Fenton试剂液相催化氧化亚硝酸盐实验研究
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摘要
氧化法烟气脱硝技术在超低排放背景下很有应用前景,解决氧化吸收后亚硝酸盐的水体二次污染问题有助于推广该技术。该文验证了碱液吸收NO_2后,亚硝酸盐生成机制。通过对比试验选定最佳NO_2~-检测方法。考察了Fenton试剂液相催化氧化NO_2~-效果。探讨了pH值、H_2O_2浓度、Fe~(2+)浓度、微波敏化等因素对NO_2~-转化效率的影响。结果显示:Fenton试剂能够氧化亚硝酸盐,其中pH值、H_2O_2浓度、Fe~(2+)浓度,以及是否施加微波等条件,是NO_2~-转化效率的重要影响因素。当NO_2~-的浓度为452.51 mg/L时,加入0.03 mol/L H_2O_2和3 mmol/L的Fe~(2+)与之反应(无微波及活性炭敏化条件),可使NO_2~-转化效率高达94.88%;pH值、H_2O_2浓度、Fe~(2+)浓度等是NO_2~-转化效率的重要影响因素,最佳p H值是3,H_2O_2浓度、Fe~(2+)浓度的增加可提高NO_2~-转化效率;微波可提高NO_2~-转化效率,施加微波可将NO_2~-转化效率从58.88%提高至68.89%,且活性炭的添加可强化微波敏化效果,其中果壳基活性炭强化效果优于椰壳基活性炭。
Oxidation flue gas denitrification technology is very promising in the background of ultra-low emission and the solution of nitrite’s secondary pollution problem which is occurred after oxidation and absorption is helpful to popularize this technology.In this paper,the problem of nitrite’s formation after alkali absorption of NO_2was verified at first,the best detection method of NO_2~-was selected,and the effects of pH value,H_2O_2concentration,Fe~(2+)concentration,microwave sensitization and other factors on the conversion efficiency of NO_2~-were studied.The results indicated that Fenton's reagent can oxidize nitrite,and the conversion efficiency of NO_2~-is 94.88%when NO_2~-concentration is 452.51 mg/L,H_2O_2concentration is 0.03mol/L,and Fe~(2+)concentration is 3 mmol/L;p H,H_2O_2concentration and Fe~(2+)concentration are the important factors which affect the conversion efficiency of NO_2~-,3 is the best pH value,and the increases of H_2O_2concentration and Fe~(2+)concentration can raise the conversion efficiency of NO_2~-.Microwave can improve the conversion efficiency of NO_2~-which can increase the conversion efficiency of NO_2~-from 58.88%to 68.89%,the addition of activated carbon can enhance the effect of microwave sensitization,and the enhancing effect of fruit-shell activated carbon is better than coconut-based activated carbon.
Oxidation flue gas denitrification technology is very promising in the background of ultra-low emission and the solution of nitrite’s secondary pollution problem which is occurred after oxidation and absorption is helpful to popularize this technology.In this paper,the problem of nitrite’s formation after alkali absorption of NO_2was verified at first,the best detection method of NO_2~-was selected,and the effects of pH value,H_2O_2concentration,Fe~(2+)concentration,microwave sensitization and other factors on the conversion efficiency of NO_2~-were studied.The results indicated that Fenton's reagent can oxidize nitrite,and the conversion efficiency of NO_2~-is 94.88%when NO_2~-concentration is 452.51 mg/L,H_2O_2concentration is 0.03mol/L,and Fe~(2+)concentration is 3 mmol/L;p H,H_2O_2concentration and Fe~(2+)concentration are the important factors which affect the conversion efficiency of NO_2~-,3 is the best pH value,and the increases of H_2O_2concentration and Fe~(2+)concentration can raise the conversion efficiency of NO_2~-.Microwave can improve the conversion efficiency of NO_2~-which can increase the conversion efficiency of NO_2~-from 58.88%to 68.89%,the addition of activated carbon can enhance the effect of microwave sensitization,and the enhancing effect of fruit-shell activated carbon is better than coconut-based activated carbon.
引文
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[18]程丽华,黄君礼,倪福祥.Fenton试剂生成·OH的动力学研究[J].环境污染治理技术与设备,2003,4(5):12-14.Cheng Lihua,Huang Junli,Ni Fuxiang.Generation kinetics of hydroxyl radicals by Fenton's reagent[J].Techniques and Equipment for Environmental Pollution Control,2003,4(5):12-14.
[19]Walling C.Fenton’s reagent revisited[J].Accounts of Chemical Research,1975,8:125-131.
[20]赵海谦,高继慧,周伟,等.Fe2+/H2O2体系内各种自由基在氧化NO中的作用[J].化工学报,2015,66(1):449-454.Zhao Haiqian,Gao Jihui,Zhou Wei,et al.Roles of varied radicals in NO oxidation by Fe2+/H2O2system[J].CIESCJournal,2015,66(1):449-454.
