基于O_3/UV法在线COD检测的气体溶解量估计方法
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摘要
针对臭氧协同紫外方法 (O_3/UV)检测化学需氧量(COD)时存在溶解性气体影响测量精度的问题,提出了一种COD检测过程中气体溶解量的估计方法,用于对COD检测模型的补偿。采集不同浓度的COD标准水样在消解过程中的测量数据和实验分析数据,基于PLS-LSSVMs建立溶解氧量和溶解二氧化碳量的估计模型,将模型的输出作为COD检测模型的补偿项。实验结果表明,基于PLS-LSSVMs建立的模型比PLS或者LSSVMs单独建立的模型估计精度高。采用溶解气体量估计模型进行补偿后的O_3/UV法检测COD与国标法测量结果相对误差均小于5%。对提高O_3/UV法检测COD精度具有重要意义。
Consider the problem of the dissolved gas influences the measurement accuracy of the chemical oxygen demand(COD) based on the method of ozone combined with ultraviolet radiation(O_3/UV), we proposed estimationmodels of dissolved gas quantity for COD determination. In terms of the parameters collected and experimentalresults from the COD standard solution digestion with different concentrations, the estimation models of dissolvedoxygen and carbon dioxide based on PLC-LSSVMs are established respectively. The outputs of the estimationmodels are used as compensation for the COD detection model. The results show that the estimation models havehigher estimation accuracy than the model established by PLS or LSSVMs alone. The relative errors of the CODmeasured by O_3/UV method after the estimated dissolved gas amount is compensated and the national standardmethod is both less than 5%. This study is of great significance for improving the accuracy of COD detection by O_3/UV method.
Consider the problem of the dissolved gas influences the measurement accuracy of the chemical oxygen demand(COD) based on the method of ozone combined with ultraviolet radiation(O_3/UV), we proposed estimationmodels of dissolved gas quantity for COD determination. In terms of the parameters collected and experimentalresults from the COD standard solution digestion with different concentrations, the estimation models of dissolvedoxygen and carbon dioxide based on PLC-LSSVMs are established respectively. The outputs of the estimationmodels are used as compensation for the COD detection model. The results show that the estimation models havehigher estimation accuracy than the model established by PLS or LSSVMs alone. The relative errors of the CODmeasured by O_3/UV method after the estimated dissolved gas amount is compensated and the national standardmethod is both less than 5%. This study is of great significance for improving the accuracy of COD detection by O_3/UV method.
引文
[1]李名升,张建辉,罗海江,等."十一五"期间中国化学需氧量减排与水环境质量变化关联分析[J].生态环境学报, 2011, 20(3):463-467.Li M S, Zhang J H, Luo H J, et al. Relation between water quality and COD discharge in China in the Eleventh Five-Year Plan[J].Ecology and Environmental Sciences, 2011, 20(3):463-467.
[2]中华人名共和国生态环境部.水质化学需氧量的测定重铬酸盐法:HJ 828—2017[S].北京:中国环境出版社, 2017.Ministry of Ecology and Environment of the People's Republic of China. Water quality determination of the chemical oxygen demand Dichromate method:HJ 828—2017[S]. Beijing:China Environmental Press, 2017.
[3]国家技术监督局.水质高锰酸盐指数的测定:GB 11892—1989[S].北京:中国标准出版社, 1991.General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China. Water quality determination of permanganate index:GB 11892—1989[S].Beijing:Standards Press of China, 1991.
[4] Gr?nroos A, Kyll?nen H, Korpij?rvi K, et al. Ultrasound assisted method to increase soluble chemical oxygen demand(SCOD)of sewage sludge for digestion[J]. Ultrasonics Sonochemistry, 2005,12(1/2):115-120.
[5]李文,汪楷健,杨守波,等.应用超声消解快速检测COD方法的实验研究[J].工业水处理, 2016, 36(6):90-93.Li W, Wang K J, Yang S B, et al. Experimental research on the rapid detection method of chemical oxygen demand by ultrasonic assisted digestion technique[J] Industrial Water Treatment, 2016,36(6):90-93.
[6] Bryce D W, Izquierdo A, De Castro M D L. Use of focused microwaves for expeditive shortening of sample pre-treatment:digestion and reduction procedures prior to selenium speciation as selenium(IV)or selenium(VI)[J]. Analyst, 1995, 120(120):2171-2174.
