O_3/UV反应体系的有机物消解动力学模型
|
摘要
为了提高O_3/UV(臭氧协同紫外)反应体系对有机物的消解效率,降低能源消耗,基于O_3分解的SHB机理和O_3、有机物在紫外辐射下的光解机理,并考虑该反应体系中存在的3种可能的有机物消解途径和反应器出口处O_3气体浓度变化,建立了O_3/UV反应体系的动力学模型.将该模型用于消解过程中有机物消解率变化规律的研究,进一步优化消解工艺参数.结果表明:使用苯酚和乙酸作为目标有机物,以该模型进行仿真,从理论上验证了O_3气体浓度与紫外辐射间存在协同作用和不同工艺参数下所建立模型的灵敏性;将该模型与其他模型、试验测量值进行对比,验证了其优越性和准确性;对比不同p H下的3种消解途径各自贡献率的仿真结果,发现O_3/UV反应体系的p H对其消解有机物效率具有重要影响.研究显示:在O_3/UV反应体系中,紫外辐射强度和投加的O_3气体浓度二者间具有协同作用,同时调节可获得更好的消解效果;在酸性条件下有机物消解以O_3直接氧化为主,碱性条件下则以自由基间接氧化为主.
In order to improve the degradation efficiency of organic compounds and reduce energy consumption for the reaction system by using the ozone( O_3) and ultra violet radiation( O_3/UV) technique,based on the SHB mechanism of O_3 decomposition and photolysis mechanism of O_3 and organic compounds UV radiation,a kinetic model of O_3/UV reaction system was established by studying 3 possible degradation pathways of organic compounds and the concentration change of gas phase O_3. The model was used to study the change rules of digestion rate for organic compounds during the degradation process and further to optimize the degradation conditions. Taking phenol and acetic acid as the target organic compounds to conduct the simulation,the sensitivity of the kinetic model to different reaction conditions and the synergy between O_3 and UV were verified theoretically. The superiority and accuracy of the proposed model was confirmed via comparison with other kinetic models and actual measurements in digestion experiments. The simulation results for the respective contribution rates of three degradation pathways under different p H values demonstrated the importance of p H value in this reaction system.This study illustrates that there is a synergy between the UV radiation intensity and O_3 concentration in the O_3/UV system,and high digestion rate can be obtained when they are adjusted together; organic compounds are directly oxidized by O_3 under acidic conditions,and by radicals under alkaline conditions.
In order to improve the degradation efficiency of organic compounds and reduce energy consumption for the reaction system by using the ozone( O_3) and ultra violet radiation( O_3/UV) technique,based on the SHB mechanism of O_3 decomposition and photolysis mechanism of O_3 and organic compounds UV radiation,a kinetic model of O_3/UV reaction system was established by studying 3 possible degradation pathways of organic compounds and the concentration change of gas phase O_3. The model was used to study the change rules of digestion rate for organic compounds during the degradation process and further to optimize the degradation conditions. Taking phenol and acetic acid as the target organic compounds to conduct the simulation,the sensitivity of the kinetic model to different reaction conditions and the synergy between O_3 and UV were verified theoretically. The superiority and accuracy of the proposed model was confirmed via comparison with other kinetic models and actual measurements in digestion experiments. The simulation results for the respective contribution rates of three degradation pathways under different p H values demonstrated the importance of p H value in this reaction system.This study illustrates that there is a synergy between the UV radiation intensity and O_3 concentration in the O_3/UV system,and high digestion rate can be obtained when they are adjusted together; organic compounds are directly oxidized by O_3 under acidic conditions,and by radicals under alkaline conditions.
引文
[1]张爱平,李民,陈炜鸣,等.高浓度富里酸在臭氧体系中的降解特性[J].环境科学研究,2017,30(3):457-463.ZHANG Aiping,LI Min,CHEN Weiming,et al. Decomposition characteristics of high fulvic acid based on ozone system[J].Research of Environmental Sciences,2017,30(3):457-463.
