改进ORP法水中臭氧杀菌效果检测仪的研制
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摘要
为了提高臭氧水处理过程中的杀菌消毒监测水平,在对水中臭氧杀菌效果检测技术国内外相关资料分析的基础之上,提出了基于电化学测试技术中的氧化还原电位(ORP)法来检测臭氧杀菌效果,并对此方法在实施过程中遇到的有关问题、改进方法以及检测仪器的研制进行了研究和探讨。
文中通过对水中臭氧杀菌效果各种检测方法优缺点的比较,指出杀菌剂残余浓度不能很好地反映杀菌效果,由于ORP与细菌杀灭效果高度相关,故采用ORP法。
本文对ORP法的基本原理、应用于杀菌检测的机理、基于ORP法的检测标准及特点等方面进行了研究。针对臭氧水溶液ORP测量的稳定性问题,通过资料分析和实验,指出臭氧水溶液ORP测量中受流速、温度影响。
针对臭氧水溶液ORP测量过程中遇到的流速、温度影响因素进行分析,并给出具体的改进办法:为了解决流速对ORP测量的影响,采用旋转溶液,控制溶液流速,快速的建立起传感器电极的动态平衡;为了解决温度对参比电极标准电位值的影响,采用温度补偿。通过流速影响实验,给出了测量的最优流速范围为1.83～2.2m/s。
本文给出了以高性能单片机ATmega8为核心的智能检测仪的总体设计方案,并分别从硬件及软件的功能方面给予具体实现。针对在仪器设计过程中所能遇到的噪声及干扰信号,分别从硬件和软件上进行电磁兼容设计,以提高仪器的抗干扰能力。
研究结果表明,基于改进ORP法制成的水中臭氧杀菌效果检测仪不仅在方案上切实可行,而且具有响应迅速、测量精度高、维护方便等优点,具有较好的应用前景。
In order to raise the monitoring level of disinfection effect in the process of water treatment that using ozone as sanitizer, a kind of oxidation-reduction potential (ORP) method which belongs to electrochemistry technology is proposed. The problems, the solutions and also the development of detecting instrument are studied when using this method.
Via the comparison of many kinds of detecting methods that using ozone as sanitizer in water, the remaining concentration of sanitizer is pointed out not to be a better instrument to reflect the disinfection effect. As highly related with the disinfection effect, the ORP method is adopted.
The principle of ORP method, the principle of disinfection detecting, together with the standard and characters of ORP are studied in this article. Via analyzing the data and experiment, the flow rate and temperature are pointed out to be the factors which influence the stability of the ORP detecting when using ozone as sanitizer in water.
In the process of ORP detecting the flow rate and temperature can affect the result, the reasons are analyzed and the improved methods are given in this article. In order to solve the flow rate problem, the method of revolving solution is adopted to control the flow rate and strike up the electrodes' homeostasis; the temperature compensation is applied in order to solve the temperature affection to the standard potential of reference electrode. The best flow rate range is 1.83～2.2m/s by the flow rate affection experiment.
The holistic design theory of the instrument whose core is the high performance ATmega8 MCU is introduced in this paper, and realized in both hardware and software. The EMC design for both hardware and software is considered to improve the instrument's anti-interference ability.
The experimental results show that the instrument for detecting the ozone disinfection effect in water based on improved ORP method is feasible; moreover it also has many advantages, such as fast response, high precision and convenient maintenance. So it will have a great application foreground.
文中通过对水中臭氧杀菌效果各种检测方法优缺点的比较,指出杀菌剂残余浓度不能很好地反映杀菌效果,由于ORP与细菌杀灭效果高度相关,故采用ORP法。
本文对ORP法的基本原理、应用于杀菌检测的机理、基于ORP法的检测标准及特点等方面进行了研究。针对臭氧水溶液ORP测量的稳定性问题,通过资料分析和实验,指出臭氧水溶液ORP测量中受流速、温度影响。
针对臭氧水溶液ORP测量过程中遇到的流速、温度影响因素进行分析,并给出具体的改进办法:为了解决流速对ORP测量的影响,采用旋转溶液,控制溶液流速,快速的建立起传感器电极的动态平衡;为了解决温度对参比电极标准电位值的影响,采用温度补偿。通过流速影响实验,给出了测量的最优流速范围为1.83～2.2m/s。
本文给出了以高性能单片机ATmega8为核心的智能检测仪的总体设计方案,并分别从硬件及软件的功能方面给予具体实现。针对在仪器设计过程中所能遇到的噪声及干扰信号,分别从硬件和软件上进行电磁兼容设计,以提高仪器的抗干扰能力。
研究结果表明,基于改进ORP法制成的水中臭氧杀菌效果检测仪不仅在方案上切实可行,而且具有响应迅速、测量精度高、维护方便等优点,具有较好的应用前景。
In order to raise the monitoring level of disinfection effect in the process of water treatment that using ozone as sanitizer, a kind of oxidation-reduction potential (ORP) method which belongs to electrochemistry technology is proposed. The problems, the solutions and also the development of detecting instrument are studied when using this method.
Via the comparison of many kinds of detecting methods that using ozone as sanitizer in water, the remaining concentration of sanitizer is pointed out not to be a better instrument to reflect the disinfection effect. As highly related with the disinfection effect, the ORP method is adopted.
The principle of ORP method, the principle of disinfection detecting, together with the standard and characters of ORP are studied in this article. Via analyzing the data and experiment, the flow rate and temperature are pointed out to be the factors which influence the stability of the ORP detecting when using ozone as sanitizer in water.
In the process of ORP detecting the flow rate and temperature can affect the result, the reasons are analyzed and the improved methods are given in this article. In order to solve the flow rate problem, the method of revolving solution is adopted to control the flow rate and strike up the electrodes' homeostasis; the temperature compensation is applied in order to solve the temperature affection to the standard potential of reference electrode. The best flow rate range is 1.83～2.2m/s by the flow rate affection experiment.
The holistic design theory of the instrument whose core is the high performance ATmega8 MCU is introduced in this paper, and realized in both hardware and software. The EMC design for both hardware and software is considered to improve the instrument's anti-interference ability.
The experimental results show that the instrument for detecting the ozone disinfection effect in water based on improved ORP method is feasible; moreover it also has many advantages, such as fast response, high precision and convenient maintenance. So it will have a great application foreground.
引文
[1]周渭,于建,刘海霞.测试与计量技术基础.西安:西安电子科技大学出版社,2004:1-7.
[2]冯玉杰,李晓岩,尤红等.电化学技术在环境工程中的应用.北京:化学工业出版社,2003:1-5.
[3]刘传桂,邵晶,张晓霞等.全固态控制电位电解型S02气体传感器的研制.传感技术学报.2003,3:363-366.
[4]冯业铭,董平,樊忠良等.控制电位电解一氧化碳监测仪的研制.中国矿业大学学报.1994,23(2):9-17.
[5]赵金农,张瑞菊,范菲.饮水中碘含量的快速测量—新型电化学传感器的研制及测量.医疗设备信息.1999,2:16-18.
[6]王康丽,严河清,刘军等.氮氧化物化学传感器.武汉大学学报.2003,49(4):428-432.
[7]陈长伦,何建波,刘伟等.电化学式气体传感器的研究进展.传感器世界.2004,4:11-15.
[8]赵清,舒为群,高京生.瓶装饮用水的水质标准及卫生学问题.卫生研究.2004,33(3):386-388.
[9]徐显干,陈为民,萧贤明.O_3_UV高级氧化杀菌系统在瓶装饮用纯净水中的应用.净水技术.2006,25:33-35.
[10]李卫国,郑群.臭氧在纯净水中的应用及控制.饮料工业.2002,5:41-44.
[11]王芳.臭氧水消毒处理的细菌超微结构变化的观察.中国消毒学杂志.2006,23(5):413-145.
[12]谭桂霞,陈烨璞.关于臭氧研究的进展.上海大学学报.2004,10(5):537-542.
[13]朱星明,王浩静.臭氧化法水处理技术.环境保护科学.2005,31(130):14-17.
[14]张介轩.臭氧的应用及生成.城市管理与科技.2002,4(4):39.
[15]储金宁,吴春笃,陈万金等编著,臭氧技术及应用.北京:化学工业出版社,2002:4-9,186-189.
[16]Aurelie G.Use ozone for treatment of water in fishfarming.Proceeding of IOA14th Ozone World Congress.gerlin:International Ozone Association,2000:755-767.
[17]李素芬.控制电位型水中臭氧电化学传感器的试验研究:(硕士学位论文).大连:大连理工大学,2005.
[18]Jacques M S,Catherine P.ORP sensor response in chlorined water.NSPI Water Chemistry Symposium,USA:Phoenix,AZ,1996:231-239.
[19]Jacques M S.ORP Testing and chemical automation for swimming pools and spas.National Environmental Health Association.CEHA California Education Symposium-Monterey,CA,1990,12:192-195.
[20]沈敏,刘钟阳,水中臭氧浓度自动检测有关问题的研究.计算机测量与控制.2004,12(11):1027-1029.
[21]Yen P C,Yung Y L,Cheng N C.Differentiating ozone direct and indirect reactions in decomposition of humic substances.Chemosphere,2006,65:2395-2400
[22]Urs yon Gunten.Ozonation of drinking water:Part I.Oxidation kinetics and product formation.Water Research,2003,37:1443-1467.
[23]Urs V G.Ozonation of drinking water:Part Ⅱ.Disinfection and by-product formation in presence of bromide,iodide or chlorine.Water Research,2003,3?:1469-148?.
[24]谭梓霞,陈烨璞,徐晓萍.臭氧在气态和水溶液中的分解规律.上海大学学报.2005,11(5):510-512.
[25]王业耀,卢醒,王占生.消除DPD法测定水中臭氧浓度干扰因素的研究.化工环保.1996,16:178-180.
[26]唐晓,王佳.海水ORP的影响因素.装备环境工程.2004,4:37-39.
[27]张延青,冯亚鹏,刘鹰.用氧化还原电位法测定臭氧处理海水生成氧化物的研究.渔业现代化.2006,3:11-14.
[28]王爱军,王聪,马传芳.海水ORP常规流动测量装置计量特性初探.海洋技术.2007,26(2):78-83.
[29]俞汝勤.离子选择性电极分析法.北京:人民教育出版社,1980.
[30]Bard A J,Faulkener L R.Electrochemical methods fundamentals and applications.New York:John Wiley & Sons,2002.
[31]陈韬,彭永臻,田文军等.ORP检测在水处理中的应用.中国给水排水.2003,19:20-22.
[32]Jacques M S.PPM or ORP:Which should be used.Swimming Pool Age and Spa Merchandiser.1985,6:1-6.
[33]邓小虹,彭国克,李风玲.强氧化离子水杀菌性能试验研究.中华医院感染学杂志.1998,8(1):38-39.
[34]李景芹,丁津华.酸化电位水对微生物的杀菌效果.中华流行病学杂志.1999,20(6):394.
[35]张洁宏,韩彦彬,石子伦.酸化电位水杀菌效果及有机物影响的实验观察.中国消毒学杂志,2004,21(1):36-37.
[36]何志刚,邵爱仙,顾青.酸化电位水杀灭细菌微生物效果的试验.浙江实用医学.2006,11(1):64-65.
[37]陈贵秋,李爱斌,梁进军等.氧化电位水杀微生物效果及影响因素的实验研究.实用预防医学.2001,8(4):269-271.
[38]陈小立,刘海雄,李国维.臭氧水溶液的ORP、PH与灭大肠杆菌的研究.纺织高校基础科学学报.2001,14(4):333-336.
[39]Shun Y H.Effects of flow rate,temperature and salt concentration on chemical and physical properties of electrolyzed oxidizing water.Journal of Food Engineering.2005,66:171-176.
[40]Ren(?) Knake,Peter C H.Sensitive electrochemical detection of ozone.Analytica Chimica Acta,2002,459:199-207.
[41]刘钟阳.放电等离子体合成臭氧及应用中的一些问题的研究:(博士学位论文).大连:大连理工大学,2002.
[2]冯玉杰,李晓岩,尤红等.电化学技术在环境工程中的应用.北京:化学工业出版社,2003:1-5.
[3]刘传桂,邵晶,张晓霞等.全固态控制电位电解型S02气体传感器的研制.传感技术学报.2003,3:363-366.
[4]冯业铭,董平,樊忠良等.控制电位电解一氧化碳监测仪的研制.中国矿业大学学报.1994,23(2):9-17.
[5]赵金农,张瑞菊,范菲.饮水中碘含量的快速测量—新型电化学传感器的研制及测量.医疗设备信息.1999,2:16-18.
[6]王康丽,严河清,刘军等.氮氧化物化学传感器.武汉大学学报.2003,49(4):428-432.
[7]陈长伦,何建波,刘伟等.电化学式气体传感器的研究进展.传感器世界.2004,4:11-15.
[8]赵清,舒为群,高京生.瓶装饮用水的水质标准及卫生学问题.卫生研究.2004,33(3):386-388.
[9]徐显干,陈为民,萧贤明.O_3_UV高级氧化杀菌系统在瓶装饮用纯净水中的应用.净水技术.2006,25:33-35.
[10]李卫国,郑群.臭氧在纯净水中的应用及控制.饮料工业.2002,5:41-44.