[7]黄毅.微波密封消解法测定CODCr值[J].上海环境科学, 1996,15(5):32-34.Huang Y. Determination of CODCrusing sealed vessel microwave digestion method[J]. Shanghai Environmental Sciences, 1996, 15(5):32-34
[8]王照丽,罗娅君,李薇,等.微波消解法测定工业废水中的化学需氧量[J].环境科学与技术, 2016,(S1):71-74.Wang Z L, Luo Y J, Li W, et al. Determination of COD in industrial wastewater with microwave digestion[J]. Environmental Science&Technology, 2016,(S1):71-74.
[9]杨泽玉,胡涌刚.化学发光-化学需氧量测定新方法[J].分析化学, 2003, 31(12):1430-1432.Yang Z Y, Hu Y G. A Novel Chemiluminescence method for the determination of chemical oxygen demand[J]. Chinese Journal of Analytical Chemistry, 2003, 31(12):1430-1432.
[10] Hue D T K, Hashimoto S, Nishikawa H. A 3-step chemiluminescence method for chemical oxygen demand measurement[J]. Analytical Sciences the International Journal of the Japan Society for Analytical Chemistry, 2017, 9:5797-5805.
[11] Zheng Q, Zhou B, Bai J, et al. Self-organized TiO2nanotube array sensor for the determination of chemical oxygen demand[J].Advanced Materials, 2010, 20(5):1044-1049.
[12] Zhao H, Jiang D, Zhang S, et al. Development of a direct photoelectrochemical method for determination of chemical oxygen demand[J]. Analytical Chemistry, 2015, 76(1):155-160.
[13]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.
[14] Wibowo D, Ruslan, Maulidiyah M, et al. Determination of COD based on photoelectrocatalysis of FeTiO3.TiO2/Ti electrode[J]. IOP Conference Series:Materials Science and Engineering, 2017, 267(1):012007
[15] Jing T, Zhou Y S, Hao Q L, et al. A nano-nickel electrochemical sensor for sensitive determination of chemical oxygen demand[J].Analytical Methods, 2012, 4(4):1155-1159.
[16] Kim I, Tanaka H. Energy consumption for PPCPs removal by O3and O3/UV[J]. Ozone Science&Engineering, 2011, 33(2):150-157.
[17]董洪梅. 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 H M. Effect of ozone-UV technology on treatment of 2, 2',4, 4'-tetra BDE in aqueous medium[J]. China Environmental Science, 2013,(S1):19-25.
[18] Mert B K,?zge S, 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.
[19]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, 30(6):89-91.Zhang L, Yang H Z. COD detection device based on ozone coupled with UV[J]. China Water&Wastewater, 2014, 30(6):89-91.
[20]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.
[21] Suykens J A K, Vandewalle J. Least squares support machineclassifiers[J]. Neural Processing Letters, 1999, 9(3):293-300.
[22]杨小梅,刘文琦,杨俊.基于分阶段的LSSVM发酵过程建模[J].化工学报, 2013, 64(9):3262-3269.Yang X M, Liu W Q, Yang J. LSSVM modeling for fermentation process based on dividing stages[J] CIESC Journal, 2013, 64(9):3262-3269.
[23]郑蓉建,潘丰.基于PLS-LSSVM的谷氨酸发酵产物浓度预测建模[J].化工学报, 2017, 68(3):976-983Zheng R J, Pan F. Prediction of product concentration in glutamate fermentation process using partial least squares and least square support vector machine[J]. CIESC Journal, 2017, 68(3):976-983
[24]冯凯,卢建刚,陈金水.基于最小二乘支持向量机的MIMO线性参数变化模型辨识及预测控制[J].化工学报, 2015,(1):197-205.Feng K, Lu J G, Chen J S. Identification and model predictive control of LPV models based on LS-SVM for MIMO system[J].CIESC Journal, 2015,(1):197-205.
[25]欧阳爱国,唐天义,周鑫,等.最小二乘支持向量机结合中红外光谱测定甲醇柴油甲醇含量[J].发光学报, 2016,(10):1253-1258.Ouyang A G, Tang T Y, Zhou X, et al. Methanol content determination in methanol diesel with mid infrared spectroscopy analysis using least square support vector machine[J]. Chinese Journal of Lumine Science, 2016,(10):1253-1258
[26]张福东,刘杰,王智宏.基于最小二乘支持向量机的油页岩含油率近红外光谱分析[J].高等学校化学学报, 2016, 37(10):1792-1798.Zhang F D, Liu J, Wang Z H. Analysis of oil yield from oil shale minerals based on near-infrared spectroscopy with least squares support vector machines[J]. Chemical Journal of Chinese Universities, 2016, 37(10):1792-1798.
