CN102046287A - 颗粒燃烧催化剂、颗粒过滤器和废气净化设备 - Google Patents
颗粒燃烧催化剂、颗粒过滤器和废气净化设备 Download PDFInfo
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Abstract
本发明提供了一种颗粒燃烧催化剂,其包括由单斜晶氧化锆颗粒形成的载体,和充当催化剂组分并且担载在该载体上的金属Ag或Ag氧化物,其中基于该载体的质量,按照还原成金属Ag计,该催化剂组分的量为0.5-10质量%,并且优选地该催化剂具有8-21m2/g的BET比表面积。本发明还提供了用该颗粒燃烧催化剂涂覆的颗粒过滤器;和包括用该颗粒燃烧催化剂涂覆的颗粒过滤器的废气清洁设备。
Description
技术领域
本发明涉及颗粒燃烧催化剂、颗粒过滤器和废气清洁设备。更具体地,本发明涉及在低温下实现除去(通过氧化)从柴油内燃机排出的颗粒物的颗粒燃烧催化剂;用该颗粒燃烧催化剂涂覆的颗粒过滤器;和包括用该颗粒燃烧催化剂涂覆的颗粒过滤器的废气清洁设备。
背景技术
从柴油机中排出的废气包含颗粒(即颗粒物),并且这类物质没有任何处理释放到大气中是空气污染的主因。因此,出现对这类物质的严格管理的要求。作为除去颗粒物的有效方式,已经提出了用于可溶性有机级分(SOF)燃烧的流过型氧化催化剂,或者使用用于捕集烟灰的柴油颗粒过滤器(DPF)的柴油废气捕集系统。然而,为了该DPF再生,其中捕集的颗粒物必须连续通过氧化除去。
迄今提出的连续再生系统包括使用这样的催化剂的体系,该催化剂包括例如由金属(例如铝、锆、铈、钛或钒)的氧化物或复合氧化物制成的载体,和担载在该载体上的昂贵贵金属(例如Pt)(参见例如专利文献1、2或3);和涉及NO2的连续再生方法(参见例如专利文献4)。该连续再生方法需要在DPF的上游提供氧化催化剂(例如Pt)用于使NO氧化成NO2,并且因此涉及高成本。另外,涉及NO2的反应被NOx/C比例影响,并且对该方法的使用施加了许多限制。
专利文献1:日本专利申请特开(kokai)No.H10-047035
专利文献2:日本专利申请特开(kokai)No.2003-334443
专利文献3:日本专利申请特开(kokai)No.2004-058013
专利文献4:日本专利No.3012249
发明内容
发明解决的问题
本发明的目的是提供不使用昂贵的贵金属在低温下通过氧化实现烟灰除去的颗粒燃烧催化剂,并且该催化剂使得能够仅借助于氧进行氧化反应并且因此在低温下通过氧化实现烟灰除去,与废气的NOx浓度无关。本发明的另一目的是提供用该颗粒燃烧催化剂涂覆的颗粒过滤器。本发明的仍然另一个目的是提供包括用该颗粒燃烧催化剂涂覆的颗粒过滤器的废气清洁设备。
解决问题的方式
为了实现上述目的,本发明人进行了广泛研究并且因此发现可以通过提供这样的颗粒燃烧催化剂实现该目的,该催化剂包括充当载体的特定氧化锆颗粒和充当催化剂组分的金属Ag或Ag氧化物,该催化剂组分担载在该载体上,其中催化剂组分的量落入特定范围,并且优选该催化剂具有落入特定范围的BET比表面积。基于该发现完成了本发明。
因此,本发明提供一种颗粒燃烧催化剂,其特征在于包含由单斜晶氧化锆颗粒形成的载体,和充当催化剂组分并且担载在该载体上的金属Ag或Ag氧化物,其中基于该载体的质量,按照还原成金属Ag计,该催化剂组分的量为0.5-10质量%。