[2] SHAMA S,PATEL S,RUPARELIA J. Feasibility study on degradation of RR120 dye from water by O3,O3/UV and O3/UV/persulfate[M].Boca Raton,USA:CRC Press,2016:233-238.
[3] WEI Chaohai,ZHANG Fengzhen,HU Yun,et al.Ozonation in water treatment:the generation,basic properties of ozone and its practical application[J]. Reviews in Chemical Engineering,2016,33(1):49-89.
[4] KONNOV A A.Modeling ozone decomposition flames[J].Energy&Fuels,2013,27(1):501-506.
[5]童少平,褚有群,马淳安,等.O3/UV降解水中的乙酸和硝基苯[J].中国环境科学,2005,25(3):366-369.TONG Shaoping,CHU Youqun,MA Chun'an,et al.The degradation of acetic acid and nitrobenzene in water by O3/UV[J]. China Environmental Science,2005,25(3):366-369.
[6] BEHIN J, FARHADIAN N. Degradation of 2, 4-dichlorophenoxyacetate isopropyl amine(2,4-DIPA)by O3/AC/UV in an internally slurry airlift photo-reactor[J]. Environmental Technology,2017,38(24):1-12.
[7]管崇武,杨菁,单建军,等.工厂化循环水养殖中臭氧/紫外线反应系统的水处理性能[J].农业工程学报,2014,30(23):253-259.GUAN Chongwu,YANG Jing,SHAN Jianjun,et al.Water treatment performance of O3/UV reaction system in recirculating aquaculture systems[J]. Transactions of the Chinese Society of Agricultural Engineering,2014,30(23):253-259.
[8]秦伟伟,肖书虎,宋永会,等.O3/UV协同氧化处理黄连素制药废水[J].环境科学研究,2010,23(7):877-881.QIN Weiwei,XIAO Shuhu,SONG Yonghui,et al. Treatment of berberine pharmaceutical wastewater by O3/UV synergetic oxidation[J].Research of Environmental Sciences,2010,23(7):877-881.
[9]邬晓东,周北海,袁蓉芳,等.臭氧投加量对臭氧/生物活性炭工艺处理水库水影响的中试[J].环境科学研究,2014,27(4):427-433.WU Xiaodong,ZHOU Beihai,YUAN Rongfang,et al. Pilot-scale study on the impact of ozone dosage on O3/BAC process for advanced treatment reservoir water[J]. Research of Environmental Sciences,2014,27(4):427-433.
[10]童少平,褚有群,马淳安,等.紫外光在臭氧降解不同有机物过程中的协同作用[J].环境科学学报,2005,25(8):1041-1045TONG Shaoping,CHU Youqun,MA Chun'an,et al. The synegetic action of UV in the ozonation of different organics[J]. Acta Sciemiae circumstalltiae,2005,25(8):1041-1045.
[11]俞潇婷,张家辉,潘循皙,等.水溶液中臭氧和溴离子的反应研究[J].环境科学,2012,33(9):3139-3143YU Xiaoting,ZHANG Jiahui,PAN Xunxi,et al.Investigation of the oxidation reaction of O3with bromide ion in aqueous solution[J].Environmental Science,2012,33(9):3139-3143.
[12] MERT B K,SIVRIOGLU O,YONAR T,et al.Treatment of jewelry manufacturing effluent containing cyanide using ozone-based photochemical advanced oxidation processes[J]. Ozone Science&Engineering,2014,36(2):196-205.
[13] IGNATIEV A N,PRYAKHIN A N,LUNIN V V. Numerical simulation of the kinetics of ozone decomposition in an aqueous solution[J].Russian Chemical Bulletin,2008,57(6):1172-1178.
[14] ZHI Chen,FANG Jingyun,FAN Chihao,et al.Oxidative degradation of N-Nitrosopyrrolidine by the ozone/UV process:kinetics and pathways[J].Chemosphere,2016,150:731-739.
