CN111939977A - 含氟聚合物修饰的脱硝催化剂及其制备方法 - Google Patents
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Abstract
本发明涉及一种含氟聚合物修饰的脱硝催化剂,含氟聚合物在脱硝催化剂中的质量含量为0.4%~23.0%,且氟元素在脱硝催化剂中的质量含量为0.3%~17.5%。其制备方法包括以下步骤:向脱硝催化剂中引入含氟聚合物乳液;将含聚合物的脱硝催化剂在80~150℃温度下烘干1~10h;将烘干后的脱硝催化剂在180~420℃温度下烧结1~5h,得到含氟聚合物修饰的脱硝催化剂。本发明制备的催化剂耐水性有明显提升,在很大程度上缓解低温催化剂规模应用过程中耐水性不足的行业难题。本发明只需通过增加一次浸渍、喷淋或喷涂等简单工艺,即可对几乎所有在用中温低温脱硝催化剂进行性能改进。
Description
技术领域
本发明属于脱硝催化剂及其制备技术领域,具体地说是一种含氟聚合物修饰的脱硝催化剂及其制备方法。
背景技术
随着火电超低排放市场逐渐接近饱和,大气污染防治工作的重点转移到污染物排放强度更高的非电行业,非电行业成为大气污染治理的主战场。为全面落实《打赢蓝天保卫战三年行动计划》有关要求,2019年2月生态环境部下发《2019年全国大气污染防治工作要点》,提出加快制订重点行业排放标准、深入开展工业企业提标改造。随着《关于推进实施钢铁行业超低排放的意见》、《工业炉窑大气污染综合治理方案》、《2019年水泥行业大气污染防治攻坚战实施方案》等相关文件相继推出,钢铁、焦化和水泥等重点行业超低排放改造升级,工业烟气治理对催化剂的应用提出新要求。
脱硝催化剂是非电行业烟气治理关键核心技术。一般传统用钒钨钛/钒钼钛催化剂的最佳操作温度范围约为300~420℃,即中温催化剂。钢铁、水泥、玻璃、焦化等非电力行业的工业窑炉设备(焦炉、球团竖炉、烧结机、高炉热风炉、石灰窑、酸洗线、焚烧炉、玻璃陶瓷窑、水泥窑、燃气锅炉、船舶柴油机等)烟气的排放温度处于120℃~300℃范围,需要开发新型低温脱硝催化剂。该类催化剂一般含有Mn、Ce、V、Zr、Fe等活性组分,该类脱硝性能在含水气氛(通常5%~20%)下性能明显下降,150℃以下时表现尤为明显,耐水性不佳限制了低温催化剂体系的规模化应用,解决催化剂耐水性是行业脱硝的当务之急。
聚四氟乙烯(PTFE)、全氟烷基醚共聚物(PFA)等含氟聚合物具有良好的憎水性和稳定性,该类聚合物用于催化剂改性的报道较少。CN103464177A公开了一种氟掺杂的二氧化铈和凹凸棒土脱硝催化剂,采用氟化铵与铈盐混合焙烧制备催化剂;CN109772374A公开了一种锰炭催化剂表面氟接枝方法,采用含氟气体与锰炭催化剂反应,接枝后材料中氟含量达20%以上,含氟气体利用率较低且反应时间较长(1~24h);CN105169807A公开了一种含金属催化剂PTFE布料与PTFE纤维混合通过机织制成功能性滤料用于脱硝和二噁英,将PTFE作为载体使用,催化剂的利用率和应用范围受限。
发明内容
本发明的之一目的是克服现有技术中存在的不足,提供一种耐水性能高的含氟聚合物修饰的脱硝催化剂。
本发明的另一目的是提供一种含氟聚合物修饰的脱硝催化剂的制备方法。
按照本发明提供的技术方案,所述含氟聚合物修饰的脱硝催化剂,含氟聚合物在脱硝催化剂中的质量含量为0.4%~23.0%,且氟元素在脱硝催化剂中的质量含量为0.3%~17.5%。
作为优选,所述脱硝催化剂含有Mn、Ce、V、Zr、Fe、Ti中的一种或几种。
作为优选,所述脱硝催化剂的型式为蜂窝状、颗粒状、卷板式、波纹板式或泡沫状。
作为优选,所述含氟聚合物为聚四氟乙烯、聚氟乙烯、四氟乙烯-六氟丙稀共聚物、四氟乙烯-全氟烷基乙烯基醚共聚物中的一种或几种。