[27]张森,石为人,石欣,等.基于偏最小二乘回归和SVM的水质预测[J].计算机工程与应用, 2015, 51(15):249-254.Zhang S, Shi W R, Shi X, et al. Water quality prediction based on partial least squares and support vector machine[J]. Computer Engineering and Applications, 2015, 51(15):249-254.
[28]李远华,陶劲松,李继庚,等.基于偏最小二乘法的纸张抗张强度预测模型[J].化工学报, 2014, 65(9):3544-3551.Li Y H, Tao J S, Li J G, et al. Building predicting model of paper tensile strength based on partial least squares approach[J] CIESC Journal, 2014, 65(9):3544-3551.
[29]李晋华,张敏娟,张德龙.氧气A吸收带偏最小二乘基线拟合方法[J].中国激光, 2017,(8):281-287.Li J H, Zhang M J, Zhang D L. Baseline fitting of partial least squares for oxygen a abscorption band[J]. Chinese Journal of Lasers. 2017,(8):281-287.
[30]陶劲松,杨亚帆,李远华.基于PLS和SVM的纸张抗张强度建模比较[J].华南理工大学学报(自然科学版), 2014,(7):132-137.Tao J S, Yang Y F, Li Y H. Comparison of paper tensile strength prediction models based on PLS and SVM methods[J]. Journal of South China University of Technology(Natural Science Edition),2014,(7):132-137.
[31] Le G, Yang H, Yu X. Improved UV/O3method for measuring the chemical oxygen demand[J]. Water Science&Technology, 2018,77(5):1271-1279.
[2]中华人名共和国生态环境部.水质化学需氧量的测定重铬酸盐法:HJ 828—2017[S].北京:中国环境出版社, 2017.Ministry of Ecology and Environment of the People's Republic of China. Water quality determination of the chemical oxygen demand Dichromate method:HJ 828—2017[S]. Beijing:China Environmental Press, 2017.
[3]国家技术监督局.水质高锰酸盐指数的测定:GB 11892—1989[S].北京:中国标准出版社, 1991.General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China. Water quality determination of permanganate index:GB 11892—1989[S].Beijing:Standards Press of China, 1991.
[4] Gr?nroos A, Kyll?nen H, Korpij?rvi K, et al. Ultrasound assisted method to increase soluble chemical oxygen demand(SCOD)of sewage sludge for digestion[J]. Ultrasonics Sonochemistry, 2005,12(1/2):115-120.
[5]李文,汪楷健,杨守波,等.应用超声消解快速检测COD方法的实验研究[J].工业水处理, 2016, 36(6):90-93.Li W, Wang K J, Yang S B, et al. Experimental research on the rapid detection method of chemical oxygen demand by ultrasonic assisted digestion technique[J] Industrial Water Treatment, 2016,36(6):90-93.
[6] Bryce D W, Izquierdo A, De Castro M D L. Use of focused microwaves for expeditive shortening of sample pre-treatment:digestion and reduction procedures prior to selenium speciation as selenium(IV)or selenium(VI)[J]. Analyst, 1995, 120(120):2171-2174.
[7]黄毅.微波密封消解法测定CODCr值[J].上海环境科学, 1996,15(5):32-34.Huang Y. Determination of CODCrusing sealed vessel microwave digestion method[J]. Shanghai Environmental Sciences, 1996, 15(5):32-34
[8]王照丽,罗娅君,李薇,等.微波消解法测定工业废水中的化学需氧量[J].环境科学与技术, 2016,(S1):71-74.Wang Z L, Luo Y J, Li W, et al. Determination of COD in industrial wastewater with microwave digestion[J]. Environmental Science&Technology, 2016,(S1):71-74.
[9]杨泽玉,胡涌刚.化学发光-化学需氧量测定新方法[J].分析化学, 2003, 31(12):1430-1432.Yang Z Y, Hu Y G. A Novel Chemiluminescence method for the determination of chemical oxygen demand[J]. Chinese Journal of Analytical Chemistry, 2003, 31(12):1430-1432.
[10] Hue D T K, Hashimoto S, Nishikawa H. A 3-step chemiluminescence method for chemical oxygen demand measurement[J]. Analytical Sciences the International Journal of the Japan Society for Analytical Chemistry, 2017, 9:5797-5805.
[11] Zheng Q, Zhou B, Bai J, et al. Self-organized TiO2nanotube array sensor for the determination of chemical oxygen demand[J].Advanced Materials, 2010, 20(5):1044-1049.
[12] Zhao H, Jiang D, Zhang S, et al. Development of a direct photoelectrochemical method for determination of chemical oxygen demand[J]. Analytical Chemistry, 2015, 76(1):155-160.
[13]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.
[14] Wibowo D, Ruslan, Maulidiyah M, et al. Determination of COD based on photoelectrocatalysis of FeTiO3.TiO2/Ti electrode[J]. IOP Conference Series:Materials Science and Engineering, 2017, 267(1):012007
[15] Jing T, Zhou Y S, Hao Q L, et al. A nano-nickel electrochemical sensor for sensitive determination of chemical oxygen demand[J].Analytical Methods, 2012, 4(4):1155-1159.
[16] Kim I, Tanaka H. Energy consumption for PPCPs removal by O3and O3/UV[J]. Ozone Science&Engineering, 2011, 33(2):150-157.
[17]董洪梅. 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 H M. Effect of ozone-UV technology on treatment of 2, 2',4, 4'-tetra BDE in aqueous medium[J]. China Environmental Science, 2013,(S1):19-25.
[18] Mert B K,?zge S, 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.
[19]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, 30(6):89-91.Zhang L, Yang H Z. COD detection device based on ozone coupled with UV[J]. China Water&Wastewater, 2014, 30(6):89-91.
[20]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.
[21] Suykens J A K, Vandewalle J. Least squares support machineclassifiers[J]. Neural Processing Letters, 1999, 9(3):293-300.
[22]杨小梅,刘文琦,杨俊.基于分阶段的LSSVM发酵过程建模[J].化工学报, 2013, 64(9):3262-3269.Yang X M, Liu W Q, Yang J. LSSVM modeling for fermentation process based on dividing stages[J] CIESC Journal, 2013, 64(9):3262-3269.
[23]郑蓉建,潘丰.基于PLS-LSSVM的谷氨酸发酵产物浓度预测建模[J].化工学报, 2017, 68(3):976-983Zheng R J, Pan F. Prediction of product concentration in glutamate fermentation process using partial least squares and least square support vector machine[J]. CIESC Journal, 2017, 68(3):976-983
[24]冯凯,卢建刚,陈金水.基于最小二乘支持向量机的MIMO线性参数变化模型辨识及预测控制[J].化工学报, 2015,(1):197-205.Feng K, Lu J G, Chen J S. Identification and model predictive control of LPV models based on LS-SVM for MIMO system[J].CIESC Journal, 2015,(1):197-205.
[25]欧阳爱国,唐天义,周鑫,等.最小二乘支持向量机结合中红外光谱测定甲醇柴油甲醇含量[J].发光学报, 2016,(10):1253-1258.Ouyang A G, Tang T Y, Zhou X, et al. Methanol content determination in methanol diesel with mid infrared spectroscopy analysis using least square support vector machine[J]. Chinese Journal of Lumine Science, 2016,(10):1253-1258
[26]张福东,刘杰,王智宏.基于最小二乘支持向量机的油页岩含油率近红外光谱分析[J].高等学校化学学报, 2016, 37(10):1792-1798.Zhang F D, Liu J, Wang Z H. Analysis of oil yield from oil shale minerals based on near-infrared spectroscopy with least squares support vector machines[J]. Chemical Journal of Chinese Universities, 2016, 37(10):1792-1798.
[27]张森,石为人,石欣,等.基于偏最小二乘回归和SVM的水质预测[J].计算机工程与应用, 2015, 51(15):249-254.Zhang S, Shi W R, Shi X, et al. Water quality prediction based on partial least squares and support vector machine[J]. Computer Engineering and Applications, 2015, 51(15):249-254.
[28]李远华,陶劲松,李继庚,等.基于偏最小二乘法的纸张抗张强度预测模型[J].化工学报, 2014, 65(9):3544-3551.Li Y H, Tao J S, Li J G, et al. Building predicting model of paper tensile strength based on partial least squares approach[J] CIESC Journal, 2014, 65(9):3544-3551.
[29]李晋华,张敏娟,张德龙.氧气A吸收带偏最小二乘基线拟合方法[J].中国激光, 2017,(8):281-287.Li J H, Zhang M J, Zhang D L. Baseline fitting of partial least squares for oxygen a abscorption band[J]. Chinese Journal of Lasers. 2017,(8):281-287.
[30]陶劲松,杨亚帆,李远华.基于PLS和SVM的纸张抗张强度建模比较[J].华南理工大学学报(自然科学版), 2014,(7):132-137.Tao J S, Yang Y F, Li Y H. Comparison of paper tensile strength prediction models based on PLS and SVM methods[J]. Journal of South China University of Technology(Natural Science Edition),2014,(7):132-137.
[31] Le G, Yang H, Yu X. Improved UV/O3method for measuring the chemical oxygen demand[J]. Water Science&Technology, 2018,77(5):1271-1279.