CN111715222A - 一种用于柴油机尾气净化氧化型doc催化剂的制备方法 - Google Patents
一种用于柴油机尾气净化氧化型doc催化剂的制备方法 Download PDFInfo
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Abstract
本发明涉及柴油车尾气净化技术领域,涉及一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,包括内层浆料的制作、外层浆料的制作和将内层浆料和外层浆料分别涂覆在载体上,先将内层浆料涂覆在载体上,进行烘干和煅烧,然后再涂覆外层浆料,进行烘干和煅烧,进行煅烧制作出催化剂,具有较低起燃温度,实现低温快速起燃,高温下耐久性能优异,采用双层涂覆技术,满足国六排放法规要求。
Description
技术领域
本发明涉及柴油车尾气净化技术领域,涉及一种用于柴油机尾气净化氧化型DOC催化剂的制备方法。
背景技术
柴油机有着优越的动力性和经济性,因此广泛用于交通运输和非道路机械领域。
《车用压燃式,气体燃料点燃式发动机与汽车排气污染物排放限制及测量方法》(中国第六阶段)(GB1769-2016)法规,与GB17691-2005《车用压燃烧式、气体点燃式发动机与汽车污染物排放限值及策略方法(中国Ⅲ、Ⅳ、Ⅴ阶段)》相比,国六标准加严了污染物排放限值,增加了粒子数量排放限值;变更了污染物排放测试循环,提供了耐久性要求等;柴油机技术已经取得重大突破,但仅依靠柴油机机内净化技术难以满足日益严格的排放法规要求。
柴油机尾气后处理技术有氧化型催化器(DOC),颗粒捕集器(DPF),催化型颗粒捕集器(CDPF),选择性催化还原***(SCR)和连续再生颗粒捕集器(DOC+CDPF)等。
其中,DOC氧化型催化器可氧化CO、THC、SOF等,可将NO氧化成NO2辅助CDPF被动再生和SCR快速反应;DPF可有效捕集颗粒物,实现达90%以上捕集效率;CDPF是在DPF的内壁涂覆含有贵金属和稀土元素催化剂涂层,其具备颗粒物捕集和被动再生能力;SCR通过喷射尿素,利用尿素分解产物NH3将NOx还原。
针对柴油机颗粒物排放控制技术,使用单一后处理器已无法满足当前排放法规对多种污染物限值的要求,同时降低多种污染物的有效手段之一就是使用后处理集成技术,例如将DOC、CDPF和SCR组合使用,可同时实现CO,THC,NOx和PM,PN的有效净化。
出现的技术路线是柴油机颗粒捕集器DPF在前端耦合DOC氧化型催化器组成连续再生颗粒捕集器,该技术达到高效的颗粒捕集效果,通过前端的DOC将排气中NO氧化成NO2,生成的NO2氧化DPF中捕集的碳烟颗粒实现DPF连续再生。在DPF载体上涂覆贵金属等催化剂涂层,即催化型颗粒捕集器CDPF,将更有利于降低堆积碳烟的起燃温度,实现DPF的低温再生。
实际应用过程中DPF主动再生与被动再生相结合,这就要求前面DOC催化器具有快速放热功能,同时具有耐高温性能,满足DPF主动再生时,提高排气温度的需求。
发明内容
本专利发明了一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,具有较低起燃温度,实现低温快速起燃,高温下耐久性能优异,采用双层涂覆技术,满足国六排放法规要求。
本发明的实施例是这样实现的:一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,包括如下步骤,
步骤1、内层浆料的制作:首先将硅改性氧化铝粉体和铈锆氧化物按2:1~3:1比例混合,缓慢滴加贵金属硝酸钯溶液,进行等体积浸渍,充分搅拌浸渍2-4h;另外称量一定质量硅改性氧化铝粉体,其中硅改性氧化铝粉体的质量占内层浆料干重30%-40%质量百分比,向硅改性氧化铝粉体中缓慢滴加Pt-A或硝酸铂溶液,充分搅拌后,配制成固含量为30-40%的泥浆,
其次将浸渍含贵金属硝酸钯的粉体加入泥浆中,充分混合搅拌;
然后研磨浆料,使得浆料粒度D90在5-9μm之间;
最后用HNO3调节浆料pH在4-5之间;
步骤2、外层浆料的制作:首先称取一定质量硅改性氧化铝粉体,其中硅改性氧化铝粉体占外层浆料干重质量的45%-55%,在搅拌的状态下,向粉体里滴加Pt-A,配制成固含量为30-40%泥浆,充分搅拌;
其次向泥浆中加入一定质量β分子筛,其中β分子筛占外层浆料干重质量的40%-44%,充分搅拌;