[2]钱伯章,李敏.世界能源结构向低碳燃料转型-BP公司发布2016年世界能源统计年鉴[J].中国石油和化工经济分析,2016(8):35-39.Qian Bozhang,Li Min.World energy structure transits to low-carbon fuel-BP company publishes 2016 World Energy Statistics Yearbook[J].China Petroleum and Chemical Economic Analysis,2016(8):35-39.
[3]Wang T,Sun B,Xiao H.Effects of gas temperature on NOx removal by dielectric barrier discharge[J].Environmental Technology,2013,34(19):2709-2716.
[4]郝吉明,马广大,王书肖.大气污染控制工程[M].北京:高等教育出版社,2013:404-411.Hao Jiming,Ma Guangda,Wang Shuxiao.Air Pollution Control Engineering[M].Beijing:Higher Education Press,2013:404-411.
[5]Ohtsuka K.Electrostatic Methods for Integrated Pollution Control of Combustion Gas[D].Tokyo:University of Tokyo,1985.
[6]Adapa S,Gaur V,Verma N.Catalytic oxidation of NO by activated carbon fiber(ACF)[J].Chemical Engineering Journal,2006,116(1):25-37.
[7]Guo R T,Pan W G,Zhang X B,et al.Removal of NO by using Fenton reagent solution in a lab-scale bubbling reactor[J].Fuel,2011,90(11):3295-3298.
[8]Zhao Y,Wen X,Guo T,et al.Desulfurization and denitrogenation from flue gas using Fenton reagent[J].Fuel Processing Technology,2014,128:54-60.
[10]柳赟.介质阻挡放电低温等离子体脱除NOx的研究[D].北京:华北电力大学,2011.Liu Yun.Research on Removal of NOxby Dielectric Barrier Discharge[D].Beijing:North China University of Electric and Electronic Engineering,2011.
[11]陈国庆.钙基吸收剂硫氮协同脱除过程的耦合促进机理及方法研究[D].哈尔滨:哈尔滨工业大学,2012.Chen Guoqing.Effect Studies on Coupling Promotion Mechanism and Methods of SO2and NOxSynergistic Removal by Calcium Based Absorbent[D].Harbin:Harbin Institute of Technology,2012.
[12]陈国庆,高继慧,黄启龙,等.钙基脱硫工艺协同脱硝技术研究进展[J].化工进展,2015,34(10):3755-3761.Chen Guoqing,Gao Jihui,Huang Qilong,et al.Research progress of SO2and NOxsynergistic removal by calciumbased desulfurization[J].Chemical Industry and Engineering Progress,2015,34(10):3755-3761.
[13]李晓东,高建民,于永川,等.耦合微波的芬顿试剂/活性炭低温催化氧化NO[J].哈尔滨工业大学学报,2018,50(1):90-95.Li Xiaodong,Gao Jianmin,Yu Yongchuan,et al.NO catalytic oxidation at low temperature through Fenton reagent/AC coupled with microwave[J].Journal of Harbin Institute of Technology,2018,50(1):90-95.
[14]Deacon E L.Gas transfer to and across an air-water interface[J].Tellus,1977,29:363-374.
[15]张国宇,王鹏,姜思朋,等.微波诱导处理雅格素红BF-3B 150%染料废水的研究[J].环境科学,2004,25(S):52-55.Zhang Guoyu,Wang Peng,Jiang Sipeng,et al.Treatment of ARGAZOL BF-3B 150%by microwave induced oxidation process[J].Environmental Science,2004,25(S):52-55.
[16]王杰,马溪平,唐凤德,等.微波催化氧化法预处理垃圾渗滤液的研究[J].中国环境科学,2011,31(7):1166-1170.Wang Jie,Ma Xiping,Tang Fengde,et al.Study on pretreatment of landfill leachate by microwave-assisted catalytic oxidation process[J].China Environmental Science,2011,31(7):1166-1170.
[17]刘龙,赵浩,徐炎华.微波-H2O2-活性炭协同催化氧化处理苯酚废水[J].南京工业大学学报,2010,32(1):46-50.Liu Long,Zhao Hao,Xu Yanhua.Synergetic oxidation of microwave and H2O2-activated carbon on phenol wastewater[J].Journal of Nanjing University of Technology,2010,32(1):46-50.
[18]程丽华,黄君礼,倪福祥.Fenton试剂生成·OH的动力学研究[J].环境污染治理技术与设备,2003,4(5):12-14.Cheng Lihua,Huang Junli,Ni Fuxiang.Generation kinetics of hydroxyl radicals by Fenton's reagent[J].Techniques and Equipment for Environmental Pollution Control,2003,4(5):12-14.
[19]Walling C.Fenton’s reagent revisited[J].Accounts of Chemical Research,1975,8:125-131.
[20]赵海谦,高继慧,周伟,等.Fe2+/H2O2体系内各种自由基在氧化NO中的作用[J].化工学报,2015,66(1):449-454.Zhao Haiqian,Gao Jihui,Zhou Wei,et al.Roles of varied radicals in NO oxidation by Fe2+/H2O2system[J].CIESCJournal,2015,66(1):449-454.
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