[15] STAEHELIN J,HOIGNE J.Decomposition of ozone in water:rate of initiation by hydroxide ions and hydrogen peroxide[J].Environmental Science&Technology,1982,16(10):621-653.
[16] BUHLER R,STAEHELIN J,HOIGNE J. Ozone decomposition in water studied by pulse radiolysis 1:HO2/O2-and HO3/O3-as intermediates-correction[J]. Chemischer Informationsdienst,1984,15(38):2560-2564.
[17] STAEHELIN J,BUEHLER R E,HOIGNE J. Ozone decomposition in water studied by pulse radiolysis 2:hydroxyl and hydrogen tetroxide(HO4)as chain intermediates[J]. Journal of Physical Chemistry,1984,88(24):5999-6004.
[18] TOMIYASU H,FUKUTOMI H,GORDON G. Kinetics and mechanism of ozone decomposition in basic aqueous solution[J].Inorganic Chemistry,1985,24(19):2962-2966.
[19] PEYTON G R,GLAZE W H.Destruction of pollutants in water with ozone in combination with ultraviolet radiation 3:photolysis of aqueous ozone[J]. Environmental Science&Technology,1988,22(7):761-767.
[20] KISHIMOTO N,NAKAMURA E. Effects of ozone-gas bubble size and p H on ozone/UV treatment[J].Ozone Science&Engineering,2011,33(5):396-402.
[21] LOVATO M E,GILLIARD M B,CASSANO A E,et al.Kinetics of the degradation of n-butyl benzyl phthalate using O3/UV,direct photolysis,direct ozonation and UV effects[J]. Environment Science Pollution Research,2015,22(2):909-917.
[22]余晓栋,杨慧中.UV/O3降解水样中COD的动力学建模[J].环境工程学报,2016(10):5561-5567.YU Xiaodong,YANG Huizhong. Kinetics modeling for degradation of COD in water sample by UV/O3[J]. Chinese Journal of Environmental Engineering,2016(10):5561-5567.
[23] RAO Yongfang,CHU Wei. A new approach to quantify the degradation kinetics of linuron with UV,ozonation and UV/O3processes[J].Chemosphere,2009,74(11):1444-1449.
[24]徐高扬,宋洪昌,贾海红,等.光催化降解过程中苯酚的分光光度法测定[J].分析实验室,2005,24(11):44-47.XU Gaoyang, SONG Hongchang, JIA Haihong, et al.Spechopjotometric determination of phenol in the process of photocatalytic degradation of phenol aqueous solution with nano titania[J].Chinese Journal of Analysis Laboratory,2005,24(11):44-47.
[25]中华人民共和国国家质量监督检验检疫总局.GB/T 601—2016化学试剂标准滴定溶液的制备[S].北京:中国标准出版社,2016.
[26] FERNANDO J B.Oxidation of polynuclear aromatic hydrocarbons in water 2:UV radiation and ozonation in the presence of UV radiation[J].Industrial&Engineering Chemistry Research,1995,34(5):662-664.
[27] GUROL M D.Factors controlling the removal of organic pollutants in ozone reactors[J].Journal,1985,77(8):55-60.
[28] GAROMA T,GUROL M D. Modeling aqueous ozone/UV process using oxalic acid as probe chemical[J]. Environmental Science&Technology,2005,39(20):7964-7969.
[29]刘小为.UV/O3降解水中新兴微污染物的特性与机理研究[D].哈尔滨:哈尔滨工业大学,2012.
[30]董洪梅,魏东洋,孙云娜,等.O3/UV工艺对水中BDE47的去除效果的影响[J].中国环境科学,2013(S1):19-25.DONG Hongmei,WEI Dongyang,SUN Yunna,et al.Effect of ozoneUV technology on treatment of 2,2,4,4-tetra BDE in aqueous medium[J].China Environmental Science,2013(S1):19-25.
[31] WOLS B A,HOFMAN-CARIS C H M. Review of photochemical reaction constants of organic micropollutants required for UV advanced oxidation processes in water[J].Water research,2012,46(9):2815-2827.
