CN107469830B - 一种基于钙钛矿结构的汽车尾气催化剂及其制备方法 - Google Patents
一种基于钙钛矿结构的汽车尾气催化剂及其制备方法 Download PDFInfo
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
本发明涉及一种基于钙钛矿结构的汽车尾气催化剂及其制备方法,属于环保技术领域。本催化剂以蜂窝陶瓷为载体,蜂窝陶瓷内孔道壁上有一层稀土复合氧化物以及TiO2‑SiO2组成的复合涂层,复合涂层上又有一层含CuO以及La‑K‑Mn‑Fe‑O组成的活性涂层,其中稀土复合氧化物为不同配比的Ce‑Zr固溶体稀土复合氧化物。本发明制备得到的催化剂中不含贵金属,起始活性好,同时本方法工艺简单。
Description
技术领域
本发明涉及一种基于钙钛矿结构的汽车尾气催化剂及其制备方法,属于环保技术领域。
背景技术
汽车尾气是世界范围的主要大气污染源,安装三元催化器是汽车尾气机外净化的有效装置,在控制空燃比的情况下,能同时净化汽车尾气中CO、HC、NOX有毒的成分。人们在三效催化剂及其制备工艺方面有过许多的研究,特别是钙钛矿型和稀土-贵金属型催化剂,但存在着贵金属含量高、起始活性差、制造工艺复杂、而且无法净化固体碳颗粒等缺点。
发明内容
针对上述现有技术存在的问题及不足,本发明提供一种基于钙钛矿结构的汽车尾气催化剂及其制备方法。本发明制备得到的催化剂中不含贵金属,起始活性好,同时本方法工艺简单,本发明通过以下技术方案实现。
一种基于钙钛矿结构的汽车尾气催化剂,以蜂窝陶瓷为载体,蜂窝陶瓷内孔道壁上有一层稀土复合氧化物以及TiO2-SiO2组成的复合涂层,复合涂层上又有一层含CuO以及La-K-Mn-Fe-O组成的活性涂层。
一种基于钙钛矿结构的汽车尾气催化剂的制备方法,其具体步骤如下:
步骤1、首先将稀土复合氧化物、TiO2、SiO2均匀混合得到混合物,混合物置于水溶液中形成混合浆液,加入分析纯硝酸并调节pH,然后将蜂窝陶瓷经脱气处理后,在室温下混合浆液中浸渍30~40min,浸渍完成后取出用高压气体吹除蜂窝陶瓷孔道壁的残余浆液,在室温***干24h,最后经干燥并在温度为550℃~800℃下焙烧3~4h得到焙烧产物;
步骤2、首先将硝酸镧、硝酸锰、硝酸铁、硝酸钾置于水溶液中形成混合溶液并调节pH,将步骤1得到的焙烧产物在室温下混合浆液中浸泡20~30min,干燥后在温度为500~700℃高温下焙烧3~4h得到催化剂半成品;
步骤3、将步骤2得到的催化剂半成品在室温下硝酸铜溶液中浸渍20~30min,干燥后在温度为700~800℃高温下焙烧3~4h得到催化剂。
所述步骤1中的稀土复合氧化物为氧化铈、氧化锆、氧化钇、氧化镨其中的两种或两种以上任意比例的混合物,稀土复合氧化物加入量为25~100g/L混合浆液。
所述步骤1中混合物与水溶液的固液比为70~190:1g/L。
所述步骤1中TiO2加入量为10~50g/L混合浆液。
所述步骤2硝酸镧、硝酸锰、硝酸铁、硝酸钾中La:Mn:Fe:K摩尔比为7:6:4:3,硝酸镧与水溶液的固液比为1~15:1g/L。
所述步骤3中硝酸铜溶液浓度为1.4~1.6g/L。
本发明的有益效果是:本方法制备得到的催化剂,以蜂窝陶瓷为载体,以CuO和La-K-Mn-Fe-O为催化剂活性组份,产品经一次或者二次高温焙烧就可直接使用,产品不经还原处理,CO、HC、NOX、固体颗粒的转化率为97%、97.8%、99%、40%;本方法中起燃温度低于300℃。
具体实施方式
下面结合具体实施方式,对本发明作进一步说明。
实施例1
该基于钙钛矿结构的汽车尾气催化剂,以蜂窝陶瓷为载体,蜂窝陶瓷内孔道壁上有一层稀土复合氧化物以及TiO2-SiO2组成的复合涂层,复合涂层上又有一层含CuO以及La-K-Mn-Fe-O组成的活性涂层。