优选地,本发明的颗粒燃烧催化剂包含由单斜晶氧化锆颗粒形成的载体,和充当催化剂组分并且担载在该载体上的金属Ag或Ag氧化物,其中基于该载体的质量,按照还原成金属Ag计,该催化剂组分的量为0.5-10质量%,并且该催化剂具有8-21m2/g的BET比表面积。
更优选地,本发明的颗粒燃烧催化剂包含由单斜晶氧化锆颗粒形成的载体,和充当催化剂组分并且担载在该载体上的金属Ag或Ag氧化物,其中基于该载体的质量,按照还原成金属Ag计,该催化剂组分的量为1-9质量%,并且该催化剂具有11-20m2/g的BET比表面积。
本发明还提供了特征在于用任一种上述颗粒燃烧催化剂涂覆的颗粒过滤器。本发明还提供了特征在于包括用任一种上述颗粒燃烧催化剂涂覆的颗粒过滤器的废气清洁设备。
发明效果
本发明的颗粒燃烧催化剂的使用实现了在低温下通过氧化除去烟灰,不需要使用昂贵的贵金属。当使用该颗粒燃烧催化剂时,由于氧化反应仅借助于氧进行,因此可以在低温下通过氧化除去烟灰,与废气的NOx浓度无关。
具体实施方式
本发明的颗粒燃烧催化剂包括由单斜晶氧化锆颗粒形成的载体,和充当催化剂组分并且担载在该载体上的金属Ag或Ag氧化物。尽管各种类型的氧化锆(例如单斜晶氧化锆和稳定的立方体氧化锆)可商购获得,但本发明的颗粒燃烧催化剂使用单斜晶氧化锆作为载体。
在本发明的颗粒燃烧催化剂中,作为催化剂组分,金属Ag或Ag氧化物必须担载在上述载体上。用于本发明的金属Ag或Ag氧化物比例如Pt或Pd廉价。另外,当金属Ag或Ag氧化物与用于本发明的特定载体组合使用时,与使用Pt或Pd组分的情形相比,获得进一步优良的效果。在本发明中,基于该载体的质量,按照还原成金属Ag计,担载在该载体上的金属Ag或Ag氧化物的量为0.5-10质量%(优选1-9质量%)。当担载的催化剂组分的量少于0.5质量%时,催化剂组分可能不能充分展现其催化效果,并且Tig(燃烧开始温度)变成高于300℃。即使当担载的催化剂组分的量超过10质量%时,也不能实现与如此大的催化剂组分量相称的效果。另外当催化剂组分的量大时,容易出现金属烧结,并且催化剂组分不能预期展现出其催化效果。当基于该载体的质量,按照还原成金属Ag计,担载的催化剂组分的量为1-9质量%并且该催化剂具有11-20m2/g的BET比表面积时,Tig变成260℃或更低,尽管其原因没有被解释。
本发明的颗粒燃烧催化剂优选具有8-21m2/g,更优选11-20m2/g的BET比表面积。当该催化剂具有小于8m2/g的BET比表面积时,Tig倾向于变成高于300℃,而当该催化剂具有超过21m2/g的BET比表面积时,Tig也倾向于变成高于300℃。如上所述,当该催化剂具有11-20m2/g的BET比表面积并且基于该载体的质量,按照还原成金属Ag计,担载的催化剂组分的量为1-9质量%时,Tig变成260℃或更低。
如下文所述的实施例和比较例中所示,包括载体和基于该载体的质量,按照还原成金属Ag计,其量为0.5-10质量%的催化剂组分的颗粒燃烧催化剂展现出足够低的Tig,而包括载体和基于该载体的质量,按照还原成金属Ag计,其量为1-9质量%的催化剂组分并且具有11-20m2/g的BET比表面积的颗粒燃烧催化剂展现出260℃或更低的Tig。
考虑到通过使本发明的颗粒燃烧催化剂保持在基底上制备本发明的颗粒过滤器,优选使该载体的表面提供粘合剂组分例如SiO2、TiO2、ZrO2或A12O3。当该粘合剂组分在该载体表面提供时,基底与载体之间的粘结性增强,并且该催化剂展现出改进的耐久性和耐热性。
