,其特征在于:CeAl固溶体包括以下组分:20wt%~80wt%的CeO2和80 wt%~20wt%的Al2O3。
3.根据权利要求1所述的促进汽车尾气净化的催化剂,其特征在于:La2O3-Al2O3包括以下组分:1 wt%~10wt%的La2O3和90 wt%~99wt%的Al2O3。
4.根据权利要求1所述的促进汽车尾气净化的催化剂,其特征在于:铈锆固溶体包括ZrO2和CeO2,其中CeO2的含量为50 wt%~95wt%。
5.根据权利要求1所述的促进汽车尾气净化的催化剂,其特征在于:所述铈锆固溶体还包括La2O3、Y2O3、Pr6O11、Nd2O3中的一种或几种,其含量为1 wt%~10wt%。
6.根据权利要求1所述的促进汽车尾气净化的催化剂,其特征在于:所述Mn的来源为醋酸锰、硝酸锰、氯化锰中的一种或几种。
7.根据权利要求1所述的促进汽车尾气净化的催化剂,其特征在于:所述进气段的涂覆量为50~300g/L,所述出气段的涂覆量为50~150g/ L。
8.根据权利要求1所述的促进汽车尾气净化的催化剂,其特征在于:所述上涂层的涂覆量为50~130g/ L。
9.根据权利要求1所述的促进汽车尾气净化的催化剂,其特征在于:所述进气段中Rh的含量为0.1~10g/ft3,所述出气段中Pd的含量为 1~150g/ft3,所述上涂层Mn的含量为0.05~10g/ft3。
10.根据权利要求1所述的促进汽车尾气净化的催化剂,其特征在于:所述二氧化钛和铈锆固溶体的质量比为1:10~10:1。
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