锌-胺改性氢氧化锆对氮氧化物的净化性能及其净化机理  

Removal performance and mechanism of nitrogen oxides by zinc-amine modified zirconium hydroxide

作　　者：王馨博[1] 栗丽[1] 李凯[1] 梁国杰[1] 赵越[1] 苏茹月 栾志强[1] 习海玲[1] WANG Xinbo;LI Li;LI Kai;LIANG Guojie;ZHAO Yue;SU Ruyue;LUAN Zhiqiang;XI Hailing(State Key Laboratory of NBC Protection for Civilian,Research Institute of Chemical Defense,Beijing 100191,China)

机构地区：[1]防化研究院,国民核生化灾害防护国家重点实验室,北京100191

出　　处：《环境工程学报》2020年第10期2761-2773,共13页Chinese Journal of Environmental Engineering

基　　金：国家重点研发计划项目(2016YFC0204205);国家自然科学基金面上资助项目(21876204);国民核生化灾害防护国家重点实验室基金资助项目(SKLNBC2018-04)。

摘　　要：通过向氢氧化锆(Zr(OH)4)颗粒表面浸渍负载活性组分Zn、三乙烯二胺(triethylenediamine,TEDA)和ZnTEDA,分别研究了Zn和TEDA单独或同时改性的Zr(OH)4对NO2的净化性能及净化机理,探讨了Zr(OH)4基体、Zn和TEDA 3种组分与NO2及所生成的NO之间的相互作用机制。结果表明:同时负载质量分数为4%的Zn和6%的TEDA,可使Zr(OH)4对NO2的净化能力得到显著提升,改性后材料的穿透时间可达84 min,NO2穿透吸附量可达24.8 mg·cm-3,NO释放比例降低至6%;Zr(OH)4基体主要通过表面端式羟基与NO2形成硝酸盐和亚硝酸盐,从而将其脱除,活性金属组分Zn主要作为表面碱性吸附位点提供辅助作用,而有机胺TEDA则能够催化NO2的表面水解反应,使之转变为酸性更强的HNO3和HNO2,进而得到快速消除;当负载Zn和TEDA时,基体、金属和有机胺可进行有效配合,形成的协同效应对材料的NO2净化性能产生了显著的提升效果,在延缓NO释放的同时大幅降低了NO的生成比例。以上研究结果可为新型氮氧化物净化材料的设计制备提供参考。By impregnating active components Zn,triethylenediamine(TEDA)and Zn-TEDA on the surface of zirconium hydroxide(Zr(OH)4)granules,the NO2 removal performance and mechanism of Zn and/or TEDA modified Zr(OH)4 were investigated.The interaction mechanisms of Zr(OH)4,Zn and TEDA with NO2 and yielded NO were discussed in detail.The results showed that the NO2 purifying ability of Zr(OH)4 was significantly improved by loading 4%Zn and 6%TEDA at the same time.The breakthrough time of the zincamine modified Zr(OH)4 could reach 84 min,the adsorption capacity for NO2 breakthrough could reach24.8 mg·cm-3,and the NO release ratio decreased to 6%.In terms of the interaction mechanism with NO2 and NO,Zr(OH)4 matrix removed NO2 mainly through the reaction between surface terminal hydroxyls and NO2,and producing nitrate and nitrite.Zn mainly acted as the assistant of terminal hydroxyls,providing new surface basic adsorption sites for NO2 or acidic intermediates.TEDA could catalyze the surface hydrolysis of NO2 and led to NO2 transformation into more acidic HNO3 and HNO2,then NO2 can be removed quickly.When both Zn and TEDA were loaded,the matrix,metal and amine could cooperate effectively.The synergistic effect among them had a significant improvement on the NO2 removal performance of the material,NO release was delayed and its production proportion was significantly reduced.This provides guidance on the design and preparation of novel air purification materials for nitrogen oxides removal.

关 键 词：氢氧化锆 锌 三乙烯二胺 氮氧化物 净化性能 净化机理 协同效应 

分 类 号：X592[环境科学与工程—环境工程]