本发明的颗粒燃烧催化剂可以通过例如以下步骤制备。将上述单斜晶氧化锆颗粒与粘合剂组分(例如SiO2或氧化铝溶胶)和水混合,并且任选地通过研磨设备(例如球磨机)将所得混合物细磨。将所得分散体与水溶性银化合物的水溶液混合,并且将混合物充分搅拌由此制备浆料。此后将该浆料干燥,并且使该催化剂组分担载的单斜晶氧化锆颗粒在通常600-900℃,优选在730-870℃,更优选在750-850℃下焙烧10小时或更长(通常约20小时)。当焙烧温度低于600℃时,所得催化剂有具有大的BET比表面积并且展现出高Tig的倾向,而当焙烧温度超过900℃时,所得催化剂有具有小的BET比表面积并且展现出高Tig的倾向(即较少可能制得实际产品)。当焙烧温度为600-900℃时,所得催化剂有具有约8-约21m2/g的BET比表面积并且展现出300℃或更低的Tig的倾向,而当焙烧温度为730-870℃时,所得催化剂有具有约11-约20m2/g的BET比表面积并且展现出260℃或更低的Tig的倾向。当焙烧时间短于10小时,则可能不能制得具有预期特征的催化剂,而即使当焙烧时间超过50小时,则也不能获得与该长焙烧时间相称的效果。
本发明的颗粒过滤器可以呈现为任何已知形式的颗粒过滤器,但优选具有三维结构。具有三维结构的过滤器的具体例子包括穿过壁型过滤器、流过型蜂窝过滤器、金属丝网过滤器、陶瓷纤维过滤器、金属多孔过滤器、颗粒装填的过滤器和泡沫过滤器。基底的材料的例子包括陶瓷材料例如堇青石和SiC;Fe-Cr-Al合金;和不锈钢合金。
其中包括上述本发明的颗粒过滤器的本发明的废气清洁设备将被本领域那些技术人员容易地理解。
接下来将描述制造本发明的颗粒过滤器的方法。将基底过滤器(例如金属丝网过滤器)用如上所述制备的浆料涂覆。使该浆料涂覆的过滤器在通常600-900℃,优选在730-870℃,更优选在750-850℃下焙烧10小时或更长(通常约20小时)。总的催化剂涂覆量优选为10-100g/L(对于壁流型PDF)或者约50-约150g/L(对于金属丝网DPF)。当总的催化剂涂覆量过小时,不能获得足够的性能,而当总的催化剂涂覆量过大时,废气的回压增加。
接下来将参照实施例和比较例详细描述本发明。
在下面描述的实施例和比较例中,粉末状催化剂的Tig(燃烧开始温度)通过以下方法确定。
<通过使用模拟的废气评价粉末状催化剂>
借助于玛瑙研钵将颗粒燃烧催化剂粉末(20mg)和碳(Printex-V(墨粉碳),Degussa的产品)(2mg)混合2分钟,并且通过使用石英棉将该混合物固定在石英反应管的中心部分。在使具有下述组成的循环气在下述流动速率下流过该石英反应管时,通过电炉在下述的温度升高速率下使该反应管的温度升高,并且在该反应管的出口通过红外分析仪测量CO和CO2浓度。当CO2浓度达到30ppm时,在该含催化剂的反应管入口处测量的温度(即电炉控制温度)被认为是Tig(燃烧开始温度)。
气体组成:O2:10%,N2:90%
流动速率:400cc/min
温度升高速率:10度(℃)/min
实施例1-6和比较例1-9
使用单斜晶氧化锆(ZrO2)颗粒或γ-氧化铝(Al2O3)颗粒作为载体。将该粉末状载体与硝酸银水溶液或者(二硝基二胺)Pt的硝酸溶液混合,使得基于该载体的质量,担载的催化剂组分的量(按照还原成金属银或金属铂计)如表1中所示调节。将所得混合物搅拌1小时。随后在加热下使水蒸发,随后在120℃下干燥。将由此干燥的产品在750℃下焙烧20小时,由此制得颗粒燃烧催化剂。表1示出了该颗粒燃烧催化剂的BET比表面积和Tig。
表1
载体 | 催化剂组分 | 担载量 | BET比表面积 | Tig | |
比较例1 | ZrO2 | Ag | 0质量% | 25.6m2/g | 384℃ |
实施例1 | ZrO2 | Ag | 0.5质量% | 20.7m2/g | 300℃ |
实施例2 | ZrO2 | Ag | 1质量% | 19.2m2/g | 251℃ |
实施例3 | ZrO2 | Ag | 2质量% | 16.0m2/g | 245℃ |
实施例4 | ZrO2 | Ag | 5质量% | 15.3m2/g | 256℃ |
实施例5 | ZrO2 | Ag | 9质量% | 13.1m2/g | 258℃ |
实施例6 | ZrO2 | Ag | 10质量% | 10.2m2/g | 264℃ |
比较例2 | Al2O3 | Ag | 0质量% | 147.8m2/g | 479℃ |
比较例3 | Al2O3 | Ag | 1质量% | 146.9m2/g | 487℃ |
比较例4 | Al2O3 | Ag | 2质量% | 146.4m2/g | 476℃ |
比较例5 | Al2O3 | Ag | 5质量% | 136.8m2/g | 441℃ |
比较例6 | Al2O3 | Pt | 0质量% | 147.8m2/g | 479℃ |
比较例7 | Al2O3 | Pt | 1质量% | 142.8m2/g | 458℃ |
比较例8 | Al2O3 | Pt | 2质量% | 151.2m2/g | 459℃ |
比较例9 | Al2O3 | Pt | 5质量% | 147.8m2/g | 461℃ |
从表1中所示数据(实施例1-6)明显看出,当Ag(即催化剂组分)担载在由单斜晶氧化锆颗粒形成的载体上使得基于该载体的质量,该催化剂组分的量调节为0.5-10质量%(按照还原成金属Ag计)时,所得催化剂展现出300℃或更低的Tig并且具有8-21m2/g的BET比表面积,并且当该催化剂组分担载在该载体上使得基于该载体的质量,该催化剂组分的量调节为1-9质量%(按照还原成金属Ag计)时,所得催化剂展现出260℃或更低的Tig并且具有11-20m2/g的BET比表面积。相反,从比较例2-9中获得的数据明显看出,当使用Al2O3作为载体代替ZrO2或者当使用Pt作为催化剂组分代替Ag时,所得催化剂的Tig不低。
实施例7-11和比较例10
使用单斜晶氧化锆(ZrO2)颗粒作为载体。将该粉末状载体与硝酸银水溶液混合,使得基于该载体的质量,担载的催化剂组分的量(按照还原成金属银计)如表2中所示调节。将所得混合物搅拌1小时。随后在加热下使水蒸发,随后在120℃下干燥。将由此干燥的产品在750℃下焙烧20小时,由此制得颗粒燃烧催化剂。表2示出了该颗粒燃烧催化剂的BET比表面积和Tig。
表2
实施例12-18
使用单斜晶氧化锆颗粒作为载体。将该粉末状载体与硝酸银水溶液混合,使得基于该载体的质量,担载的催化剂组分的量(按照还原成金属银计)调节为1质量%,并且将所得混合物搅拌1小时。随后在加热下使水蒸发,随后在120℃下干燥。将由此干燥的产品在表3所示的温度下焙烧20小时,由此制得颗粒燃烧催化剂。表3示出了该颗粒燃烧催化剂的BET比表面积和Tig。
表3
焙烧温度 | BET比表面积 | Tig | |
实施例12 | 600℃ | 27.5m2/g | 277℃ |
实施例13 | 650℃ | 23.2m2/g | 268℃ |
实施例14 | 700℃ | 21.1m2/g | 271℃ |
实施例15 | 750℃ | 19.2m2/g | 251℃ |