[2] SHAMA S,PATEL S,RUPARELIA J. Feasibility study on degradation of RR120 dye from water by O3,O3/UV and O3/UV/persulfate[M].Boca Raton,USA:CRC Press,2016:233-238.
[3] WEI Chaohai,ZHANG Fengzhen,HU Yun,et al.Ozonation in water treatment:the generation,basic properties of ozone and its practical application[J]. Reviews in Chemical Engineering,2016,33(1):49-89.
[4] KONNOV A A.Modeling ozone decomposition flames[J].Energy&Fuels,2013,27(1):501-506.
[5]童少平,褚有群,马淳安,等.O3/UV降解水中的乙酸和硝基苯[J].中国环境科学,2005,25(3):366-369.TONG Shaoping,CHU Youqun,MA Chun'an,et al.The degradation of acetic acid and nitrobenzene in water by O3/UV[J]. China Environmental Science,2005,25(3):366-369.
[6] BEHIN J, FARHADIAN N. Degradation of 2, 4-dichlorophenoxyacetate isopropyl amine(2,4-DIPA)by O3/AC/UV in an internally slurry airlift photo-reactor[J]. Environmental Technology,2017,38(24):1-12.
[7]管崇武,杨菁,单建军,等.工厂化循环水养殖中臭氧/紫外线反应系统的水处理性能[J].农业工程学报,2014,30(23):253-259.GUAN Chongwu,YANG Jing,SHAN Jianjun,et al.Water treatment performance of O3/UV reaction system in recirculating aquaculture systems[J]. Transactions of the Chinese Society of Agricultural Engineering,2014,30(23):253-259.
[8]秦伟伟,肖书虎,宋永会,等.O3/UV协同氧化处理黄连素制药废水[J].环境科学研究,2010,23(7):877-881.QIN Weiwei,XIAO Shuhu,SONG Yonghui,et al. Treatment of berberine pharmaceutical wastewater by O3/UV synergetic oxidation[J].Research of Environmental Sciences,2010,23(7):877-881.
[9]邬晓东,周北海,袁蓉芳,等.臭氧投加量对臭氧/生物活性炭工艺处理水库水影响的中试[J].环境科学研究,2014,27(4):427-433.WU Xiaodong,ZHOU Beihai,YUAN Rongfang,et al. Pilot-scale study on the impact of ozone dosage on O3/BAC process for advanced treatment reservoir water[J]. Research of Environmental Sciences,2014,27(4):427-433.
[10]童少平,褚有群,马淳安,等.紫外光在臭氧降解不同有机物过程中的协同作用[J].环境科学学报,2005,25(8):1041-1045TONG Shaoping,CHU Youqun,MA Chun'an,et al. The synegetic action of UV in the ozonation of different organics[J]. Acta Sciemiae circumstalltiae,2005,25(8):1041-1045.
[11]俞潇婷,张家辉,潘循皙,等.水溶液中臭氧和溴离子的反应研究[J].环境科学,2012,33(9):3139-3143YU Xiaoting,ZHANG Jiahui,PAN Xunxi,et al.Investigation of the oxidation reaction of O3with bromide ion in aqueous solution[J].Environmental Science,2012,33(9):3139-3143.
[12] MERT B K,SIVRIOGLU O,YONAR T,et al.Treatment of jewelry manufacturing effluent containing cyanide using ozone-based photochemical advanced oxidation processes[J]. Ozone Science&Engineering,2014,36(2):196-205.
[13] IGNATIEV A N,PRYAKHIN A N,LUNIN V V. Numerical simulation of the kinetics of ozone decomposition in an aqueous solution[J].Russian Chemical Bulletin,2008,57(6):1172-1178.
[14] ZHI Chen,FANG Jingyun,FAN Chihao,et al.Oxidative degradation of N-Nitrosopyrrolidine by the ozone/UV process:kinetics and pathways[J].Chemosphere,2016,150:731-739.
