CN1711134A - 废气净化用催化剂与废气净化方法 - Google Patents
废气净化用催化剂与废气净化方法 Download PDFInfo
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Abstract
本发明是含氧化铜、ZSM-5和/或β-沸石并进一步加入镁和/或钙的氧化物的废气净化用催化剂以及使用此催化剂的废气净化方法。利用本发明的催化剂可以有效地从如柴油机排出的废气那样的富含氧的废气中除去NOx并可抑制高温条件下的SO2的氧化。
Description
技术领域
本发明涉及废气净化用催化剂与使用该催化剂的废气净化方法。更详细地说,本发明涉及可降低从柴油机排放的NOx(氮氧化物)而且抑制二氧化硫(SO2)氧化的废气净化用催化剂与废气净化方法。
背景技术
一般使用的净化内燃机排放的废气的催化剂是把铂(Pt)、钯(Pd)、铑(Rh)等贵金属担载在活性氧化铝上的。此催化剂可以同时除去烃(HC)、一氧化碳(CO)和NOx,因此被称为三元催化剂。
然而,此催化剂是在理论空燃比(A/F)附近的条件下有效地起作用的,对于柴油机废气那样的富氧条件,例如贫燃条件,就存在有不能充分除去NOx的问题。
还有,柴油机排放的废气是由碳、可溶性有机物(SOF)、硫酸盐等构成的微粒物质,对于人体有害,已经成为法规限制的对象。所以,在把废气净化催化剂用于柴油机的废气处理时,必须减少微粒物质。
作为在贫燃条件下除去NOx的催化剂,已知有铜离子交换的铜沸石催化剂(Cu-ZSM5)(特开昭60-125250号公报),但是,由于其技术,特别是用于处理柴油机排放的废气时,在450℃以上的高温条件下把SO2氧化,生成硫酸盐类,因此就存在有不能减少微粒物质的问题。
发明内容
鉴于上述存在的问题,本发明的目的在于提供可以有效除去柴油机排放的废气那样的富含氧的废气中的NOx且可抑制在高温条件下SO2的氧化的废气净化用催化剂以及废气净化方法。
本发明的发明人等为了达到上述目的,对废气净化用催化剂进行了刻意的探索,发现含氧化铜、ZSM-5和/或β-沸石并进一步含镁和/或钙的氧化物的废气净化用催化剂具备优异的性能,至此完成了本发明。进而,还发现:当上述催化剂与HC和NOx的体积比(换算成C1的HC/NOx)是1~20的废气接触时,在可有效除去NOx的同时还可以抑制SO2的氧化。
也就是说,本发明涉及含铜(作为催化剂主要以氧化物而存在)、ZSM5和/或β-沸石以及镁和/或钙的氧化物的废气净化用催化剂。
本发明还涉及以把上述催化剂与HC/NOx的体积比为1~20的废气相接触为特征的废气净化方法。
实施发明的最佳形态
本发明的催化剂中含有氧化铜、ZSM-5和/或β-沸石并进一步含镁和/或钙的氧化物。所述ZSM-5和/或β-沸石列举的是单纯ZSM-5沸石、单纯β-沸石、ZSM-5沸石与β-沸石的混合物的方案。对于ZSM-5沸石与β-沸石的混合比例没有特别的限制,通常以1∶1~10∶1范围为优选。
ZSM-5沸石的二氧化硅/氧化铝(摩尔)比以10~200范围为优选,20~90范围为进一步优选。
β-沸石的二氧化硅/氧化铝(摩尔)比以10~200范围为优选,20~90范围为进一步优选。
本发明的催化剂中含有镁和/或钙的氧化物。其中,以氧化镁为优选。当含有氧化镁的场合,在处理由使用含硫燃料的柴油机排放的废气时,不降低对NOx的净化性能,可以抑制SO2的氧化。SO2的氧化生成大量的硫酸盐,增加微粒物质的排放量,由于抑制了SO2的氧化,就可以减少微粒物质的排放量。
上述镁和/或钙的氧化物的加入量,相对于每1质量份氧化铜是0.1~1质量份为优选。在不足0.1质量份时,不能充分抑制SO2的氧化;另一方面,超过1质量份时,则使得NOx的净化性能下降。
本发明的催化剂中,氧化铜相对于每升耐火性三维结构体在3~14g范围为优选,3~10g范围为进一步优选。铜的担载量不足3g时,活性种的量变得不够,降低了NOx的净化性能,反之,超过14g时,SO2的转化率急遽上升,就有所谓的生成硫酸盐的问题,因而不优选。进而,ZSM-5和/或β-沸石的担载量以在50~300g范围为优选。
