CN106807370A - 一种三效催化剂 - Google Patents
一种三效催化剂 Download PDFInfo
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- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 30
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
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- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 28
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 23
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
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- 150000001875 compounds Chemical class 0.000 claims 1
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- 239000010931 gold Substances 0.000 claims 1
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- 238000002360 preparation method Methods 0.000 abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
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- 239000003344 environmental pollutant Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
本发明涉及一种三效催化剂,属于催化剂制备技术领域。在所述蜂窝状载体上附着下层Pd涂层,在下层Pd涂层上附着中间Rh涂层,在中间Rh涂层上附着一层不含贵金属的碱土金属氧化物涂层;所述碱土金属氧化物由MgO、BaO、SrO、CaO中的一种氧化物或几种氧化物组成;所述中间Rh涂层和上层碱土金属氧化物涂层的质量比为10:1~30:1。本发明所述催化剂在高温老化后具有更高的一氧化碳、碳氢化合物和氮氧化合物处理能力。
Description
技术领域
本发明涉及一种三效催化剂,具体涉及一种用于汽油车尾气净化的三效催化剂,属于催化剂制备技术领域。
背景技术
汽车尾气的主要污染物是一氧化碳(CO)、碳氢化合物(HC)和氮氧化合物(NOx),利用安装在排气系统的催化剂可以将一氧化碳、碳氢化合物氧化成二氧化碳(CO2)、水(H2O),并同时使氮氧化合物还原为氮气(N2),实现尾气的净化,这种催化剂通常称为三效催化剂。三效催化剂由两部分组成:蜂窝状的陶瓷或金属载体,以及附着在载体上的催化剂涂层。催化剂涂层通常由具有较大比表面积的氧化物材料(如氧化铝)、储氧材料和分散在氧化物或储氧材料表面的贵金属活性组分(常为Pd(钯)、Rh(铑)中的一种或几种)组成。其中的储氧材料一般为含铈锆的复合氧化物,它通过吸附储存尾气中的氧或释放出氧来调节尾气中氧化性组分和还原性组分的比例,使一氧化碳和碳氢化合物被氧化的同时氮氧化合物被还原。为了提高汽车冷启动时污染物的转化效率,三效催化剂常被安装在靠近发动机排气歧管出口的位置,在汽车高速行驶时,三效催化剂的床层温度可达到900~1050℃的高温。
主要为了抑制高温条件下Rh与Pd的合金化作用而使催化剂活性下降,目前的三效催化剂通常都采用双涂层结构,即附着在蜂窝载体上的下涂层担载Pd,而附着在下涂层上的上涂层担载Rh,通过分层在空间上分离了Pd与Rh。但是,即使采用Pd和Rh分离的双涂层结构,在高温(如900~1050℃)条件下,依然会有部分Rh向下层迁移并与Pd发生相互作用而使催化剂活性下降。所以,如果能够进一步约束Rh向Pd涂层的高温迁移,那么可以进一步提高催化剂的抗高温老化性能。
发明内容
本发明的目的在于克服上述不足之处,提供一种三效催化剂,使其具有更高的抗高温老化能力。
按照本发明提供的技术方案,一种三效催化剂,包括蜂窝状载体,在所述蜂窝状载体上附着下层Pd涂层,在下层Pd涂层上附着中间Rh涂层,在中间Rh涂层上附着一层不含贵金属的碱土金属氧化物涂层;
所述中间Rh涂层和上层碱土金属氧化物涂层的质量比为10~30:1。
所述上层碱土金属氧化物涂层中碱土金属氧化物质量占上层涂层质量的99%以上。
所述碱土金属氧化物由BaO、SrO或CaO中的一种或几种氧化物组成,氧化物的前驱体是水溶性的碱土金属盐或碱土氢氧化物。
所述下层Pd涂层包括负载Pd的铈锆固溶体和La2O3掺杂的氧化铝La2O3-Al2O3;铈锆固溶体与La2O3-Al2O3的质量比为1:10~10:1。
所述中间层Rh涂层包括负载Rh的铈锆固溶体和La2O3掺杂的氧化铝La2O3-Al2O3;铈锆固溶体与La2O3-Al2O3的质量比为1:10~10:1。
所述的铈锆固溶体按重量份计组份为:5~60份CeO2、30~90份ZrO2和5~15份的La2O3、Y2O3、Pr6O11或Nd2O3中的一种或几种。
所述的La2O3-Al2O3中,La2O3的含量占La-Al2O3质量的1%~5%。
所述下层Pd涂层的涂层涂覆量为30~200g/L,负载的Pd的含量为5~200g/ft3。
所述中间Rh涂层的涂层涂覆量为30~200g/L,负载的Rh的含量为0.5~20g/ft3。
本发明的有益效果:本发明所述三效催化剂,在传统的Pd/Rh双涂层催化剂技术的基础上,在Rh涂层上额外负载一层碱土金属氧化物涂层,可以更有效抑制高温条件下Rh向下层Pd的迁移,避免Pd与Rh的合金化作用,提高了三效催化剂的抗高温老化性能。
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
一种三效催化剂,包括蜂窝状载体,规格为Ф101.6mm×123.3mm,孔密度为600cpsi,孔道壁厚为4.3mil,体积为1.0L;在所述蜂窝状载体上附着下层涂层,下层涂层的涂覆量为101g/L,在下层涂层上负载Pd,Pd负载在铈锆固溶体上,Pd的含量为28.3g/ft3;在所述下层涂层上附着中间Rh涂层,中间Rh涂层的涂覆量为100g/L,Rh的含量为2.83g/ft3;在所述中间Rh涂层上附着上层碱土金属氧化物涂层,涂覆量为5g/L,碱土金属氧化物为BaO。
所述三效催化剂的制备方法,采用以下工艺步骤:
(1)所述下层Pd涂层的涂覆过程:将50g的铈锆固溶体(30wt%CeO2、60wt%ZrO2、5wt%La2O3和5wt%Y2O3)、50g的La2O3-Al2O3(La2O3占La2O3-Al2O3的4wt%)、和6.90g硝酸钯溶液(溶液中Pd含量14.5wt%)和适量去离子水混合,并经球磨后配制得到涂层浆液;将该涂层浆液涂覆到蜂窝状载体上,并在550℃温度下焙烧2小时,得到下层Pd涂层;
(2)所述中间Rh涂层的涂覆过程:将50g的铈锆固溶体(30wt%CeO2、60wt%ZrO2、5wt%La2O3和5wt%Y2O3)、50g的La2O3-Al2O3(La2O3占La2O3-Al2O3的4wt%)、和2.00g硝酸钯溶液(溶液中Rh含量5.0wt%)和适量去离子水混合,并经球磨后配制得到涂层浆液;将该涂层浆液涂覆到下层Pd涂层上,并在550℃温度下焙烧2小时,得到中间层Rh涂层;
(3)所述上层碱土金属氧化物涂层的涂覆过程:用Ba(CH3COO)2(醋酸钡)、PVP(聚乙烯吡咯烷酮)配制BaO含量为5wt%的Ba(CH3COO)2(醋酸钡)水溶液,将100g该溶液涂覆到中间层Rh涂层上,并在550℃温度下焙烧2小时,得到BaO涂覆量为5g/L的碱土金属氧化物涂层。
整车排放测试结果如表1所示。
实施例2