[15] STAEHELIN J,HOIGNE J.Decomposition of ozone in water:rate of initiation by hydroxide ions and hydrogen peroxide[J].Environmental Science&Technology,1982,16(10):621-653.
[16] BUHLER R,STAEHELIN J,HOIGNE J. Ozone decomposition in water studied by pulse radiolysis 1:HO2/O2-and HO3/O3-as intermediates-correction[J]. Chemischer Informationsdienst,1984,15(38):2560-2564.
[17] STAEHELIN J,BUEHLER R E,HOIGNE J. Ozone decomposition in water studied by pulse radiolysis 2:hydroxyl and hydrogen tetroxide(HO4)as chain intermediates[J]. Journal of Physical Chemistry,1984,88(24):5999-6004.
[18] TOMIYASU H,FUKUTOMI H,GORDON G. Kinetics and mechanism of ozone decomposition in basic aqueous solution[J].Inorganic Chemistry,1985,24(19):2962-2966.
[19] PEYTON G R,GLAZE W H.Destruction of pollutants in water with ozone in combination with ultraviolet radiation 3:photolysis of aqueous ozone[J]. Environmental Science&Technology,1988,22(7):761-767.
[20] KISHIMOTO N,NAKAMURA E. Effects of ozone-gas bubble size and p H on ozone/UV treatment[J].Ozone Science&Engineering,2011,33(5):396-402.
[21] LOVATO M E,GILLIARD M B,CASSANO A E,et al.Kinetics of the degradation of n-butyl benzyl phthalate using O3/UV,direct photolysis,direct ozonation and UV effects[J]. Environment Science Pollution Research,2015,22(2):909-917.
[22]余晓栋,杨慧中.UV/O3降解水样中COD的动力学建模[J].环境工程学报,2016(10):5561-5567.YU Xiaodong,YANG Huizhong. Kinetics modeling for degradation of COD in water sample by UV/O3[J]. Chinese Journal of Environmental Engineering,2016(10):5561-5567.
[23] RAO Yongfang,CHU Wei. A new approach to quantify the degradation kinetics of linuron with UV,ozonation and UV/O3processes[J].Chemosphere,2009,74(11):1444-1449.
[24]徐高扬,宋洪昌,贾海红,等.光催化降解过程中苯酚的分光光度法测定[J].分析实验室,2005,24(11):44-47.XU Gaoyang, SONG Hongchang, JIA Haihong, et al.Spechopjotometric determination of phenol in the process of photocatalytic degradation of phenol aqueous solution with nano titania[J].Chinese Journal of Analysis Laboratory,2005,24(11):44-47.
[25]中华人民共和国国家质量监督检验检疫总局.GB/T 601—2016化学试剂标准滴定溶液的制备[S].北京:中国标准出版社,2016.
[26] FERNANDO J B.Oxidation of polynuclear aromatic hydrocarbons in water 2:UV radiation and ozonation in the presence of UV radiation[J].Industrial&Engineering Chemistry Research,1995,34(5):662-664.
[27] GUROL M D.Factors controlling the removal of organic pollutants in ozone reactors[J].Journal,1985,77(8):55-60.
[28] GAROMA T,GUROL M D. Modeling aqueous ozone/UV process using oxalic acid as probe chemical[J]. Environmental Science&Technology,2005,39(20):7964-7969.
[29]刘小为.UV/O3降解水中新兴微污染物的特性与机理研究[D].哈尔滨:哈尔滨工业大学,2012.
[30]董洪梅,魏东洋,孙云娜,等.O3/UV工艺对水中BDE47的去除效果的影响[J].中国环境科学,2013(S1):19-25.DONG Hongmei,WEI Dongyang,SUN Yunna,et al.Effect of ozoneUV technology on treatment of 2,2,4,4-tetra BDE in aqueous medium[J].China Environmental Science,2013(S1):19-25.
[31] WOLS B A,HOFMAN-CARIS C H M. Review of photochemical reaction constants of organic micropollutants required for UV advanced oxidation processes in water[J].Water research,2012,46(9):2815-2827.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |