CN111151257A - 一种整体式钙钛矿催化剂、制备方法及其应用 - Google Patents
一种整体式钙钛矿催化剂、制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种整体式钙钛矿催化剂、制备方法及其应用,属于催化剂的制备技术领域。其结构为ABO3,A位为Pr1‑xCax,X=0.1、0.2或0.3,B位为Co、Mn、Fe、Cu中的一种或两种。其制备方法包括:首先选取堇青石蜂窝陶瓷作为载体,并对其进行预处理;然后按照一定的化学计量比称取相关原料溶解,溶解在一定量的去离子水,搅拌,水浴加热溶解,再加入一定量的柠檬酸,搅拌溶解,得催化剂前驱体溶液;最后,将预处理后的载体浸渍在催化剂前驱体溶液中,浸渍完成后取出,经干燥、煅烧,即得。本发明整体式钙钛型催化剂的制备成本低、耗能少,且具有较高的催化活性。
Description
技术领域
本发明属于催化剂的制备技术领域,具体涉及一种高效减少燃油车污染物排放的整体式钙钛矿催化剂及制备方法。
背景技术
近年来,随着煤矿开采机械化水平的提高,井下燃油车在工作过程中产生碳烟颗粒物及各种有毒有害气体都对井下工作人员产生巨大的危害,所以对于井下燃油车尾气的治理至关重要。
目前对于井下燃油车尾气难以扩散,污染严重的问题,我国采用催化剂进行治理是一种有效手段,四效催化剂主要包括贵金属四效催化剂和非贵金属四效催化剂,贵金属催化剂相对于过渡金属有较高的活性,但是成本高,热稳定性差。而钙钛矿催化剂具有成分灵活、成本较低、热稳定性好的优点成为人们进行催化治理的有效方法。
但是目前治理井下燃油车尾气的催化剂仍然存在一些问题,比如催化活性低,而且不能同时去除有毒有害气体及颗粒物,针对以上问题,本发明提供了一种整体式钙钛矿催化剂。
发明内容
本发明的目的在于提供一种整体式钙钛矿催化剂、制备方法及其应用,该催化剂具有固定的形状和大小,其通过选用堇青石为载体,并且结合对载体进行前处理等步骤,提高了催化剂的催化活性。
本发明的任务之一在于提供一种整体式钙钛矿催化剂,其采用了以下技术方案:
一种整体式钙钛矿催化剂,其结构为ABO3,其特征在于:A位为Pr1-xCax,X=0.1、0.2或0.3,B位为Co、Mn、Fe、Cu中的一种或两种。
本发明的另一任务在于提供上述整体式钙钛矿催化剂的制备方法,依次包括以下步骤:
a、对载体预处理
选取堇青石蜂窝陶瓷作为载体,将堇青石蜂窝陶瓷载体浸渍在一定质量分数的草酸溶液中,然后密封处理并对其进行干燥,干燥后取出载体,用清水清洗达到中性,室内自然晾干,最后放置在马弗炉中煅烧,得到预处理后的载体;
b、制备催化剂前驱体溶液
按照一定的化学计量比称取相关原料,溶解在一定量的去离子水,搅拌,90℃水浴加热溶解,再加入一定量的柠檬酸,搅拌溶解,得催化剂前驱体溶液;
c、将步骤a所述的预处理后的载体浸渍在步骤b所述的催化剂前驱体溶液中,浸渍完成后取出,经干燥、煅烧,即得。
进一步的,步骤a中,草酸溶液的质量分数为10%~20%,浸渍时间为30~60min,放入电热鼓风干燥箱中对其进行干燥,干燥温度为70℃~90℃,干燥时间为3~5h;在马弗炉中煅烧温度为400℃~500℃,煅烧时间为1~2h。
进一步的,步骤b中,加入柠檬酸后所得混合溶液中柠檬酸的浓度在0.5~0.6mol/L。
进一步的,步骤c中,浸渍时间为20~40min,干燥温度为80℃~90℃,干燥时间为11~12h,煅烧温度为600℃~800℃,煅烧时间为4~5h。
本发明的再一任务在于提供上述一种整体式钙钛矿催化剂的应用。
上述的一种整体式钙钛矿催化剂在减少燃油车污染物排放中的应用。
上述的应用中,燃油车污染物主要包括氮氧化物、碳氧化物、碳氢化合物等有毒有害气体及颗粒物。
与现有技术相比,本发明带来了以下有益技术效果:
(1)本发明采用堇青石蜂窝陶瓷为载体,堇青石蜂窝陶瓷载体是柴油车、汽油车催化剂、DOC、SCR等催化剂的主要载体,它可以提供有效的表面积及合适的孔结构,使得催化剂的活性组分有效散开;提高催化剂的抗压强度,使催化剂具有固定的大小和形状。单单采用堇青石蜂窝陶瓷为载体还无法提高催化剂活性,还需对该堇青石蜂窝陶瓷载体进行预处理,通过预处理,降低蜂窝陶瓷载体的热膨胀系数,使得蜂窝陶瓷载体的热稳定性更高;通过草酸对载体进行预处理,可以增加载体的粗糙度,使催化剂更有利于附着,而且也可以提高蜂窝陶瓷载体的比表面积,使催化剂更好地分散。
(2)预处理后的载体浸渍在催化剂前驱体溶液中,浸渍一段时间后达到所要求的负载量,此时催化剂负载于载体上,实现催化剂溶液与载体的结合,得到整体式催化剂,此种结合提高了催化剂的比表面积及热稳定性,使得催化剂的催化活性更高。
(3)本发明整体式钙钛型催化剂的制备成本低、耗能少,且具有较高的催化活性。
具体实施方式
本发明提出了一种整体式钙钛矿催化剂、制备方法及其应用,为了使本发明的优点、技术方案更加清楚、明确,下面结合具体实施例对本发明做详细说明。
本发明所需原料均可通过商业渠道购买获得。
实施例1:
一种高效减少燃油车污染物排放的整体式钙钛矿催化剂,所述催化剂的结构为ABO3,其催化剂的简单表达式为Pr0.9Ca0.1FeO3,此时X取0.1。
制备该催化剂主要包括以下步骤:
(1)载体的预处理。首先将堇青石蜂窝陶瓷载体浸渍在质量分数为10%的草酸溶液当中,大约浸渍30min,密封之后放到电热鼓风干燥箱中70℃干燥3h,然后取出载体,同清水清洗达到中性,室内自然晾干,最后放置马弗炉400℃煅烧1h。
(2)催化剂前驱体溶液的制备。称取Pr(NO3)3·6H2O 0.783g、Ca(NO3)2·4H2O0.0472g和Fe(NO3)3·9H2O 0.808g溶解在一定量的去离子水中,使得溶液的体积为100mL,然后搅拌,90℃水浴加热溶解,再加入一定量的柠檬酸,使得柠檬酸的浓度为0.5mol/L,搅拌溶解,得到催化剂前驱体溶液。
(3)将预处理后的堇青石蜂窝陶瓷载体浸渍在催化剂前驱体溶液当中,大约浸渍20min,室内自然晾干,然后放置电热鼓风干燥箱中80℃干燥11h,取出后放置马弗炉中600℃煅烧4h,得到整体式催化剂。
对样品进行模拟尾气活性评价,采用常压固定床反应器进行催化活性的评价,分别测得尾气各成分的进口浓度和出口浓度,经计算得出尾气中CO、NOx、HC和PM的转化率分别是69%、56%、73%、76%,该催化剂的活性较高,催化性能较好,可以达到对尾气中有毒有害气体及颗粒物的同时去除。
实施例2:
一种高效减少燃油车污染物排放的整体式钙钛矿催化剂,所述催化剂的结构为ABO3,其催化剂的简单表达式为Pr0.8Ca0.2MnO3,此时X取0.2。
制备该催化剂主要包括以下步骤:
(1)载体的预处理。首先将堇青石蜂窝陶瓷载体浸渍在质量分数为14%的草酸溶液当中,大约浸渍40min,密封之后放到电热鼓风干燥箱中75℃干燥3.5h,然后取出载体,同清水清洗达到中性,室内自然晾干,最后放置马弗炉450℃煅烧1.5h。
(2)催化剂前驱体溶液的制备。称取Pr(NO3)3·6H2O 0.696g、Ca(NO3)2·4H2O0.0944g和Mn(CH3COO)2·4H2O 4.9g溶解在一定量的去离子水中,使得溶液的体积为100mL,然后搅拌,90℃水浴加热溶解,再加入一定量的柠檬酸,使得柠檬酸的浓度为0.55mol/L,搅拌溶解,得到催化剂前驱体溶液。
(3)将预处理后的堇青石蜂窝陶瓷载体浸渍在催化剂前驱体溶液当中,大约浸渍30min,室内自然晾干,然后放置电热鼓风干燥箱中85℃干燥11.5h,取出后放置马弗炉中700℃煅烧4.5h,得到整体式催化剂。
对样品进行模拟尾气活性评价,采用常压固定床反应器进行催化活性的评价,分别测得尾气各成分的进口浓度和出口浓度,经计算得出尾气中CO、NOx、HC和PM的转化率分别是76%、58%、72%、78%,该催化剂的活性较高,催化性能较好,可以达到对尾气中有毒有害气体及颗粒物的同时去除。
实施例3:
一种高效减少燃油车污染物排放的整体式钙钛矿催化剂,所述催化剂的结构为ABO3,其催化剂的简单表达式为Pr0.7Ca0.3Co0.5Mn0.5O3,此时X取0.3。
制备该催化剂主要包括以下步骤:
(1)载体的预处理。首先将堇青石蜂窝陶瓷载体浸渍在质量分数为17%的草酸溶液当中,大约浸渍50min,密封之后放到电热鼓风干燥箱中85℃干燥4h,然后取出载体,同清水清洗达到中性,室内自然晾干,最后放置马弗炉450℃煅烧1.5h。
(2)催化剂前驱体溶液的制备。称取Pr(NO3)3·6H2O 0.609g、Ca(NO3)2·4H2O0.1416g、Mn(CH3COO)2·4H2O 0.245g和Co(NO3)2·4H2O 0.291g溶解在一定量的去离子水中,使得溶液的体积为100mL,然后搅拌,90℃水浴加热溶解,再加入一定量的柠檬酸,使得柠檬酸的浓度为0.55mol/L,搅拌溶解,得到催化剂前驱体溶液。
(3)将预处理后的堇青石蜂窝陶瓷载体浸渍在催化剂前驱体溶液当中,大约浸渍30min,室内自然晾干,然后放置电热鼓风干燥箱中85℃干燥11.5h,取出后放置马弗炉中700℃煅烧4.5h,得到整体式催化剂。
对样品进行模拟尾气活性评价,采用常压固定床反应器进行催化活性的评价,分别测得尾气各成分的进口浓度和出口浓度,经计算得出尾气中CO、NOx、HC和PM的转化率分别是69%、60%、75%、73%,与实例1、2对比,该催化剂的活性较高,催化性能较好,可以达到对尾气中有毒有害气体及颗粒物的同时去除。
实施例4:
一种高效减少燃油车污染物排放的整体式钙钛矿催化剂,所述催化剂的结构为ABO3,其催化剂的简单表达式为Pr0.7Ca0.3Fe0.5Cu0.5O3,此时X取0.3。
制备该催化剂主要包括以下步骤:
(1)载体的预处理。首先将堇青石蜂窝陶瓷载体浸渍在质量分数为20%的草酸溶液当中,大约浸渍60min,密封之后放到电热鼓风干燥箱中90℃干燥5h,然后取出载体,同清水清洗达到中性,室内自然晾干,最后放置马弗炉500℃煅烧2h。
(2)催化剂前驱体溶液的制备。称取Pr(NO3)3·6H2O 0.609g、Ca(NO3)2·4H2O0.1416g、Fe(NO3)3·9H2O 0.404g和Cu(NO3)2·3H2O 0.242g溶解在一定量的去离子水中,使得溶液的体积为100mL,然后搅拌,90℃水浴加热溶解,再加入一定量的柠檬酸,使得柠檬酸的浓度为0.6mol/L,搅拌溶解,得到催化剂前驱体溶液。
(3)将预处理后的堇青石蜂窝陶瓷载体浸渍在催化剂前驱体溶液当中,大约浸渍40min,室内自然晾干,然后放置电热鼓风干燥箱中90℃干燥12h,取出后放置马弗炉中800℃煅烧5h,得到整体式催化剂。
对样品进行模拟尾气活性评价,采用常压固定床反应器进行催化活性的评价,分别测得尾气各成分的进口浓度和出口浓度,经计算得出尾气中CO、NOx、HC和PM的转化率分别是70%、59%、77%、76%,与实例1、2对比,该催化剂的活性较高,催化性能较好,可以达到对尾气中有毒有害气体及颗粒物的同时去除。
对比例1:
一种用于净化燃油尾气颗粒及有害气体的复合式高效催化剂,该催化剂的结构为ABO3,其中A位为Ce1-xSrx,B位为Mn1-yPdy,此时x取0,y取0.2。
一种用于净化燃油尾气颗粒及有害气体的复合式高效催化剂的制备方法,包括以下步骤:
(1)按照以下质量标准分别称取:硝酸铈Ce(NO3)3·6H2O 17.36g、乙酸锰Mn(CH3COO)2·4H2O 7.84g和硝酸钯Pd(NO3)2 1.84g溶解在一定量的去离子水中,溶解后溶液的体积为200mL,搅拌溶解后加入柠檬酸16.8g,继续搅拌溶解。
(2)为使金属离子充分络合,一边搅拌,一边用氨水调节PH到7左右。
(3)设定温度为80℃,持续搅拌,使其形成干凝胶状,然后将其放置电热鼓风干燥箱内105℃烘干11h达到完全脱水。
(4)最后把样品置于马弗炉中进行煅烧,设置4℃/min升温到400℃,保温2h,然后同样的升温速度条件升温到800℃,保温4h,最后得到所需要的钙钛矿催化剂。