一种含氟聚合物修饰的脱硝催化剂的制备方法包括以下步骤:
(1)、向脱硝催化剂中引入含氟聚合物乳液;
(2)将含聚合物的脱硝催化剂在80~150℃温度下烘干1~10h;
(3)将烘干后的脱硝催化剂在180~420℃温度下烧结1~5h,得到含氟聚合物修饰的脱硝催化剂。
作为优选,步骤(1)中,含氟聚合物乳液引入的方式为直混、浸渍、涂布或者喷淋方式。
作为优选,步骤(1)中,含氟聚合物在乳液中的质量含量为0.5~50.0%。。
本发明与无含氟聚合物修饰的催化剂相比,特别是针对低温型工业脱硝催化剂,按本发明制备的催化剂耐水性有明显提升,在很大程度上缓解低温催化剂规模应用过程中耐水性不足的行业难题。
本发明只需通过增加一次浸渍、喷淋或喷涂等简单工艺,即可对几乎所有在用中温低温脱硝催化剂进行性能改进。
附图说明
图1是实施例1和对比例1的催化效率评价结果对比图。
图2是实施例2和对比例2的NOx转化率评价结果对比图。
图3是实施例3和对比例3的脱硝转化率评价结果对比图。
图4是实施例4和对比例4的脱硝转化率评价结果对比图。
图5是实施例5和对比例5的脱硝转化率评价结果对比图。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
以下实施例和对比例中,催化剂小样评价条件:GHSV=15000h-1,450ppm NO,500ppm NH3,6%O2,5%CO2,8%H2O,N2为平衡气。除实施例1和对比例1外,其余实施例和对比例评价温度均为160℃。
实施例1
中温V2O5/WO3-TiO2脱硝催化剂,采用聚四氟乙烯修饰,修饰后聚四氟乙烯在脱硝催化剂中的质量含量为0.4%,氟元素在脱硝催化剂中的质量含量为0.3%,主要步骤如下:
(1)、取规格尺寸150mm*150mm*100mm,孔密度100目的工业用中温V2O5/WO3-TiO2脱硝蜂窝催化剂,将整块催化剂没入稀释至含聚四氟乙烯浓度为0.5%的乳液中,30s后取出沥干;
(2)、催化剂经120℃、4h烘干;
(3)、将烘干后的催化剂在420℃烧结2h。
在修饰后的催化剂中取13mm*13mm*40mm尺寸样品,以未修饰样品为对比例1,将实施例1与对比例1进行脱硝性能评价,评价结果见表1,以表1的数据绘制成脱硝性能评价对比图1。
表1
实施例2
低温MnCe/ZrO2-TiO2脱硝催化剂,采用聚氟乙烯修饰,修饰后聚氟乙烯在脱硝催化剂中的质量含量为6.7%,氟元素在脱硝催化剂中的质量含量为4.1%,主要步骤如下:
(1)取规格为50mm*50mm*100mm的波纹板式催化剂,孔密度为200目的工业用低温MnCe/ZrO2-TiO2脱硝催化剂,将稀释至含聚氟乙烯共聚物浓度为3.0%的乳液沿平行于孔道方向喷淋至催化剂表面,直至下端淋透,将催化剂沥干;
(2)催化剂经120℃、4h烘干;
(3)将烘干后的催化剂在180℃烧结2h。
在修饰后的催化剂中取13mm*13mm*40mm尺寸样品,以未修饰样品为对比例2,将实施例2与对比例2进行脱硝性能评价,评价结果见表2,以表2的数据绘制成脱硝性能对比图2。以表2的数据可以得出:实施例2的平均脱硝转化率约为83.2%,对比例2的平均脱硝转化率约为58.6%。
表2
实施例3
低温MnCe/ZrO2-TiO2脱硝催化剂,采用聚氟乙烯、四氟乙烯-六氟丙稀共聚物混合修饰,修饰后共聚物在脱硝催化剂中的质量含量为5.2%,氟元素在脱硝催化剂中的质量含量为3.7%,主要步骤如下:
(1)取规格为50mm*50mm的纺织纤维催化剂,MnCe/ZrO2-TiO2催化剂含量约5%,将催化剂放入0.6倍催化剂质量、共聚物浓度为10.0%的乳液浸渍,完全吸收乳液后取出;
(2)催化剂经120℃、4h烘干;
(3)将烘干后的催化剂在180℃烧结2h。
在修饰后的催化剂中取13mm*13mm*40mm尺寸样品,以未修饰样品为对比例3,将实施例3与对比例3进行脱硝性能评价,评价结果见表3,以表3的数据绘制成脱硝性能对比图3。以表3的数据可以得出:实施例3的脱硝转化率约为76.6%,对比例3的脱硝转化率约为58.6%。
表3
实施例4
低温MnV/ZrO2-TiO2脱硝催化剂,采用四氟乙烯-全氟烷基乙烯基醚共聚物修饰,修饰后四氟乙烯-全氟烷基乙烯基醚共聚物在脱硝催化剂中的质量含量为9.0%,氟元素在脱硝催化剂中的质量含量为6.5%,制备步骤如下:
(1)取40~60目颗粒大小MnV/Fe2O3-TiO2催化剂,将催化剂质量0.6倍、含四氟乙烯-全氟烷基乙烯基醚共聚物浓度为15.0%的乳液加入催化剂,乳液被完全吸收;
(2)催化剂经120℃、4h烘干;
(3)将烘干后的催化剂在250℃烧结2h。
在修饰后的催化剂中取13mm*13mm*40mm尺寸样品,以未修饰样品为对比例4,将实施例4与对比例4进行脱硝性能评价,评价结果见表4,以表4的数据绘制成脱硝性能对比图4。以表4的数据可以得出:实施例4的脱硝转化率约为69.1%,对比例4的脱硝转化率约63.2%。
表4
实施例5
低温MnCe/Fe2O3-TiO2脱硝催化剂,采用聚四氟乙烯修饰,修饰后聚四氟乙烯在脱硝催化剂中的质量含量为23.0%,氟元素在脱硝催化剂中的质量含量为17.5%,主要步骤如下:
(1)取40~60目颗粒大小的MnCe/Fe2O3-TiO2催化剂,将含聚四氟乙烯浓度为50.0%的乳液喷涂至颗粒润湿;
(2)催化剂经120℃、4h烘干;
(3)将烘干后的催化剂在350℃烧结2h。
在修饰后的催化剂中取13mm*13mm*40mm尺寸样品,以未修饰样品为对比例5,将实施例5与对比例5进行脱硝性能评价,评价结果见表5,以表5的数据绘制成脱硝性能对比图5。以表5的数据可以得出:实施例5的脱硝转化率约为71.6%,对比例5的脱硝转化率约为66.8%。
表5
由上述结果可知,含氟聚合物修饰对脱硝催化剂低温脱硝性能有促进作用。根据聚合物种类和用量的差异,在相同测试条件下,NOx转化率可提升4.8~24.6%。
Claims (7)
1.一种含氟聚合物修饰的脱硝催化剂,其特征是:含氟聚合物在脱硝催化剂中的质量含量为0.4%~23.0%,且氟元素在脱硝催化剂中的质量含量为0.3%~17.5%。
2.根据权利要求1所述的含氟聚合物修饰的脱硝催化剂,其特征是:所述脱硝催化剂含有Mn、Ce、V、Zr、Fe、Ti中的一种或几种。
3.根据权利要求1或2所述的含氟聚合物修饰的脱硝催化剂,其特征是:所述脱硝催化剂的型式为蜂窝状、颗粒状、卷板式、波纹板式或泡沫状。
4.根据权利要求1所述的含氟聚合物修饰的脱硝催化剂,其特征是:所述含氟聚合物为聚四氟乙烯、聚氟乙烯、四氟乙烯-六氟丙稀共聚物、四氟乙烯-全氟烷基乙烯基醚共聚物中的一种或几种。
5.一种含氟聚合物修饰的脱硝催化剂的制备方法包括以下步骤:
(1)、向脱硝催化剂中引入含氟聚合物乳液;
(2)将含聚合物的脱硝催化剂在80~150℃温度下烘干1~10h;
(3)将烘干后的脱硝催化剂在180~420℃温度下烧结1~5h,得到含氟聚合物修饰的脱硝催化剂。
6.根据权利要求5所述的含氟聚合物修饰的脱硝催化剂的制备方法,其特征是:步骤(1)中,含氟聚合物乳液引入的方式为直混、浸渍、涂布或者喷淋方式。
7.根据权利要求5所述的含氟聚合物修饰的脱硝催化剂的制备方法,其特征是:步骤(1)中,含氟聚合物在乳液中的质量含量为0.5~50.0%。
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