CN112295568A - 一种CeO2改性的铁基SCR脱硝催化剂的制备方法 - Google Patents
一种CeO2改性的铁基SCR脱硝催化剂的制备方法 Download PDFInfo
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 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 claims abstract description 26
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Abstract
一种CeO2改性的铁基SCR脱硝催化剂的制备方法,取去离子水加热,加入草酸、硝酸铁、七钼酸铵、硝酸铈,之后在磁力搅拌下水浴加热2小时,待水温降低到50℃以下,加入一乙醇胺,搅拌得到混合溶液;将载体加入到混合溶液中,混合均匀,之后加热陈化、煅烧得到催化剂粉体,将其均匀涂覆在基材表面制成板式或波纹式脱硝催化剂。本发明制备的催化剂烟气温度在150℃~300℃脱硝效果好,克服了目前制备方法存在的活性组分分布不均、晶粒出现团聚现象等不足。
Description
技术领域
本发明涉及一种CeO2改性的铁基SCR脱硝催化剂的制备方法,属于低温脱硝技术领域。
背景技术
NOx是造成大气污染的主要污染物,容易导致酸雨、光化学烟雾和臭氧层的消耗以及温室效应等环境问题。同时,在工业生产与人们的生活中,他们可以直接危害人体的健康。SCR法是目前国内外燃煤电厂应用最多且最成熟的有效去除控制NOx的技术,脱硝效率可达到90%以上,稳定性好,脱除效率高。
目前,工业应用最广泛的催化剂为V2O5-WO3(MoO3)/TiO2催化剂,但其存在以下三个主要缺点,脱硝温度偏高及窗口窄(300-400℃),催化剂需要布置于除尘器和脱硫塔之前;高温时易将烟气中SO2氧化为SO3,腐蚀尾部烟道;活性组分钒有剧毒,易对环境和人类造成毒害。因此需要开发研究SCR脱硝活性更高、反应温度低的新型催化剂。
与传统商用钒钛钨催化剂相比,铁基催化剂具有良好的抗H2O和SO2毒化作用,且脱硝成本低,但采用常规离子交换-浸渍法或共沉淀法或溶胶-凝胶法等方法制备的铁基催化剂的中低温(150℃~300℃)脱硝性能较低,主要原因是常规搅拌加热为由外及内的加热搅拌过程,促使铁基氧化物前驱体盐与其他助剂前驱体盐存在温度梯度,水解速率不一,易造成各晶粒分布不均、出现团聚现象,在与钛白粉等载体混合时极容易出现活性组分分布不均而影响脱硝性能。
发明内容
本发明的目的在于提供一种CeO2改性的铁基SCR脱硝催化剂的制备方法,通过添加一定量的氧化铈,以及磁化、水浴加热、捏合等改性手段合成的铁基SCR脱硝催化剂,制备出的催化剂烟气温度在150℃~300℃脱硝效果好,以克服目前制备方法存在的活性组分分布不均、晶粒出现团聚现象等不足。
本发明采用以下技术方案:
一种CeO2改性的铁基SCR脱硝催化剂的制备方法,包括以下步骤:
步骤一:量取去离子水并加热至90-100℃;将草酸加入到上述去离子水中,然后在搅拌状态下缓慢加入硝酸铁、七钼酸铵和硝酸铈(其中七钼酸铵的引入是为了扩大脱硝反应的温度范围,提高催化剂载体机械性能、热稳定性和低温催化选择性,防止催化剂砷中毒等。),之后在磁力搅拌下水浴加热2小时,待水温降低到50℃以下,再加入一乙醇胺(其中一乙醇胺是防止酸性物质对设备的腐蚀和酸性环境对催化剂粉末活性的影响,以及调节混合溶液PH值。)搅拌1小时得到混合溶液;
步骤二:将载体溶解在混合溶液中,通过捏合机充分混合均匀,再在电热鼓风烘箱中110℃陈化24小时,最后在马弗炉中充足空气氛围下煅烧5小时得到CeO2改性的铁基SCR脱硝催化剂粉体。
一种CeO2改性的铁基SCR脱硝催化剂的制备方法,包括以下步骤:
步骤一:按重量分数进行计量,取80-130份去离子水,并加热至90-100℃,加入12.0-14.0份草酸,然后在搅拌状态下缓慢加入6.8-7.5份硝酸铁、4.2-7.9份的七钼酸铵和8.3-8.7份硝酸铈,之后在磁力搅拌下水浴加热2小时,待水温降低到50℃以下,再加入6.1-7.0份一乙醇胺,搅拌1小时得到混合溶液;
步骤二:称取载体75.9-80.7份,加入到上述混合溶液中,通过捏合机充分混合均匀,再在电热鼓风烘箱中110℃陈化24小时,最后在马弗炉中充足空气氛围下煅烧5小时得到CeO2改性的铁基SCR脱硝催化剂粉体。
进一步的,各组分加量分别为:80份去离子水,12.0份草酸,6.8份硝酸铁,4.2份的七钼酸铵,8.3份硝酸铈,6.1份一乙醇胺,载体80.7份。
进一步的,各组分加量分别为:130份去离子水,14.0份草酸,7.5份硝酸铁,7.9份的七钼酸铵,8.7份硝酸铈,7.0份一乙醇胺,载体75.9份。
进一步的,所述载体为TiO2、γ-Al2O3或分子筛中的一种或者多种组合。
进一步的,将所述CeO2改性的铁基SCR脱硝催化剂粉体均匀涂覆在不锈钢网或者玻璃纤维毡基材表面,制成板式脱硝催化剂或波纹式脱硝催化剂。
本发明的有益效果:
本发明CeO2改性的铁基催化剂的制备方法,采用磁化和水浴加热会提高各氧化物前驱体盐的水解速率,减少水解时间,降低能耗,且前驱体盐表面的弱键与磁场发生局部效应,抑制由于温度梯度而造成晶粒团聚现象的发生,得到均一、分散度高的混合溶液,后续采用捏合机将混合溶液与载体充分捏合,得到活性物质分布均匀的铁基复合催化剂,温度在150℃~300℃表现出较好的SCR脱硝性能。
本发明制造出的CeO2改性的铁基催化剂,具有良好的低温催化活性,抗硫抗水中毒能力强。
与传统钒钛钨商用催化剂相比应用温度窗口低,为150℃~300℃,催化剂可布置于除尘器和脱硫塔之后,延长催化剂使用机械寿命;由于使用在烟气温度较低的环境,烟气中SO2氧化为SO3的转化率低;活性组分不含钒等剧毒物质,不会对环境和人类造成毒害,也有利于催化剂的二次回收和再生。
具体实施方式
下面结合具体实施例对本发明做进一步详细描述。
一种CeO2改性的铁基SCR脱硝催化剂的制备方法,按重量分数进行计量,取80-130份去离子水,将其加热至90-100℃,加入12.0-14.0份草酸,然后在搅拌状态下缓慢加入6.8-7.5份硝酸铁、4.2-7.9份的七钼酸铵和8.3-8.7份硝酸铈,之后在磁力搅拌下水浴加热2小时,待水温降低到50℃以下,再加入6.1-7.0份一乙醇胺,搅拌1小时得到混合溶液。
将TiO2、γ-Al2O3或分子筛中的一种或者多种为载体称取75.9-80.7份,加入到上述混合溶液中,通过捏合机充分混合均匀,再在电热鼓风烘箱中110℃陈化24小时,最后在马弗炉中充足空气氛围下煅烧5小时得到CeO2改性的铁基SCR脱硝催化剂粉体,将其均匀涂覆在不锈钢网或者玻璃纤维毡基材表面制成板式脱硝催化剂或波纹式脱硝催化剂。
实例1
一种CeO2改性的铁基SCR脱硝催化剂的制备方法,包括以下步骤:
步骤1,称取80份去离子水,将其加热至90-100℃,加入12.0份草酸;
步骤2,在搅拌状态下缓慢加入6.8份硝酸铁、4.2份的七钼酸铵和8.3份硝酸铈,之后在磁力搅拌下水浴加热2小时;
步骤3,待水温降低到50℃以下,再加入6.1份一乙醇胺,搅拌1小时得到混合溶液;
步骤4,将TiO2为载体称取80.7份,加入到上述混合溶液中,通过捏合机充分混合均匀,再在电热鼓风烘箱中110℃陈化24小时;
步骤5,在马弗炉中充足空气氛围下煅烧5小时得到CeO2改性的铁基SCR脱硝催化剂粉体;
步骤6,将其均匀涂覆在不锈钢网表面制成板式脱硝催化剂。
实例2
一种CeO2改性的铁基SCR脱硝催化剂的制备方法,包括以下步骤:
步骤1,称取130份去离子水,将其加热至90-100℃,加入14.0份草酸;
步骤2,在搅拌状态下缓慢加入7.5份硝酸铁、7.9份的七钼酸铵和8.7份硝酸铈,之后在磁力搅拌下水浴加热2小时;
步骤3,待水温降低到50℃以下,再加入7.0份一乙醇胺,搅拌1小时得到混合溶液;
步骤4,将γ-Al2O3载体称取75.9份,加入到上述混合溶液中,通过捏合机充分混合均匀,再在电热鼓风烘箱中110℃陈化24小时;
步骤5,在马弗炉中充足空气氛围下煅烧5小时得到CeO2改性的铁基SCR脱硝催化剂粉体;
步骤6,将其均匀涂覆在玻璃纤维毡基材表面制成波纹式脱硝催化剂。
实例3
一种CeO2改性的铁基SCR脱硝催化剂的制备方法,包括以下步骤:
步骤1,称取100份去离子水,将其加热至90-100℃,加入13.0份草酸;
步骤2,在搅拌状态下缓慢加入7.0份硝酸铁、6.5份的七钼酸铵和8.5份硝酸铈,之后在磁力搅拌下水浴加热2小时;
步骤3,待水温降低到50℃以下,再加入6.6份一乙醇胺,搅拌1小时得到混合溶液;
步骤4,将γ-Al2O3载体称取79份,加入到上述混合溶液中,通过捏合机充分混合均匀,再在电热鼓风烘箱中110℃陈化24小时;
步骤5,在马弗炉中充足空气氛围下煅烧5小时得到CeO2改性的铁基SCR脱硝催化剂粉体;
步骤6,将其均匀涂覆在不锈钢网表面制成波纹式脱硝催化剂。
Claims (6)
1.一种CeO2改性的铁基SCR脱硝催化剂的制备方法,其特征在于,包括以下步骤:
步骤一:量取去离子水并加热至90-100℃;将草酸加入到上述去离子水中,然后在搅拌状态下缓慢加入硝酸铁、七钼酸铵和硝酸铈,之后在磁力搅拌下水浴加热2小时,待水温降低到50℃以下,再加入一乙醇胺搅拌1小时得到混合溶液;
步骤二:将载体溶解在混合溶液中,通过捏合机充分混合均匀,再在电热鼓风烘箱中110℃陈化24小时,最后在马弗炉中充足空气氛围下煅烧5小时得到CeO2改性的铁基SCR脱硝催化剂粉体。
2.一种CeO2改性的铁基SCR脱硝催化剂的制备方法,其特征在于,包括以下步骤:
步骤一:按重量分数进行计量,取80-130份去离子水,并加热至90-100℃,加入12.0-14.0份草酸,然后在搅拌状态下缓慢加入6.8-7.5份硝酸铁、4.2-7.9份的七钼酸铵和8.3-8.7份硝酸铈,之后在磁力搅拌下水浴加热2小时,待水温降低到50℃以下,再加入6.1-7.0份一乙醇胺,搅拌1小时得到混合溶液;
步骤二:称取载体75.9-80.7份,加入到上述混合溶液中,通过捏合机充分混合均匀,再在电热鼓风烘箱中110℃陈化24小时,最后在马弗炉中充足空气氛围下煅烧5小时得到CeO2改性的铁基SCR脱硝催化剂粉体。
3.如权利要求2所述的CeO2改性的铁基SCR脱硝催化剂的制备方法,其特征在于,各组分加量分别为:80份去离子水,12.0份草酸,6.8份硝酸铁,4.2份的七钼酸铵,8.3份硝酸铈,6.1份一乙醇胺,载体80.7份。
4.如权利要求2所述的CeO2改性的铁基SCR脱硝催化剂的制备方法,其特征在于,各组分加量分别为:130份去离子水,14.0份草酸,7.5份硝酸铁,7.9份的七钼酸铵,8.7份硝酸铈,7.0份一乙醇胺,载体75.9份。
5.如权利要求1~4任一所述CeO2改性的铁基SCR脱硝催化剂的制备方法,其特征在于,所述载体为TiO2、γ-Al2O3或分子筛中的一种或者多种组合。
6.如权利要求1~4任一所述CeO2改性的铁基SCR脱硝催化剂的制备方法,其特征在于,将所述CeO2改性的铁基SCR脱硝催化剂粉体均匀涂覆在不锈钢网或者玻璃纤维毡基材表面,制成板式脱硝催化剂或波纹式脱硝催化剂。
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