CN115430459B - 一种协同脱硝脱VOCs催化剂及其制备方法和应用 - Google Patents
一种协同脱硝脱VOCs催化剂及其制备方法和应用 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
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- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 4
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
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- 239000011148 porous material Substances 0.000 description 1
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- 239000002912 waste gas Substances 0.000 description 1
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Abstract
本发明提供了一种协同脱硝脱VOCs催化剂及其制备方法和应用。本发明的协同脱硝脱VOCs催化剂的制备方法,包括如下步骤:S1:对金属蜂窝载体进行超声处理、洗涤、干燥、煅烧,制得预处理金属蜂窝载体;S2:将分子筛浸渍于含有铜盐、锰盐和铁盐的混合溶液中,水浴搅拌后干燥、研磨,制得催化剂粉末;S3:将催化剂粉末与铝溶胶混合制成浆液;S4:将预处理金属蜂窝载体浸渍于浆液中,浸渍后干燥、煅烧,制得协同脱硝脱VOCs催化剂。本发明的协同脱硝脱VOCs催化剂制造成本低,脱硝脱VOCs效率高,脱硝脱VOCs活性温度窗口宽,抗SO2、H2O性能强,兼具优异的脱硝脱VOCs性能。
Description
技术领域
本发明涉及催化剂制备技术领域,尤其是涉及一种协同脱硝脱VOCs催化剂及其制备方法和应用。
背景技术
氮氧化物(NOx)和挥发性有机物(VOCs)都是常见的大气污染物,NOx会导致酸雨、臭氧空洞、光化学烟雾等环境问题,VOCs则会引发灰霾、光化学烟雾等问题。通常,在工业燃煤锅炉所排放的烟气中,会同时含有NOx和VOCs,现有技术通常是分别对NOx和VOCs进行脱除。因此,若能开发具备协同脱除NOx和VOCs的催化剂,可以简化工业企业的废气治理工艺流程,降低环保成本,具有显著的经济价值和社会效益。
鉴于此,特提出本发明。
发明内容
本发明的目的在于提供一种协同脱硝脱VOCs催化剂及其制备方法和应用,该协同脱硝脱VOCs催化剂制造成本低,脱硝脱VOCs效率高,脱硝脱VOCs活性温度窗口宽,抗SO2、H2O性能强,兼具优异的脱硝脱VOCs性能。
本发明提供一种协同脱硝脱VOCs催化剂的制备方法,包括如下步骤:
S1:对金属蜂窝载体进行超声处理、洗涤、干燥、煅烧,制得预处理金属蜂窝载体;
S2:将分子筛浸渍于含有铜盐、锰盐和铁盐的混合溶液中,水浴搅拌后干燥、研磨,制得催化剂粉末;
S3:将催化剂粉末与铝溶胶混合制成浆液;
S4:将预处理金属蜂窝载体浸渍于浆液中,浸渍后干燥、煅烧,制得协同脱硝脱VOCs催化剂。
上述步骤S1中,金属蜂窝载体的材质为FeCrAl合金,FeCrAl合金的Cr含量为15-20%,Al含量为3-6%,金属蜂窝载体的目数为300-500目。
此外,步骤S1中,超声处理的频率为40-80kHz,超声处理的时间为10-20min;干燥的温度为115-125℃;煅烧的温度为900-1100℃,煅烧的时间为1-5h。
上述步骤S2中,水浴搅拌的温度为80-90℃,水浴搅拌的时间为1-4h;催化剂粉末的粒径为2-10μm。
此外,步骤S2中,催化剂粉末中CuO的质量分数为3-6%,MnO2的质量分数为2-6%,Fe2O3的质量分数为1-5%。
上述步骤S3中,铝溶胶的固含量为5-10%;混合包括:在800-1000rpm的转速下剧烈搅拌1-4h;浆液的固含量为40-50%。
上述步骤S4中,分子筛选自SSZ-13和SSZ-39中的至少一种;浸渍时间为1-10min;干燥的温度为115-125℃;煅烧的温度为400-550℃,煅烧的时间为1-5h。
本发明还提供一种协同脱硝脱VOCs催化剂,按照上述制备方法制得。
本发明还提供上述协同脱硝脱VOCs催化剂在脱硝脱VOCs中的应用。
具体地,脱硝脱VOCs时的温度为200-500℃。
本发明的实施,至少具有以下优势:
1、本发明的协同脱硝脱VOCs催化剂以特定预处理的金属蜂窝载体为基底,具备高几何比表面积、高机械强度、导热性能优异、强耐腐蚀性能等优势,有利于实现催化剂与NOx、VOCs的充分接触和反应,能够有效避免催化过程中因放热而产生的局部热点,此外还具备更好的抗堵灰性能;
2、本发明的协同脱硝脱VOCs催化剂以SSZ-13和/或SSZ-39分子筛作为催化剂载体,通过特定的制备方式使其具备高比表面积、高热稳定性和水热稳定性、优良的孔道结构,从而有利于保障活性组分的高度分散,增强了活性组分与载体之间的相互作用,拓宽了催化剂的活性温度窗口;
3、本发明的协同脱硝脱VOCs催化剂采用廉价的Cu、Mn、Fe金属氧化物作为活性组分,不添加任何贵金属,大大降低了催化剂的制造成本;同时,采用特定的方式将其负载于载体和基底上,在高效脱硝的同时,实现VOCs的催化氧化,催化剂的脱硝脱VOCs效率高,抗SO2、H2O性能强。
具体实施方式
应该指出,以下详细说明都是例示性的,旨在对本申请提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本申请的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也包括复数形式,此外,还应当理解的是,当在本说明中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
下面将结合实施例对本发明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。基于本发明中的实施例,本领域普通技术人员在没有做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。
实施例1
本实施例的协同脱硝脱VOCs催化剂的制备方法,步骤如下:
1、金属蜂窝载体预处理
取FeCrAl合金制备的金属蜂窝载体,FeCrAl合金的Cr含量15%,Al含量3%,金属蜂窝载体目数为400目。将金属蜂窝载体浸入丙酮中,在40kHz下超声处理20min,随后用去离子水洗涤,经120℃烘干后,再在空气气氛中于900℃煅烧5h,制得预处理金属蜂窝载体。
2、制备催化剂粉末
将SSZ-13分子筛浸渍在含有硝酸铜、硝酸锰、硝酸铁的水溶液中,在80℃水浴搅拌4h,随后烘干,再研磨成催化剂粉末;其中,催化剂粉末中CuO的质量分数为6%,MnO2的质量分数为2%,Fe2O3的质量分数为3%,催化剂粉末粒径为5μm。
3、制备浆液
将上述催化剂粉末加入铝溶胶(固含量为5%)中,在1000rpm的转速下剧烈搅拌2h,形成浆液(固含量为40%)。
4、制备协同脱硝脱VOCs催化剂
将预处理金属蜂窝载体浸入浆液中,浸渍1min后取出,使用压缩空气吹扫除去预处理金属蜂窝载体中多余的浆液,将预处理金属蜂窝载体水平放置,于120℃烘干后,再在空气气氛中于500℃煅烧2h,制得协同脱硝脱VOCs催化剂。
实施例2
本实施例的协同脱硝脱VOCs催化剂的制备方法,步骤如下:
1、金属蜂窝载体预处理
取FeCrAl合金制备的金属蜂窝载体,FeCrAl合金的Cr含量20%,Al含量6%,金属蜂窝载体目数为300目。将金属蜂窝载体浸入丙酮中,在80kHz下超声处理10min,随后用去离子水洗涤,经120℃烘干后,再在空气气氛中于1000℃煅烧2h,制得预处理金属蜂窝载体。
2、制备催化剂粉末
将SSZ-39分子筛浸渍在含有硝酸铜、硝酸锰、硝酸铁的水溶液中,在85℃水浴搅拌3h,随后烘干,再研磨成催化剂粉末;其中,催化剂粉末中4%,MnO2的质量分数为4%,Fe2O3的质量分数为1%,催化剂粉末粒径为2μm。
3、制备浆液
将上述催化剂粉末加入铝溶胶(固含量为8%),在900rpm的转速下剧烈搅拌1h,形成浆液(固含量为45%)。
4、制备协同脱硝脱VOCs催化剂
将预处理金属蜂窝载体浸入浆液中,浸渍10min后取出,使用压缩空气吹扫除去预处理金属蜂窝载体中多余的浆液,将预处理金属蜂窝载体水平放置,于120℃烘干后,再在空气气氛中于400℃煅烧5h,制得协同脱硝脱VOCs催化剂。
实施例3
本实施例的协同脱硝脱VOCs催化剂的制备方法,步骤如下:
1、金属蜂窝载体预处理
取FeCrAl合金制备的金属蜂窝载体,FeCrAl合金的Cr含量15%,Al含量5%,金属蜂窝载体目数为500目。将金属蜂窝载体浸入丙酮中,在60kHz下超声处理15min,随后用去离子水洗涤,经120℃烘干后,再在空气气氛中于1100℃煅烧1h,制得预处理金属蜂窝载体。
2、制备催化剂粉末
将SSZ-39分子筛浸渍在含有硝酸铜、硝酸锰、硝酸铁的水溶液中,在85℃水浴搅拌2h,随后烘干,再研磨成催化剂粉末;其中,催化剂粉末中CuO的质量分数为3%,MnO2的质量分数为6%,Fe2O3的质量分数为2%,催化剂粉末粒径为10μm。