本发明的催化剂以担载在耐火性三维结构体上为优选。所述耐火性三维结构体可以使用通常称之为陶瓷蜂窝载体的,特别是以堇青石、富铝红柱石、α-氧化铝、氧化锆、二氧化钛、磷酸钛、钛酸铝、硅铝酸盐、硅酸镁等作为材料的蜂窝载体为优选,其中以堇青石制的为优选。此外,也可以使用不锈钢、Fe-Cr-Al合金等抗氧化性的耐热性金属而制成整体结构体的。
接着来说明此催化剂的制造方法。
本发明的催化剂中含有氧化铜、ZSM-5和/或β-沸石,以氧化铜担载于ZSM-5和/或β-沸石上为优选。担载的方法可以采用浸渍法、浸没法等已知方法。以浸没法为例来说明。铜使用其可溶性盐,例如乙酸铜、硝酸铜、硫酸铜等。沸石以粉末状沸石为优选。在不是粉末状时,希望使用前要粉碎成平均粒径(二次粒径)150μm以下,优选0.01~10μm范围。进而,ZSM5型沸石以用电子显微镜测定的平均结晶直径(一次粒径)在0.5μm以下(零除外)为优选,从提高NOx净化率的初期活性观点来说,0.1μm以下(零除外)为进一步优选。
具体说,例如,把ZSM-5和β型的混合沸石粉末加入到预先溶解了硝酸铜的水溶液中,充分混合。还有,硝酸铜可以与ZSM-5或β型中的任何一方或者仅与ZSM-5的一部分或β型的一部分混合。混合时所用的水溶液的量以所用沸石粉末的吸水量为基准,加上进一步考虑混合器等的大小,完全浸没沸石粉末而余出部分的水。混合后在例如100~150℃下干燥10~20h,进而在空气中以例如400~800℃烧结1~3h。所得到的担载了铜的沸石可以直接或者经过必要的粉碎后用于下面的工序。
把担载了铜的沸石粉末、前述镁和/或钙的氧化物的前体与二氧化硅等粘合剂一起用球磨机等湿式粉碎装置粉碎,淤浆化并担载在耐火性三维结构体上。镁源的例子可以列举有,硝酸镁、氧化镁、乙酸镁;钙源可以列举有硝酸钙、氧化钙、碳酸钙。担载后,在例如100~150℃下干燥10分钟~1h,进而根据需要在空气中以例如400~800℃烧结1~3h。上述前体在得到上述担载铜的沸石的湿式粉碎的同时来进行粉碎、担载也行,把担载了铜的沸石粉末担载于所述结构体后,以水溶液等液体状来含浸也行。
这样所得到的催化剂尤其对净化使用含硫燃料的柴油机排放的含NOx废气是有效的。含硫量通常在0.001~0.5质量%范围,以在0.001~0.05质量%范围为优选。由于在废气中HC等还原剂少的场合NOx不能被充分还原,有必要加入HC源。以把作为柴油机燃料的轻油加入到废气中为优选。从催化剂的上游一侧向废气中加入轻油的方法可以采用向废气中滴入的方法、向废气中喷雾的方法等已知的方法。此时,为了在把NOx充分还原的同时所加入的轻油并没有作为未处理的有害成分被排放,废气中的HC与NOx的体积比(换算为C1的HC/NOx)通常为1~20,以1~10范围为优选。当HC/NOx比不到1的场合,NOx的净化率变得不充分,另一方面,当轻油的加入量超过20时,恐有未燃烧的HC作为有害成分被排放出来之虞,不优选。
还有,在上述催化剂的上游一侧加入轻油可以进一步抑制SO2的转化率。
实施例
下面用实施例来更具体说明本发明,不过,本发明并不限于实施例。
(废气净化性能的试验方法)
使用涡流室式柴油机(4缸,3100cc)作为内燃机,用含硫0.05质量%的轻油为内燃机的燃料。
首先,把废气净化用催化剂装在与上述柴油机连接的排气管内,在发动机转速2200rpm预载荷、废气净化用催化剂上游一侧端部的温度(下面称为催化剂入口温度)为500℃的条件下,流通废气1h。
在催化剂入口温度充分稳定于500℃之后,用连续式气体分析仪测定加入轻油之前的废气中的NOx、HC、一氧化碳、SO2的浓度。即,分别用化学发光分析仪(CLD)测定NOx,用氢火焰离子化学分析仪(FID)测定烃、用非色散型红外分析仪(NDIR)测定一氧化碳、用火焰光度分析仪(FPD)测定SO2。结果是,加轻油前的废气组成为:NOx 320ppm,HC60ppm,一氧化碳180ppm,SO2 15ppm。
在上述条件下,以2mL/min的比例从废气用催化剂上游一侧的位置向废气中注入成为NOx还原剂的轻油。从加轻油前的含量与各成分在与催化剂接触之后的含量出发,求出由这样得到的各成分的NOx净化率(转化率)和SO2转化率。表2示出了它的结果。
实施例1
在含有51.6g硝酸铜(II)三水合物的水溶液中加入250g的BET表面积450m2/g、SiO2/Al2O3摩尔比80、平均结晶直径不到0.05μm的H型ZSM-5,充分混合之后,在120℃干燥13h,进一步在电炉中于500℃烧结1h,由此得到了分散担载有氧化铜的Cu-ZSM5粉末。