然后研磨浆料,使得浆料粒度D90在5-9μm;
最后用HNO3调节浆料PH值在4-5之间;
步骤3、将内层浆料和外层浆料分别涂覆在载体上:先将内层浆料涂覆在载体上,进行烘干和煅烧,然后再涂覆外层浆料,进行烘干和煅烧,煅烧后制作出催化剂。
具体地,步骤3中,内层浆料和外层浆料涂覆的载体为陶瓷堇青石,涂层上载量为80~120g/L。
具体地,步骤3中,在120℃条件下烘干,烘干时间2-4h,在烘干过程中同时吹扫陶瓷蜂窝载体,避免浆料在烘干过程中出现堵塞或隐堵。
具体地,步骤3中,内层涂层制作时煅烧时间30min,外层涂层制作时煅烧时间为2h,并以5℃/min的升温速率升温。
进一步地,步骤1中,配制贵金属上载量为80g/ft3,内层浆料中pt:pd=2:1,内层浆料上载量为80g/L浆料,步骤1中内层浆料上载量为80g/L。
进一步地,内层浆料中硅改性氧化铝的含量为79%的;铈锆氧化物的含量为18.26%;贵金属的总含量2.74%;Pt的含量为1.57%;Pd的含量为1.17%;
外层浆料中硅改性氧化铝的含量为55%,β分子的筛含量为44.22%,Pt-A的含量为0.78%。
本发明实施例的有益效果是:一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,具有较低起燃温度,实现低温快速起燃,高温下耐久性能优异,采用双层涂覆技术,满足国六排放法规要求。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,应当理解,以下附图仅示出了本发明的某些实施例,因此不应被看作是对范围的限定,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他相关的附图。
图1是本发明一种用于柴油机尾气净化氧化型DOC催化剂的制备方法实施例1中CO转换的测试结果;
图2是本发明一种用于柴油机尾气净化氧化型DOC催化剂的制备方法实施例1中C3H6转换的测试结果。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。通常在此处附图中描述和示出的本发明实施例的组件可以以各种不同的配置来布置和设计。
因此,以下对在附图中提供的本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围,而是仅仅表示本发明的选定实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
应注意到:相似的标号和字母在下面的附图中表示类似项,因此,一旦某一项在一个附图中被定义,则在随后的附图中不需要对其进行进一步定义和解释。
在本发明的描述中,需要说明的是,术语“上”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系,或者是该发明产品使用时惯常摆放的方位或位置关系,仅是为了便于描述本发明和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本发明的限制。此外,术语“第一”、“第二”等仅用于区分描述,而不能理解为指示或暗示相对重要性。
在本发明的描述中,还需要说明的是,除非另有明确的规定和限定,术语“设置”、“相连”、“连接”应做广义理解,例如,可以是固定连接,也可以是可拆卸连接,或一体地连接;可以是机械连接,也可以是电连接;可以是直接相连,也可以通过中间媒介间接相连,可以是两个元件内部的连通。对于本领域的普通技术人员而言,可以具体情况理解上述术语在本发明中的具体含义。其中DPM指柴油机颗粒再生器,DPF为柴油机颗粒捕捉再生器,HC为氢碳,DOC为柴油氧化型催化剂,SCR为选择性催化还原***,POC为颗粒氧化净化器。
实施例
一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,包括如下步骤,
1、制作内层浆料:
1.1
称取395g硅改性氧化铝粉体,182.6g铈锆氧化物粉体,将两者混合,在搅拌调节下,向粉体中缓慢滴加如固含量为11.26%硝酸钯溶液103.9g,进行等体积浸渍,充分搅拌,浸渍2-4h后备用;
1.2
另外称取395g硅改性氧化铝,在搅拌的调节下向该粉体滴加Pt-A溶液,固含量为12.23%Pt-A 128.37g充分搅拌后,添加去离子水,配制成固含量为30-40%泥浆;
