基于O_3/UV法的消解终止自动确定方法
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摘要
为了提高基于臭氧协同紫外(O_3/UV)法的COD在线监测装置的检测效率和检测精度,分析了不同水样在消解过程中二氧化碳气体生成浓度的变化率与有机物消解率之间的关系,提出了一种消解终止自动确定的检测方法.通过采集消解过程中各传感器的数据,基于使用滑动标准偏差法计算二氧化碳气体浓度变化率的标准差自动确定消解终止时间.对不同种类、不同浓度的有机物进行消解实验,发现在二氧化碳实时浓度的标准差小于0.003时,有机物基本消解完全,可认为达到反应终点.该方法不仅可用于COD的在线监测提高检测效率和检测精度,也对基于臭氧协同紫外(O_3/UV)法的废水处理具有指导意义.
In order to improve the detection accuracy and efficiency for the on-line monitoring device of chemical oxygen demand(COD) by using Ozone in combination with Ultraviolet Radiation(O_3/UV), the relationship between the concentration change rate of the produced carbon dioxide(CO_2) and the digestion rate of organics is analyzed in the digestion of different water samples, a method is further proposed to automatically determine the termination of digestion. Based on the data collected by each sensor during the digestion process, the standard deviation of CO_2 gas concentration change rate is calculated using the moving block standard deviation(MBSD) method, which is applied to automatically determine the termination time of digestion. Digestion experiments with organics of different types and different centration reveal that organics are completely degraded when the standard deviation of CO_2 concentration is less than 0.003, which can be considered as the end point of the reaction. This method can not only improve the detection accuracy and efficiency for the on-line monitoring device of COD, but also has guiding significance to the treatment of wastewater based on O_3/UV method.
In order to improve the detection accuracy and efficiency for the on-line monitoring device of chemical oxygen demand(COD) by using Ozone in combination with Ultraviolet Radiation(O_3/UV), the relationship between the concentration change rate of the produced carbon dioxide(CO_2) and the digestion rate of organics is analyzed in the digestion of different water samples, a method is further proposed to automatically determine the termination of digestion. Based on the data collected by each sensor during the digestion process, the standard deviation of CO_2 gas concentration change rate is calculated using the moving block standard deviation(MBSD) method, which is applied to automatically determine the termination time of digestion. Digestion experiments with organics of different types and different centration reveal that organics are completely degraded when the standard deviation of CO_2 concentration is less than 0.003, which can be considered as the end point of the reaction. This method can not only improve the detection accuracy and efficiency for the on-line monitoring device of COD, but also has guiding significance to the treatment of wastewater based on O_3/UV method.
引文
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[6]Garoma T,Gurol M D.Oxidation of methyl tert-butyl ether in aqueous solution by an Ozone/UV process[J].Journal of Environmental Engineering,2016,132(11):1404-1412.
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[12]Yao H,Wu B,Qu H,et al.A high throughput chemiluminescence method for determination of chemical oxygen demand in waters[J].Analytica Chimica Acta,2009,633(1):76-80.
[13]Almeida C A,Savio M,González P,et al.Determination of chemical oxygen demand employed manganese as an environmentally friendly oxidizing reagent by a flow injection method based on microwave digestion and speciation coupled to ICP-OES[J].Microchemical Journal,2013,106(1):351-356.
[14]汤哲人,陈泉源,邓东升,等.以黄铜矿作为颗粒三维电极的电Fenton氧化处理维尼纶废水中的COD研究[J].中国环境科学,2017,37(1):95-101.Tang Z R,Chen Q Y,Deng D S,et al.COD of vinylon waste-water oxidizing treatment by three-dimensional-electrode electricity-fenton using brass copper grains[J].China Environmental Science,2017,37(1):95-101.
[15]Badr I H A,Hassan H H,Hamed E,et al.Sensitive and green method for determination of chemical oxygen demand using a nano-copper based electrochemical sensor[J].Electroanalysis,2017.29:2401-2409.
[16]Liao J,Lin S,Zeng M,et al.A miniature photoelectrochemical sensor based on organic electrochemical transistor for sensitive determination of chemical oxygen demand in wastewaters[J].Water Research,2016,94:296-304.
[17]Kim H,Lim H,Colosimo M F.Determination of chemical oxygen demand(COD)using ultrasound digestion and oxidation-reduction potential-based titration[J].Journal of Environmental Science and Health part A-Toxic/Hazardous Substang Es&Environmental Engineering,2007,42(11):1665-1670.
[18]Dharmadhikari D M,Vanerkar A P,Barhate N M.Chemical oxygen demand using closed microwave digestion system[J].Environmental Science&Technology,2005,39(16):6198-6201.
[19]汤斌.一种紫外-可见光谱检测水质COD预测模型优化方法[J].中国环境科学,2015,35(2):478-483.Tang B.A method of optimizing the prediction model for the determination of water COD by using UV-visible spectroscopy[J].China Environmental Science,2015,35(2):478-483.
[20]张龙,杨慧中.基于臭氧协同紫外的COD在线检测装置[J].中国给水排水,2014,(6):89-91.Zhang L,Yang H Z.COD detection device based on ozone coupled with UV[J].China Water&Wastewater,2014,(6):89-91.
[21]张龙,薛佩姣,杨慧中.基于臭氧紫外协同在线检测水体COD的研究[J].环境工程学报,2015,9(1):235-239.Zhang L,Xue P J,Yang H Z.Study of on-line detection of COD based on ozone/UV[J].Chinese Journal of Environmental Engineering,2015,9(1):235-239.
[22]Yu X,Yang H,Sun L.Determination of chemical oxygen demand using UV/O3[J].Water Air&Soil Pollution,2016,227(12):458.
[23]薛佩姣,杨慧中.多传感器集成的COD在线检测与补偿方法[J].传感器与微系统,2015,34(9):135-137.Xue P J,Yang H Z.Online detection and compensation method of COD with multi-sensor integration[J].Transducer and Microsystem Technologies,2015,34(9):135-137.
[24]Le G,Yang H,Yu X.Improved UV/O 3method for measuring the chemical oxygen demand[J].Water Science&Technology,2018,77(5):1271-1279.
[25]余晓栋.基于紫外臭氧的COD在线检测方法研究[D].无锡:江南大学,2017.Yu X D.Study of On-Line COD Detection Method by Using UV/O3[D].Wuxi:Jiangnan University,2017.
[26]Li W,Yan X,Chen H,et al.In-line Vis-NIR spectral analysis for the column chromatographic processes of Ginkgo biloba,part I:End-point determination of the elution process[J].Chemometrics&Intelligent Laboratory Systems,2018,172:159-166.
[27]林兆洲,杨婵,徐冰,等.中药混合过程终点在线判定方法研究[J].中国中药杂志,2017,42(6):1089-1094.Lin Z Z,Yang C,Xu B,et al.Online endpoint detection algorithm for blending process of Chinese materia medica[J].China Journal of Chinese Materia Medica,2017,42(6):1089-1094.
[2]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.
[3]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):1041-1045.Tong S P,Chu Y Q,Ma C A,et al.The synergetic action of UV in the ozonation of different organics[J].Acta Scientiae Circumstantiae,2005,25(8):1041-1045.
[4]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 S P,Chu Y Q,Ma C A,et al.The degradation of acetic acid and nitrobenzene in water by O3/UV[J].China Environmental Science,2005,25(3):366-369.
[5]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].Environmental Science&Pollution Research,2015,22(2):909-917.
[6]Garoma T,Gurol M D.Oxidation of methyl tert-butyl ether in aqueous solution by an Ozone/UV process[J].Journal of Environmental Engineering,2016,132(11):1404-1412.
[7]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,2013,33(s1):19-25.Dong H M,Wei D Y,Sun Y N,et al.Effect of ozone-UV technology on treatment of 2,2’,4,4’-tetra BDE in aqueous medium[J].China Environmental Science,2013,33(s1):19-25.
[8]Geerdink R B,Sebastiaan v d H R,Epema O J.Chemical oxygen demand:Historical perspectives and future challenges[J].Analytica Chimica Acta,2017,961:1-11.
[9]HJ 828-2017水质-化学需氧量的测定-重铬酸盐法[S].2017.HJ 828-2017 Water quality-Determination of the chemical oxygen demand-Dichromate method[S].2017.
[10]GB 11892-1989水质-高锰酸盐指数的测定[S].1991.GB 11892-1989 Water quality-determination of permanganate index[S].1991.
[11]Kolb M,Bahadir M,Teichgr?ber B.Determination of chemical oxygen demand(COD)using an alternative wet chemical method free of mercury and dichromate[J].Water Research,2017,122:645-654.
[12]Yao H,Wu B,Qu H,et al.A high throughput chemiluminescence method for determination of chemical oxygen demand in waters[J].Analytica Chimica Acta,2009,633(1):76-80.
[13]Almeida C A,Savio M,González P,et al.Determination of chemical oxygen demand employed manganese as an environmentally friendly oxidizing reagent by a flow injection method based on microwave digestion and speciation coupled to ICP-OES[J].Microchemical Journal,2013,106(1):351-356.
[14]汤哲人,陈泉源,邓东升,等.以黄铜矿作为颗粒三维电极的电Fenton氧化处理维尼纶废水中的COD研究[J].中国环境科学,2017,37(1):95-101.Tang Z R,Chen Q Y,Deng D S,et al.COD of vinylon waste-water oxidizing treatment by three-dimensional-electrode electricity-fenton using brass copper grains[J].China Environmental Science,2017,37(1):95-101.
[15]Badr I H A,Hassan H H,Hamed E,et al.Sensitive and green method for determination of chemical oxygen demand using a nano-copper based electrochemical sensor[J].Electroanalysis,2017.29:2401-2409.
[16]Liao J,Lin S,Zeng M,et al.A miniature photoelectrochemical sensor based on organic electrochemical transistor for sensitive determination of chemical oxygen demand in wastewaters[J].Water Research,2016,94:296-304.
[17]Kim H,Lim H,Colosimo M F.Determination of chemical oxygen demand(COD)using ultrasound digestion and oxidation-reduction potential-based titration[J].Journal of Environmental Science and Health part A-Toxic/Hazardous Substang Es&Environmental Engineering,2007,42(11):1665-1670.
[18]Dharmadhikari D M,Vanerkar A P,Barhate N M.Chemical oxygen demand using closed microwave digestion system[J].Environmental Science&Technology,2005,39(16):6198-6201.
[19]汤斌.一种紫外-可见光谱检测水质COD预测模型优化方法[J].中国环境科学,2015,35(2):478-483.Tang B.A method of optimizing the prediction model for the determination of water COD by using UV-visible spectroscopy[J].China Environmental Science,2015,35(2):478-483.
[20]张龙,杨慧中.基于臭氧协同紫外的COD在线检测装置[J].中国给水排水,2014,(6):89-91.Zhang L,Yang H Z.COD detection device based on ozone coupled with UV[J].China Water&Wastewater,2014,(6):89-91.
[21]张龙,薛佩姣,杨慧中.基于臭氧紫外协同在线检测水体COD的研究[J].环境工程学报,2015,9(1):235-239.Zhang L,Xue P J,Yang H Z.Study of on-line detection of COD based on ozone/UV[J].Chinese Journal of Environmental Engineering,2015,9(1):235-239.
[22]Yu X,Yang H,Sun L.Determination of chemical oxygen demand using UV/O3[J].Water Air&Soil Pollution,2016,227(12):458.
[23]薛佩姣,杨慧中.多传感器集成的COD在线检测与补偿方法[J].传感器与微系统,2015,34(9):135-137.Xue P J,Yang H Z.Online detection and compensation method of COD with multi-sensor integration[J].Transducer and Microsystem Technologies,2015,34(9):135-137.
[24]Le G,Yang H,Yu X.Improved UV/O 3method for measuring the chemical oxygen demand[J].Water Science&Technology,2018,77(5):1271-1279.
[25]余晓栋.基于紫外臭氧的COD在线检测方法研究[D].无锡:江南大学,2017.Yu X D.Study of On-Line COD Detection Method by Using UV/O3[D].Wuxi:Jiangnan University,2017.
[26]Li W,Yan X,Chen H,et al.In-line Vis-NIR spectral analysis for the column chromatographic processes of Ginkgo biloba,part I:End-point determination of the elution process[J].Chemometrics&Intelligent Laboratory Systems,2018,172:159-166.
[27]林兆洲,杨婵,徐冰,等.中药混合过程终点在线判定方法研究[J].中国中药杂志,2017,42(6):1089-1094.Lin Z Z,Yang C,Xu B,et al.Online endpoint detection algorithm for blending process of Chinese materia medica[J].China Journal of Chinese Materia Medica,2017,42(6):1089-1094.