对样品进行活性测试,在固定床反应器催化评价装置上进行催化剂的活性测试,分别测定了加入催化剂前后尾气中的CO、NOx、HC(碳氢化合物)、PM(碳烟颗粒物)的数值,并计算出转化效率。测得CO的转化率为57%,NOx的转化率为61%,HC的转化率为55%,PM的转化率为63%。该催化剂的催化活性较好。
对比例2:
一种高效减少燃油车污染物排放的整体式钙钛矿催化剂,所述催化剂的结构为ABO3,其催化剂的简单表达式为Pr0.9Ca0.1FeO3,此时X取0.1。
制备该催化剂主要包括以下步骤:
(1)催化剂前驱体溶液的制备。称取Pr(NO3)3·6H2O 0.783g、Ca(NO3)2·4H2O0.0472g和Fe(NO3)3·9H2O 0.808g溶解在一定量的去离子水中,使得溶液的体积为100mL,然后搅拌,90℃水浴加热溶解,再加入一定量的柠檬酸,使得柠檬酸的浓度为0.5mol/L,搅拌溶解,得到催化剂前驱体溶液。
(2)将未经预处理的堇青石蜂窝陶瓷载体浸渍在催化剂前驱体溶液当中,大约浸渍20min,室内自然晾干,然后放置电热鼓风干燥箱中80℃干燥11h,取出后放置马弗炉中600℃煅烧4h,得到整体式催化剂。
对样品进行模拟尾气活性评价,采用常压固定床反应器进行催化活性的评价,分别测得尾气各成分的进口浓度和出口浓度,经计算得出尾气中CO、NOx、HC和PM的转化率分别是59%、56%、53%、55%,该催化剂的活性较高,催化性能较好,可以达到对尾气中有毒有害气体及颗粒物的同时去除。
通过与对比例1、2相比,发现本发明整体式催化剂的催化活性更高。
本发明整体式钙钛矿催化剂可以提高燃油车尾气中CO、NOx、HC以及颗粒物的转化率,能够达到对尾气中有毒有害气体及颗粒物的同时去除,减少燃油尾气污染物的排放,降低燃油车尾气污染物对工作人员的危害。
本发明中未述及的部分借鉴现有技术即可实现。
需要说明的是:在本说明的教导下本领域技术人员所做出的任何等同方式,或明显变型方式均应在本发明的保护范围内。
Claims (7)
1.一种整体式钙钛矿催化剂,其结构为ABO3,其特征在于:A位为Pr1-xCax,X=0.1、0.2或0.3,B位为Co、Mn、Fe、Cu中的一种或两种。
2.根据权利要求1所述的一种整体式钙钛矿催化剂的制备方法,其特征在于,依次包括以下步骤:
a、对载体预处理
选取堇青石蜂窝陶瓷作为载体,将堇青石蜂窝陶瓷载体浸渍在一定质量分数的草酸溶液中,然后密封处理并对其进行干燥,干燥后取出载体,用清水清洗达到中性,室内自然晾干,最后放置在马弗炉中煅烧,得到预处理后的载体;
b、制备催化剂前驱体溶液
按照一定的化学计量比称取相关原料,溶解在一定量的去离子水,搅拌,90℃水浴加热溶解,再加入一定量的柠檬酸,搅拌溶解,得催化剂前驱体溶液;
c、将步骤a所述的预处理后的载体浸渍在步骤b所述的催化剂前驱体溶液中,浸渍完成后取出,经干燥、煅烧,即得。
3.根据权利要求2所述的一种整体式钙钛矿催化剂的制备方法,其特征在于:步骤a中,草酸溶液的质量分数为10%~20%,浸渍时间为30~60min,放入电热鼓风干燥箱中对其进行干燥,干燥温度为70℃~90℃,干燥时间为3~5h;在马弗炉中煅烧温度为400℃~500℃,煅烧时间为1~2h。
4.根据权利要求2所述的一种整体式钙钛矿催化剂的制备方法,其特征在于:步骤b中,加入柠檬酸后所得混合溶液中柠檬酸的浓度在0.5~0.6mol/L。
5.根据权利要求2所述的一种整体式钙钛矿催化剂的制备方法,其特征在于:步骤c中,浸渍时间为20~40min,干燥温度为80℃~90℃,干燥时间为11~12h,煅烧温度为600℃~800℃,煅烧时间为4~5h。
6.根据权利要求1所述的一种整体式钙钛矿催化剂在减少燃油车污染物排放中的应用。
7.根据权利要求6所述的应用,其特征在于:所述的燃油车污染物主要包括氮氧化物、碳氧化物、碳氢化合物等有毒有害气体及颗粒物。
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