该基于钙钛矿结构的汽车尾气催化剂的制备方法,其具体步骤如下:
步骤1、首先将稀土复合氧化物(质量比为1:1的氧化铈和氧化锆复合氧化物)、TiO2、SiO2均匀混合得到混合物,混合物置于2L水溶液中形成混合浆液,加入0.2L分析纯硝酸并用氨水调节pH4.5-5,其中稀土复合氧化物加入量为100g/L混合浆液,混合物与水溶液的固液比为190:1g/L,TiO2加入量为50g/L混合浆液,SiO2加入量为40g/L混合浆液;然后将蜂窝陶瓷(尺寸为φ144×152mm,孔数为400目/平方英寸的堇青石蜂窝陶瓷)经脱气处理后(在300℃马弗炉中烘干3小时),在室温下混合浆液中浸渍30min,浸渍完成后取出用高压气体吹除蜂窝陶瓷孔道壁的残余浆液,重复1-2次,使载体的涂覆率达到12%-18%,在室温***干24h,最后经干燥并在温度为600℃下焙烧4h得到焙烧产物;
步骤2、首先将硝酸镧、硝酸锰、硝酸铁、硝酸钾置于水溶液中形成混合溶液并采用氨水调节pH至4~5,将步骤1得到的焙烧产物在室温下混合浆液中浸泡30min,干燥后在温度为500℃高温下焙烧4h得到催化剂半成品;其中硝酸镧、硝酸锰、硝酸铁、硝酸钾中La:Mn:Fe:K摩尔比为7:6:4:3,硝酸镧与水溶液的固液比为1:1g/L;
步骤3、将步骤2得到的催化剂半成品在室温下硝酸铜溶液(硝酸铜溶液浓度为1.4g/L)中浸渍20min,干燥后在温度为800℃高温下焙烧4h得到催化剂A。
实施例2
该基于钙钛矿结构的汽车尾气催化剂,以蜂窝陶瓷为载体,蜂窝陶瓷内孔道壁上有一层稀土复合氧化物以及TiO2-SiO2组成的复合涂层,复合涂层上又有一层含CuO以及La-K-Mn-Fe-O组成的活性涂层。
该基于钙钛矿结构的汽车尾气催化剂的制备方法,其具体步骤如下:
步骤1、首先将稀土复合氧化物(质量比为1:1:1的氧化铈、氧化锆和氧化钇复合氧化物)、TiO2、SiO2均匀混合得到混合物,混合物置于2L水溶液中形成混合浆液,加入0.23L分析纯硝酸并用氨水调节pH4.5-5,其中稀土复合氧化物加入量为25g/L混合浆液,混合物与水溶液的固液比为70:1g/L,TiO2加入量为10g/L混合浆液,SiO2加入量为35g/L混合浆液;然后将蜂窝陶瓷(尺寸为φ144×152mm,孔数为400目/平方英寸的堇青石蜂窝陶瓷)经脱气处理后(在300℃马弗炉中烘干3小时),在室温下混合浆液中浸渍40min,浸渍完成后取出用高压气体吹除蜂窝陶瓷孔道壁的残余浆液,重复1-2次,使载体的涂覆率达到12%-18%,在室温***干24h,最后经干燥并在温度为800℃下焙烧3h得到焙烧产物;
步骤2、首先将硝酸镧、硝酸锰、硝酸铁、硝酸钾置于水溶液中形成混合溶液并采用氨水调节pH至4~5,将步骤1得到的焙烧产物在室温下混合浆液中浸泡20min,干燥后在温度为700℃高温下焙烧3h得到催化剂半成品;其中硝酸镧、硝酸锰、硝酸铁、硝酸钾中La:Mn:Fe:K摩尔比为7:6:4:3,硝酸镧与水溶液的固液比为10:1g/L;
步骤3、将步骤2得到的催化剂半成品在室温下硝酸铜溶液(硝酸铜溶液浓度为1.6g/L)中浸渍30min,干燥后在温度为700℃高温下焙烧3h得到催化剂B。
将实施例1制备得到的催化剂A和实施例2制备得到的催化剂B进行催化剂活性检测:R180柴油发动机,当温度325℃,转速2600/min,α=2(α为过量空气系数)时的转化率时,催化剂对柴油机尾气中CO、HC、NOX、PM的转化率如下表1所示:
表1
从表1中可以看出催化剂A和B对CO、HC、NOX表现出较高的催化活性,说明催化剂A、B的可操作窗口较宽。同时通过实验可以得出,该催化剂对PM固体颗粒也有一定的催化活性。
实施例3
该基于钙钛矿结构的汽车尾气催化剂,以蜂窝陶瓷为载体,蜂窝陶瓷内孔道壁上有一层稀土复合氧化物以及TiO2-SiO2组成的复合涂层,复合涂层上又有一层含CuO以及La-K-Mn-Fe-O组成的活性涂层,其中稀土复合氧化物为不同配比的Ce-Zr固溶体稀土复合氧化物。