3、制备浆液
将上述催化剂粉末加入铝溶胶(固含量为6%),在800rpm的转速下剧烈搅拌4h,形成浆液(固含量为45%)。
4、制备协同脱硝脱VOCs催化剂
将预处理金属蜂窝载体浸入浆液中,浸渍5min后取出,使用压缩空气吹扫除去预处理金属蜂窝载体中多余的浆液,将预处理金属蜂窝载体水平放置,于120℃烘干后,再在空气气氛中于450℃煅烧3h,制得协同脱硝脱VOCs催化剂。
实施例4
本实施例的协同脱硝脱VOCs催化剂的制备方法,步骤如下:
1、金属蜂窝载体预处理
取FeCrAl合金制备的金属蜂窝载体,FeCrAl合金的Cr含量20%,Al含量5%,金属蜂窝载体目数为400目。将金属蜂窝载体浸入丙酮中,在40kHz下超声处理20min,随后用去离子水洗涤,经120℃烘干后,再在空气气氛中于1050℃煅烧3h,制得预处理金属蜂窝载体。
2、制备催化剂粉末
将SSZ-13分子筛与SSZ-39分子筛按质量比1:1混合,将混合后的混合物浸渍在含有硝酸铜、硝酸锰、硝酸铁的水溶液中,在90℃水浴搅拌1h,随后烘干,再研磨成催化剂粉末;其中,催化剂粉末中CuO的质量分数为5%,MnO2的质量分数为3%,Fe2O3的质量分数为5%,催化剂粉末粒径为4μm。
3、制备浆液
将上述催化剂粉末加入铝溶胶(固含量为10%),在900rpm的转速下剧烈搅拌3h,形成浆液(固含量为50%)。
4、制备协同脱硝脱VOCs催化剂
将预处理金属蜂窝载体浸入浆液中,浸渍4min后取出,使用压缩空气吹扫除去预处理金属蜂窝载体中多余的浆液,将预处理金属蜂窝载体水平放置,于120℃烘干后,再在空气气氛中于550℃煅烧1h,制得协同脱硝脱VOCs催化剂。
试验例1
对实施例1-4制备的催化剂进行性能测试;其中:脱硝测试条件如下:
测试温度200-500℃,NH3浓度600ppm,NH3/NO=1,SO2浓度200ppm,H2O浓度10%,甲苯浓度80ppm,GHSV=60000h-1。
此外,采用甲苯作为VOCs的特征分子进行脱VOCs测试;各催化剂的脱硝效率和脱VOCs分别见表1、表2。
表1各催化剂的脱硝效率
由表1可见:
采用本发明方法制备的催化剂在200-500℃温度区间内的脱硝效率较高,脱硝活性温度窗口宽,抗SO2、H2O性能强,脱硝性能优异。
表2各催化剂的脱甲苯效率
由表2可见:
采用本发明方法制备的催化剂在200-500℃温度区间内的脱甲苯效率较高,脱甲苯活性温度窗口宽,抗SO2、H2O性能强,脱VOCs性能优异。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (6)
1.一种协同脱硝脱VOCs催化剂的制备方法,其特征在于,包括如下步骤:
S1:对金属蜂窝载体进行超声处理、洗涤、干燥、煅烧,制得预处理金属蜂窝载体;
S2:将分子筛浸渍于含有铜盐、锰盐和铁盐的混合溶液中,水浴搅拌后干燥、研磨,制得催化剂粉末;
S3:将催化剂粉末与铝溶胶混合制成浆液;
S4:将预处理金属蜂窝载体浸渍于浆液中,浸渍后干燥、煅烧,制得协同脱硝脱VOCs催化剂;
步骤S1中,金属蜂窝载体的材质为FeCrAl合金,FeCrAl合金的Cr含量为15-20%,Al含量为3-6%,金属蜂窝载体的目数为300-500目;超声处理的频率为40-80kHz,超声处理的时间为10-20min;干燥的温度为115-125℃;煅烧的温度为900-1100℃,煅烧的时间为1-5h;
步骤S2中,分子筛选自SSZ-13和SSZ-39中的至少一种;催化剂粉末中CuO的质量分数为3-6%,MnO2的质量分数为2-6%,Fe2O3的质量分数为1-5%;
步骤S4中,浸渍时间为1-10min;干燥的温度为115-125℃;煅烧的温度为400-550℃,煅烧的时间为1-5h。
2.根据权利要求1所述的制备方法,其特征在于,步骤S2中,水浴搅拌的温度为80-90℃,水浴搅拌的时间为1-4h;催化剂粉末的粒径为2-10μm。
3.根据权利要求1所述的制备方法,其特征在于,步骤S3中,铝溶胶的固含量为5-10%;混合包括:在800-1000rpm的转速下剧烈搅拌1-4h;浆液的固含量为40-50%。
4.一种协同脱硝脱VOCs催化剂,其特征在于,按照权利要求1-3任一所述的制备方法制得。
5.权利要求4所述的协同脱硝脱VOCs催化剂在脱硝脱VOCs中的应用。
6.根据权利要求5所述的应用,其特征在于,脱硝脱VOCs时的温度为200-500℃。
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