[11]王芳.臭氧水消毒处理的细菌超微结构变化的观察.中国消毒学杂志.2006,23(5):413-145.
[12]谭桂霞,陈烨璞.关于臭氧研究的进展.上海大学学报.2004,10(5):537-542.
[13]朱星明,王浩静.臭氧化法水处理技术.环境保护科学.2005,31(130):14-17.
[14]张介轩.臭氧的应用及生成.城市管理与科技.2002,4(4):39.
[15]储金宁,吴春笃,陈万金等编著,臭氧技术及应用.北京:化学工业出版社,2002:4-9,186-189.
[16]Aurelie G.Use ozone for treatment of water in fishfarming.Proceeding of IOA14th Ozone World Congress.gerlin:International Ozone Association,2000:755-767.
[17]李素芬.控制电位型水中臭氧电化学传感器的试验研究:(硕士学位论文).大连:大连理工大学,2005.
[18]Jacques M S,Catherine P.ORP sensor response in chlorined water.NSPI Water Chemistry Symposium,USA:Phoenix,AZ,1996:231-239.
[19]Jacques M S.ORP Testing and chemical automation for swimming pools and spas.National Environmental Health Association.CEHA California Education Symposium-Monterey,CA,1990,12:192-195.
[20]沈敏,刘钟阳,水中臭氧浓度自动检测有关问题的研究.计算机测量与控制.2004,12(11):1027-1029.
[21]Yen P C,Yung Y L,Cheng N C.Differentiating ozone direct and indirect reactions in decomposition of humic substances.Chemosphere,2006,65:2395-2400
[22]Urs yon Gunten.Ozonation of drinking water:Part I.Oxidation kinetics and product formation.Water Research,2003,37:1443-1467.
[23]Urs V G.Ozonation of drinking water:Part Ⅱ.Disinfection and by-product formation in presence of bromide,iodide or chlorine.Water Research,2003,3?:1469-148?.
[24]谭梓霞,陈烨璞,徐晓萍.臭氧在气态和水溶液中的分解规律.上海大学学报.2005,11(5):510-512.
[25]王业耀,卢醒,王占生.消除DPD法测定水中臭氧浓度干扰因素的研究.化工环保.1996,16:178-180.
[26]唐晓,王佳.海水ORP的影响因素.装备环境工程.2004,4:37-39.
[27]张延青,冯亚鹏,刘鹰.用氧化还原电位法测定臭氧处理海水生成氧化物的研究.渔业现代化.2006,3:11-14.
[28]王爱军,王聪,马传芳.海水ORP常规流动测量装置计量特性初探.海洋技术.2007,26(2):78-83.
[29]俞汝勤.离子选择性电极分析法.北京:人民教育出版社,1980.
[30]Bard A J,Faulkener L R.Electrochemical methods fundamentals and applications.New York:John Wiley & Sons,2002.
[31]陈韬,彭永臻,田文军等.ORP检测在水处理中的应用.中国给水排水.2003,19:20-22.
[32]Jacques M S.PPM or ORP:Which should be used.Swimming Pool Age and Spa Merchandiser.1985,6:1-6.
[33]邓小虹,彭国克,李风玲.强氧化离子水杀菌性能试验研究.中华医院感染学杂志.1998,8(1):38-39.
[34]李景芹,丁津华.酸化电位水对微生物的杀菌效果.中华流行病学杂志.1999,20(6):394.
[35]张洁宏,韩彦彬,石子伦.酸化电位水杀菌效果及有机物影响的实验观察.中国消毒学杂志,2004,21(1):36-37.
[36]何志刚,邵爱仙,顾青.酸化电位水杀灭细菌微生物效果的试验.浙江实用医学.2006,11(1):64-65.
[37]陈贵秋,李爱斌,梁进军等.氧化电位水杀微生物效果及影响因素的实验研究.实用预防医学.2001,8(4):269-271.
[38]陈小立,刘海雄,李国维.臭氧水溶液的ORP、PH与灭大肠杆菌的研究.纺织高校基础科学学报.2001,14(4):333-336.
[39]Shun Y H.Effects of flow rate,temperature and salt concentration on chemical and physical properties of electrolyzed oxidizing water.Journal of Food Engineering.2005,66:171-176.
[40]Ren(?) Knake,Peter C H.Sensitive electrochemical detection of ozone.Analytica Chimica Acta,2002,459:199-207.
[41]刘钟阳.放电等离子体合成臭氧及应用中的一些问题的研究:(博士学位论文).大连:大连理工大学,2002.