该基于钙钛矿结构的汽车尾气催化剂的制备方法,其具体步骤如下:
步骤1、首先将稀土复合氧化物(质量比为1:1:1:1的氧化铈、氧化锆、氧化钇和氧化镨复合氧化物)、TiO2、SiO2均匀混合得到混合物,混合物置于2L水溶液中形成混合浆液,加入0.23L分析纯硝酸并用氨水调节pH4.5-5,其中稀土复合氧化物加入量为80g/L混合浆液,混合物与水溶液的固液比为130:1g/L,TiO2加入量为40g/L混合浆液,SiO2加入量为10g/L混合浆液;然后将蜂窝陶瓷(尺寸为φ144×152mm,孔数为400目/平方英寸的堇青石蜂窝陶瓷)经脱气处理后(在300℃马弗炉中烘干3小时),在室温下混合浆液中浸渍35min,浸渍完成后取出用高压气体吹除蜂窝陶瓷孔道壁的残余浆液,重复1-2次,使载体的涂覆率达到12%-18%,在室温***干24h,最后经干燥并在温度为550℃下焙烧3.5h得到焙烧产物;
步骤2、首先将硝酸镧、硝酸锰、硝酸铁、硝酸钾置于水溶液中形成混合溶液并采用氨水调节pH至4~5,将步骤1得到的焙烧产物在室温下混合浆液中浸泡25min,干燥后在温度为600℃高温下焙烧3.5h得到催化剂半成品;其中硝酸镧、硝酸锰、硝酸铁、硝酸钾中La:Mn:Fe:K摩尔比为7:6:4:3,硝酸镧与水溶液的固液比为15:1g/L;
步骤3、将步骤2得到的催化剂半成品在室温下硝酸铜溶液(硝酸铜溶液浓度为1.5g/L)中浸渍25min,干燥后在温度为750℃高温下焙烧3.5h得到催化剂。
以上对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (5)
1.一种基于钙钛矿结构的汽车尾气催化剂,其特征在于:以蜂窝陶瓷为载体,蜂窝陶瓷内孔道壁上有一层稀土复合氧化物以及TiO2-SiO2组成的复合涂层,复合涂层上又有一层含CuO以及La-K-Mn-Fe-O组成的活性涂层;
该基于钙钛矿结构的汽车尾气催化剂的制备方法,其具体步骤如下:
步骤1、首先将稀土复合氧化物、TiO2、SiO2均匀混合得到混合物,混合物置于水溶液中形成混合浆液,加入分析纯硝酸并调节pH,然后将蜂窝陶瓷经脱气处理后,在室温下混合浆液中浸渍30~40min,浸渍完成后取出用高压气体吹除蜂窝陶瓷孔道壁的残余浆液,在室温***干24h,最后经干燥并在温度为550℃~800℃下焙烧3~4h得到焙烧产物;
步骤2、首先将硝酸镧、硝酸锰、硝酸铁、硝酸钾置于水溶液中形成混合溶液并调节pH,将步骤1得到的焙烧产物在室温下混合溶液中浸泡20~30min,干燥后在温度为500~700℃高温下焙烧3~4h得到催化剂半成品;
步骤3、将步骤2得到的催化剂半成品在室温下硝酸铜溶液中浸渍20~30min,干燥后在温度为700~800℃高温下焙烧3~4h得到催化剂;
所述步骤2硝酸镧、硝酸锰、硝酸铁、硝酸钾中La:Mn:Fe:K摩尔比为7:6:4:3,硝酸镧与水溶液的固液比为1~15g:1L。
2.根据权利要求1所述的基于钙钛矿结构的汽车尾气催化剂,其特征在于:所述步骤1中的稀土复合氧化物为氧化铈、氧化锆、氧化钇、氧化镨其中的两种或两种以上任意比例的混合物,稀土复合氧化物加入量为25~100g/L混合浆液。
3.根据权利要求1所述的基于钙钛矿结构的汽车尾气催化剂,其特征在于:所述步骤1中混合物与水溶液的固液比为70~190g:1L。
4.根据权利要求1所述的基于钙钛矿结构的汽车尾气催化剂,其特征在于:所述步骤1中TiO2加入量为10~50g/L混合浆液。
5.根据权利要求1所述的基于钙钛矿结构的汽车尾气催化剂,其特征在于:所述步骤3中硝酸铜溶液浓度为1.4~1.6g/L。
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