一种三效催化剂,包括蜂窝状载体,规格为Ф101.6mm×123.3mm,孔密度为600cpsi,孔道壁厚为4.3mil,体积为1.0L;在所述蜂窝状载体上附着下层涂层,下层涂层的涂覆量为101g/L,在下层涂层上负载Pd,Pd负载在铈锆固溶体上,Pd的含量为28.3g/ft3;在所述下层涂层上附着中间Rh涂层,中间Rh涂层的涂覆量为100g/L,Rh的含量为2.83g/ft3;在所述中间Rh涂层上附着上层碱土金属氧化物涂层,碱土金属氧化物为2.5g/L的BaO和2.5g/L的SrO。
所述三效催化剂的制备方法,采用以下工艺步骤:
(1)所述下层Pd涂层的涂覆过程:将50g的铈锆固溶体(30wt%CeO2、60wt%ZrO2、5wt%La2O3和5wt%Y2O3)、50g的La2O3-Al2O3(La2O3占La2O3-Al2O3的4wt%)、和6.90g硝酸钯溶液(溶液中Pd含量14.5wt%)和适量去离子水混合,并经球磨后配制得到涂层浆液;将该涂层浆液涂覆到蜂窝状载体上,并在550℃温度下焙烧2小时,得到下层Pd涂层;
(2)所述中间Rh涂层的涂覆过程:将50g的铈锆固溶体(30wt%CeO2、60wt%ZrO2、5wt%La2O3和5wt%Y2O3)、50g的La2O3-Al2O3(La2O3占La2O3-Al2O3的4wt%)、和2.00g硝酸钯溶液(溶液中Rh含量5.0wt%)和适量去离子水混合,并经球磨后配制得到涂层浆液;将该涂层浆液涂覆到下层Pd涂层上,并在550℃温度下焙烧2小时,得到中间层Rh涂层;
(3)所述上层碱土金属氧化物涂层的涂覆过程:用Ba(CH3COO)2(醋酸钡)、Sr(CH3COO)2(醋酸锶)、PVP(聚乙烯吡咯烷酮)配制BaO含量为2.5wt%、SrO含量为2.5wt%的混合碱土金属盐水溶液,将100g该溶液涂覆到中间层Rh涂层上,并在550℃温度下焙烧2小时,得到BaO和SrO涂覆量各为2.5g/L的碱土金属氧化物涂层。
整车排放测试结果如表1所示。
实施例3
一种三效催化剂,包括蜂窝状载体,规格为Ф101.6mm×123.3mm,孔密度为600cpsi,孔道壁厚为4.3mil,体积为1.0L;在所述蜂窝状载体上附着下层涂层,下层涂层的涂覆量为101g/L,在下层涂层上负载Pd,Pd负载在铈锆固溶体上,Pd的含量为28.3g/ft3;在所述下层涂层上附着中间Rh涂层,中间Rh涂层的涂覆量为100g/L,Rh的含量为2.83g/ft3;在所述中间Rh涂层上附着上层碱土金属氧化物涂层,碱土金属氧化物为10g/L的BaO。
所述三效催化剂的制备方法,采用以下工艺步骤:
(1)所述下层Pd涂层的涂覆过程:将50g的铈锆固溶体(30wt%CeO2、60wt%ZrO2、5wt%La2O3和5wt%Y2O3)、50g的La2O3-Al2O3(La2O3占La2O3-Al2O3的4wt%)、和6.90g硝酸钯溶液(溶液中Pd含量14.5wt%)和适量去离子水混合,并经球磨后配制得到涂层浆液;将该涂层浆液涂覆到蜂窝状载体上,并在550℃温度下焙烧2小时,得到下层Pd涂层;
(2)所述中间Rh涂层的涂覆过程:将50g的铈锆固溶体(30wt%CeO2、60wt%ZrO2、5wt%La2O3和5wt%Y2O3)、50g的La2O3-Al2O3(La2O3占La2O3-Al2O3的4wt%)、和2.00g硝酸钯溶液(溶液中Rh含量5.0wt%)和适量去离子水混合,并经球磨后配制得到涂层浆液;将该涂层浆液涂覆到下层Pd涂层上,并在550℃温度下焙烧2小时,得到中间层Rh涂层;
(3)所述上层碱土金属氧化物涂层的涂覆过程:用Ba(CH3COO)2(醋酸钡)、PVP(聚乙烯吡咯烷酮)配制BaO含量为5wt%的碱土金属盐水溶液,将200g该溶液涂覆到中间层Rh涂层上,并在550℃温度下焙烧2小时,得到BaO涂覆量为10g/L的碱土金属氧化物涂层。
整车排放测试结果如表1所示。
实施例4
一种三效催化剂,包括蜂窝状载体,规格为Ф101.6mm×123.3mm,孔密度为600cpsi,孔道壁厚为4.3mil,体积为1.0L;在所述蜂窝状载体上附着下层涂层,下层涂层的涂覆量为101g/L,在下层涂层上负载Pd,Pd负载在铈锆固溶体上,Pd的含量为28.3g/ft3;在所述下层涂层上附着中间Rh涂层,中间Rh涂层的涂覆量为100g/L,Rh的含量为2.83g/ft3;在所述中间Rh涂层上附着上层碱土金属氧化物涂层,碱土金属氧化物为5g/L的SrO。