1.3
将浸渍含贵金属硝酸钯的粉体加入到上述泥浆中,充分混合搅拌;研磨浆料,浆料粒度D90在5-9μm之间;用HNO3调节浆料pH在4-5之间;测试浆料固含量备用;调整固含量为35%;
2、外层浆料制作:
2.1
称取550g硅改性氧化铝粉体,搅拌混合均匀,在搅拌的状态下,缓慢滴加固含量为12.35%Pt-A贵金属溶液63.16g,搅拌20-30min贵金属溶液浸渍在粉体上,加入去离子水781g,配制成固含量为40%泥浆,搅拌20-30min,加入HNO3调节浆料pH值在4-5之间;
2.2
搅拌4-8h后,向上述泥浆中加入442.2gβ分子筛,继续搅拌20-30min后;进入研磨阶段,研磨泥浆D90在5-9μm之间;用HNO3调节浆料pH在4-5之间;测试浆料固含量备用;调整固含量为30%;
3、DOC催化剂载体制作-涂覆、烘干,煅烧载体
按照上述1、2步骤得到贵金属上载量为80g/ft3,pt:pd=2:1,涂层上载量为80g/L浆料;涂覆载体规格为高度*直径*目数*壁厚143.8mm*101.6mm/400cpsi/4miL
经计算陶瓷载体体积为:1.65L,应上载涂层干重为132g+132g;
测试内外层浆料固含量均为35%,先手工涂覆内层浆料,涂覆前称量空白载体质量,记录为M0;将整个载体浸渍在内层浆料中,取出,用压缩空***吹扫多余浆料,上载湿浆重量为377.1g,120℃条件下烘干,烘干时间2-4h,在烘干过程中注意吹扫陶瓷蜂窝载体,避免浆料在烘干过程中出现堵塞或隐堵;
烘干后550℃恒温煅烧30min,以5℃/min的升温速率升温;
在干燥器中冷却到室温,称量载体重量为M1,内层涂层干重M2=M1-M0,理论干重132g,
控制内层涂层干重重量=理论干重±5%范围内;即实际涂层干重在125.4-138.6g范围内;
称量计算得到内层干重为133.4g;
同样方法涂覆外层浆料,涂覆完成后,经过烘干,煅烧,煅烧温度550℃恒温2h;冷却到室温,最后称量计算得到外层干重为134.2g。完成催化剂成品制作。
一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,配制贵金属上载量为80g/ft3,pt:pd=2:1涂层内层上载量为80g/L浆料,涂层外层上载量为80g/L;
内层浆料组成为含79%的硅改性氧化铝,铈锆氧化物含量为18.26%%浆料;贵金属总含量2.74%;其中Pt的含量为1.57%;Pd的含量为1.17%;
外层浆料组成为55%硅改性氧化铝,44.22%β分子筛,0.78%为Pt-A的含量;
涂覆载体规格为高度*直径*目数*壁厚143.8mm*101.6mm/400cpsi/4miL。
对催化剂在新鲜态,预处理和热老化条件下性能测试;取样器钻取直径*高度为1"*3"小柱子4个:
1)吹扫干净标记为:新鲜态-Fresh进行测试;
2)小柱子经过测试设备加热预处理570℃15min,后再进行测试标件为:
预处理-Degreened;
3)新鲜态的小柱子经过750℃16h热老化后,标记为老化态--750℃16h
4)新鲜态的小柱子经过800℃10h热老化后,标记为老化态---800℃10h
试设备:柴油机尾气模拟小样评价装置
测试条件,如下表所示:
测试成分 | CO | C3H6 | C3H8 | CO2 | H2O | O2 | N2 | SV |
含量 | 500ppm | 500ppm | 250ppm | 5% | 5% | 5% | Balanced | 40kh-1 |
测试结果如下表所示,请查阅图1和2:
内层浆料制备方法:
1、按一定比例混合硅改性氧化铝粉体,其中硅改性氧化铝粉体和铈锆氧化物按2:1~3:1比例混合,铈锆氧化物,缓慢滴加贵金属硝酸钯溶液,进行等体积浸渍,充分搅拌浸渍2-4h;备用;
2、另外称量一定质量硅改性氧化铝粉体,其中硅改性氧化铝粉体的质量占内层浆料干重30%-40%质量百分比,向该粉体中缓慢滴加Pt-A或硝酸铂溶液,充分搅拌后,配制成固含量为30-40%泥浆;
3、将浸渍含贵金属硝酸钯的粉体加入到上述泥浆中,充分混合搅拌;研磨浆料,浆料粒度D90在5-9μm之间;用HNO3调节浆料pH在4-5之间;
4、测试浆料固含量备用;
外层浆料制备方法:
1、称取一定质量硅改性氧化铝粉体,其中硅改性氧化铝粉体占外层浆料干重质量的45%-55%,在搅拌的状态下,向粉体里滴加Pt-A,配制成固含量为30-40%泥浆,充分搅拌;