接着,把198g所得到的Cu-ZSM粉末加入到含37g硝酸镁六水合物和240g硅溶胶(日产化学生产的“Snowtex 0”:SiO2为20重量%)的水溶液中,充分混合后,用球磨机湿式粉碎14h。
把用堇青石制造的open flow型蜂窝载体浸渍于所得到的淤浆中。上述蜂窝载体是53mm(直径)×126mm(长度)的圆筒状,每平方英寸横截面有约400个气体流通胞孔。
然后,把在淤浆中浸渍了的蜂窝载体中的多余淤浆排除之后,横置吹干,接着在500℃下烧结1h。由此得到了废气净化用催化剂。
相对于1L载体,所得到的催化剂中担载有7g氧化铜(CuO)、95gZSM-5、3g氧化镁,这些担载量示出于表1中。用上述方法评价此催化剂的NOX转化率和SO2转化率,结果示出于表2中。
实施例2
除了硝酸镁六水合物用量用12g替代37g之外,与实施例1同样调制催化剂。相对于1L载体,所得到的催化剂中担载有7g氧化铜(CuO)、95gZSM-5、1g氧化镁。
实施例3
除了硝酸镁六水合物用量用61g替代37g之外,与实施例1同样调制催化剂。相对于1L载体,所得到的催化剂中担载有7g氧化铜(CuO)、95gZSM-5、5g氧化镁。
实施例4
除了用24g硝酸钙四水合物替代37g硝酸镁六水合物之外,与实施例1同样调制催化剂。相对于1L载体,所得到的催化剂中担载有7g氧化铜(CuO)、95gZSM-5、3g氧化钙。
实施例5
除了用185g与实施例1同样的ZSM5和72g的SiO2/Al2O3摩尔比为25的NH4型β沸石代替250gZSM-5之外,与实施例1同样调制催化剂。相对于1L载体,所得到的催化剂中担载有7g氧化铜(CuO)、70gZSM-5、β沸石25g、3g氧化镁。
比较例1
把SiO2/Al2O3摩尔比为80的H型ZSM-5浸渍于乙酸铜水溶液(加氨调节pH=11)中,充分混合之后,120℃下干燥一夜,进一步在500℃烧结1h,得到铜/ZSM5粉末。
接着,把150g所得到的粉末加入到含184g硅溶胶(日产化学生产的“Snowtex N”:SiO2为20重量%)的水溶液中,充分混合后,用球磨机湿式粉碎14h。在与实施例1同样方法得到的催化剂中,相对于1L载体,含7g氧化铜、95gZSM5。
表1示出了实施例2~5和比较例1的催化剂的担载量。与实施例1同样,用上述试验方法评价各自的NOx转化率和SO2转化率,表2示出了结果。
表1
CuO | ZSM5(MFI型沸石) | BEA(β型沸石) | Mg或Ca |
H型SiO2/Al2O3=80平均结晶直径不到0.05μm | NH4型SiO2/Al2O3=25 | ||
实施例1 7实施例2 7实施例3 7实施例4 7实施例5 7比较例1 7 | 959595957095 | 25 | Mg3(氧化物计)Mg1(氧化物计)Mg5(氧化物计)Ca3(氧化物计)Mg3(氧化物计) |
表2(500℃下NOx转化率和SO2转化率)
NOx转化率 | SO2转化率 | |
实施例1实施例2实施例3实施例4实施例5比较例1 | 181616161716 | 224115332460 |
由表2中的实施例1~5与比较例1的Cu-ZSM5催化剂比较可知,NOx净化率没有降低,SO2转化率被抑制了。
产业上应用可能性
本发明的催化剂可以用于净化废气特别是由柴油机排放的废气的催化剂。
Claims (5)
1.一种废气净化用催化剂,其特征在于含有氧化铜和ZSM-5和/或β沸石,并进一步含有镁和/或钙的氧化物。
2.权利要求项1中所记载的催化剂,其特征在于所述氧化铜与所述镁和/或钙的氧化物的质量比是,相对于1质量份氧化铜,所述镁和/或钙氧化物为0.1~1质量份范围。
3.权利要求项1或2中所记载的催化剂,其特征在于相对于1L耐火性三维结构体,担载有3~14g所述氧化铜和50~300g所述ZSM-5和/或β沸石。
4.一种废气净化方法,其特征在于使权利要求项1~3中的任何一项所记载的废气净化用催化剂与烃与氮氧化物的体积比为1~20的废气接触。
5.权利要求项4所记载的方法,其特征在于所述废气是柴油机排放的废气。
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