所述三效催化剂的制备方法,采用以下工艺步骤:
(1)所述下层Pd涂层的涂覆过程:将50g的的铈锆固溶体(30wt%CeO2、60wt%ZrO2、5wt%La2O3和5wt%Y2O3)、50g的La2O3-Al2O3(La2O3占La2O3-Al2O3的4wt%)、和6.90g硝酸钯溶液(溶液中Pd含量14.5wt%)和适量去离子水混合,并经球磨后配制得到涂层浆液;将该涂层浆液涂覆到蜂窝状载体上,并在550℃温度下焙烧2小时,得到下层Pd涂层;
(2)所述中间Rh涂层的涂覆过程:将50g的铈锆固溶体(30wt%CeO2、60wt%ZrO2、5wt%La2O3和5wt%Y2O3)、50g的La2O3-Al2O3(La2O3占La2O3-Al2O3的4wt%)、和2.00g硝酸钯溶液(溶液中Rh含量5.0wt%)和适量去离子水混合,并经球磨后配制得到涂层浆液;将该涂层浆液涂覆到下层Pd涂层上,并在550℃温度下焙烧2小时,得到中间层Rh涂层;
(3)所述上层碱土金属氧化物涂层的涂覆过程:用Sr(OH)2(氢氧化锶)、PVP(聚乙烯吡咯烷酮)配制SrO含量为2.5wt%的碱土金属盐水溶液,将200g该溶液涂覆到中间层Rh涂层上,并在550℃温度下焙烧2小时,得到SrO涂覆量为5g/L的碱土金属氧化物涂层。
整车排放测试结果如表1所示。
对比实施例1
各参数、组成和制备过程与实施例1相同,除了不进行步骤(3),即Rh层上不涂覆碱土金属氧化物涂层。
整车排放测试结果如表1所示。
对比实施例2
各参数、组成和制备过程与实施例1相同,除了上层碱土金属氧化物涂层中的BaO涂覆量为15g/L。
整车排放测试结果如表1所示。
对比实施例3
各参数、组成和制备过程与实施例1相同,除了上层碱土金属氧化物涂层中的BaO涂覆量为0.5g/L。
整车排放测试结果如表1所示。
将实施例1~5和对比实施例1~3所得到的催化剂样品在高温马弗炉中1000℃老化20小时后,按ECE+EUDC循环进行整车排放测试,测试车辆的发动机排量为1.2L。排放测试结果如表1所示。
表1
如表1所示,催化剂性能评价的结果表明,与对比实施例1~3相比,本发明实施例1~4所公开的三效催化剂具有更高的污染物处理能力,尤其是更优异的抗高温老化性能。
Claims (9)
1.一种三效催化剂,包括蜂窝状载体,其特征是:在所述蜂窝状载体上附着下层Pd涂层,在下层Pd涂层上附着中间Rh涂层,在中间Rh涂层上附着一层不含贵金属的碱土金属氧化物涂层;
所述中间Rh涂层和上层碱土金属氧化物涂层的质量比为10~30:1。
2.如权利要求1所述的三效催化剂,其特征是:所述上层碱土金属氧化物涂层中碱土金属氧化物质量占上层涂层质量的99%以上。
3.如权利要求1所述的三效催化剂,其特征是:所述碱土金属氧化物由BaO、SrO或CaO中的一种或几种氧化物组成,氧化物的前驱体是水溶性的碱土金属盐或碱土氢氧化物。
4.如权利要求1所述的三效催化剂,其特征是:所述下层Pd涂层包括负载Pd的铈锆固溶体和La2O3掺杂的氧化铝La2O3-Al2O3;铈锆固溶体与La2O3-Al2O3的质量比为1:10~10:1。
5.如权利要求1所述的三效催化剂,其特征是:所述中间层Rh涂层包括负载Rh的铈锆固溶体和La2O3掺杂的氧化铝La2O3-Al2O3;铈锆固溶体与La2O3-Al2O3的质量比为1:10~10:1。
6.如权利要求4或5所述的三效催化剂,其特征是:所述的铈锆固溶体按重量份计组份为:5~60份CeO2、30~90份ZrO2和5~15份的La2O3、Y2O3、Pr6O11或Nd2O3中的一种或几种。
7.如权利要求4或5所述的三效催化剂,其特征是:所述的La2O3-Al2O3中,La2O3的含量占La-Al2O3质量的1%~5%。
8.如权利要求4所述的三效催化剂,其特征是:所述下层Pd涂层的涂层涂覆量为30~200g/L,负载的Pd的含量为5~200g/ft3。
9.如权利要求4所述的三效催化剂,其特征是:所述中间Rh涂层的涂层涂覆量为30~200g/L,负载的Rh的含量为0.5~20g/ft3。
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