2、向上述泥浆中加入一定质量β分子筛,其中β分子筛占外层浆料干重质量的40%-44%,;充分搅拌;
3、将上述混合泥浆充分搅拌,研磨,D90在5-9μm;用HNO3调节浆料PH值在4-5之间;
4、测试浆料固含量备用。
一种用于满足国六柴油机尾气排放耐高温DOC氧化型催化剂,该催化剂成分包括大比表面积硅改性氧化铝、铈锆氧化物、β分子筛,硝酸或氨水,其中β分子筛,硝酸或氨水作为pH值调节助剂;以陶瓷堇青石为载体,该催化剂分层涂覆在载体上,涂覆为内层和外层,涂层上载量在80~120g/L之间,具有优异的耐高温性能;该催化剂内层由Pt和Pd两种贵金属组成,外层由Pt一种贵金属组成;该催化剂具有较低的起燃温度;
其中催化剂包括硅改性氧化铝,β分子筛组成,该催化剂具有较高耐高温老化性能。
其中该催化剂弱酸条件下制备的,pH值在4-5之间;该催化剂粒度D90在5-9μm之间
以上仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,其特征在于:包括如下步骤,
步骤1、内层浆料的制作:首先将硅改性氧化铝粉体和铈锆氧化物按2:1~3:1比例混合,缓慢滴加贵金属硝酸钯溶液,进行等体积浸渍,充分搅拌浸渍2-4h;另外称量一定质量硅改性氧化铝粉体,其中硅改性氧化铝粉体的质量占内层浆料干重30%-40%质量百分比,向硅改性氧化铝粉体中缓慢滴加Pt-A或硝酸铂溶液,充分搅拌后,配制成固含量为30-40%的泥浆,
其次将浸渍含贵金属硝酸钯的粉体加入泥浆中,充分混合搅拌;
然后研磨浆料,使得浆料粒度D90在5-9μm之间;
最后用HNO3调节浆料pH在4-5之间;
步骤2、外层浆料的制作:首先称取一定质量硅改性氧化铝粉体,其中硅改性氧化铝粉体占外层浆料干重质量的45%-55%,在搅拌的状态下,向粉体里滴加Pt-A,配制成固含量为30-40%泥浆,充分搅拌;
其次向泥浆中加入一定质量β分子筛,其中β分子筛占外层浆料干重质量的40%-44%,充分搅拌;
然后研磨浆料,使得浆料粒度D90在5-9μm;
最后用HNO3调节浆料PH值在4-5之间;
步骤3、将内层浆料和外层浆料分别涂覆在载体上:先将内层浆料涂覆在载体上,进行烘干和煅烧,然后再涂覆外层浆料,进行烘干和煅烧,进行煅烧制作出催化剂。
2.根据权利要求1所述的一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,其特征在于,步骤3中,内层浆料和外层浆料涂覆的载体为陶瓷堇青石,涂层上载量为80~120g/L。
3.根据权利要求1所述的一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,其特征在于,
步骤3中,在120℃条件下烘干,烘干时间2-4h,在烘干过程中同时吹扫陶瓷蜂窝载体,避免浆料在烘干过程中出现堵塞或隐堵。
4.根据权利要求3所述的一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,其特征在于,步骤3中,内层涂层制作时煅烧时间30min,外层涂层制作时煅烧时间为2h,并以5℃/min的升温速率升温。
5.根据权利要求1所述的一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,其特征在于,
步骤1中,配制贵金属上载量为80g/ft3,内层浆料中pt:pd=2:1,内层浆料上载量为80g/L浆料,步骤1中内层浆料上载量为80g/L。
6.根据权利要求1所述的一种用于柴油机尾气净化氧化型DOC催化剂的制备方法,其特征在于,
内层浆料中硅改性氧化铝的含量为79%的;铈锆氧化物的含量为18.26%;贵金属的总含量2.74%;Pt的含量为1.57%;Pd的含量为1.17%;
外层浆料中硅改性氧化铝的含量为55%,β分子的筛含量为44.22%,Pt-A的含量为0.78%。
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CN115487824B (zh) * | 2022-08-18 | 2023-10-13 | 无锡双翼汽车环保科技有限公司 | 一种矿用防爆柴油机尾气净化装置 |
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