实施例16 | 800℃ | 13.9m2/g | 259℃ |
实施例17 | 850℃ | 11.9m2/g | 252℃ |
实施例18 | 900℃ | 6.2m2/g | 275℃ |
实施例19-24
使用单斜晶氧化锆颗粒作为载体。将该粉末状载体与硝酸银水溶液混合,使得基于该载体的质量,担载的催化剂组分的量(按照还原成金属银计)调节为1质量%,并且将所得混合物搅拌1小时。随后在加热下使水蒸发,随后在120℃下干燥。将由此干燥的产品在750℃下焙烧表4中所示的时间,由此制得颗粒燃烧催化剂。表4示出了该颗粒燃烧催化剂的BET比表面积和Tig。
表4
焙烧时间 | BET比表面积 | Tig | |
实施例19 | 10小时 | 19.1m2/g | 259℃ |
实施例20 | 15小时 | 18.0m2/g | 256℃ |
实施例21 | 20小时 | 19.2m2/g | 251℃ |
实施例22 | 25小时 | 15.1m2/g | 254℃ |
实施例23 | 30小时 | 14.7m2/g | 255℃ |
实施例24 | 50小时 | 12.9m2/g | 258℃ |
Claims (9)
1.一种颗粒燃烧催化剂,其特征在于包含由单斜晶氧化锆颗粒形成的载体,和充当催化剂组分并且担载在该载体上的金属Ag或Ag氧化物,其中基于该载体的质量,按照还原成金属Ag计,该催化剂组分的量为0.5-10质量%。
2.根据权利要求1的颗粒燃烧催化剂,其通过在600-900℃下焙烧10小时或更长来制备。
3.根据权利要求1或2的颗粒燃烧催化剂,其具有8-21m2/g的BET比表面积。
4.根据权利要求1、2或3的颗粒燃烧催化剂,其展现出300℃或更低的燃烧开始温度(Tig)。
5.一种颗粒燃烧催化剂,其特征在于包含由单斜晶氧化锆颗粒形成的载体,和充当催化剂组分并且担载在该载体上的金属Ag或Ag氧化物,其中基于该载体的质量,按照还原成金属Ag计,该催化剂组分的量为1-9质量%,并且该催化剂具有11-20m2/g的BET比表面积。
6.根据权利要求5的颗粒燃烧催化剂,其展现出260℃或更低的燃烧开始温度(Tig)。
7.根据权利要求1-6中任一项的颗粒燃烧催化剂,其通过在730-870℃下焙烧10小时或更长来制备。
8.一种颗粒过滤器,其特征在于包括用权利要求1-7中任一项所述的颗粒燃烧催化剂涂覆的基底。
9.一种废气清洁设备,其特征在于包括用权利要求1-7中任一项所述的颗粒燃烧催化剂涂覆的颗粒过滤器。
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JP5328783B2 (ja) | 2013-10-30 |
US9393522B2 (en) | 2016-07-19 |
CN104279025A (zh) | 2015-01-14 |
US20110076202A1 (en) | 2011-03-31 |
EP2289619A1 (en) | 2011-03-02 |
JPWO2009144847A1 (ja) | 2011-10-06 |
WO2009144847A1 (ja) | 2009-12-03 |
US20140004026A1 (en) | 2014-01-02 |
EP2289619B1 (en) | 2019-04-24 |
EP2289619A4 (en) | 2011-12-14 |
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