基于荧光技术的水中油浓度在线测量仪的研究
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摘要
石油对水资源的污染已成为主要的环境污染,由于饮用水资源极其有限,所以对水质实施及时的监测和污染处理就显得十分必要。
基于荧光的分析法具有简便、检测灵敏度高、易于实现在线测量等优点,这使其已成为当前水中微量矿物油浓度监测的一个研究热点。
本文对荧光测量法进行了详尽的研究,提出了一种在线测量系统的设计方法。
论文从荧光测量的基本原理出发,研究了石油荧光检测机理、分析了荧光法和全光纤实现水中油浓度测量的可行性以及荧光法相对于现有国标采用的红外法的优点,为在线测量系统的实现奠定了理论基础。
论文论述了吸收光谱、激发光谱、荧光光谱等荧光理论并通过实验的方法确定了矿物油的最佳激发波长和荧光波长。为激发光滤光片与荧光滤光片的选取提供了依据。
研究了光源的光谱特性、光源的驱动电路设计、光纤的传输特性、光电检测器件的选择等。设计了荧光测量仪器的系统原理图、信号检测系统控制电路图并勾画了在线测量系统的工程架构。从工程实践角度讲,该设计具有很强的可操作性。
通过对光纤荧光在线检测系统的噪声抑制方法进行分析,采用一种小波去噪方法——小波熵阈值去噪方法,进行小波阈值去噪,并将去噪后的荧光光谱图与用传统模拟低通滤波器去噪后的光谱图进行比较。结果表明,经小波去噪后的荧光光谱图更多地保留了原信号的信息,有助于提高系统的检测精度。
Oil contaminated to water is serious environment pollution and the water resource is very limit to human, so it is very important that the quality of water is monitored and polluted water is processed.
The analysis of oil in water base on the fluorescence is simpler and higher sensitive and easier in situ measurement. And because of this advantage, the fluorescence analysis became research hotspot in the concentration detection of oil in water.
This paper research the fluorescence measure way and given a new in situ measurement system.
Based on the fundamental theory of fluorescence measurement, this paper demonstrated the oil fluorescence detection principle and the feasibility of all optical fibers and fluorescence method in measuring oil concentration and also this paper describe the advantage of the fluorescence method compare with infrared method that was adopted by GB. All this can be used as the basis of theory and experiment for oil contamination measurement.
The paper describe the absorption spectra and excitation spectra and the fluorescence spectrum properties and also selected the best excitation wavelength and fluorescence wavelength. All these were done for selecting excitation light filter and fluorescence filter.
The paper studied the spectrum property of the excitation light, described the transmission property of fiber optic and selected photoelectric detector and so on. Described the blueprint of the fluorescence measuring instrument, design the control circuit of signal detection system and also described the system construction of the in situ measurement machine. It looked very suit for doing the real project.
Through analysis and research of noise control for in situ detection system, we get a new method for wavelet de-noising that based wavelet entropy. And the de-noised fluorescence spectrum via the wavelet transformation using this threshold method is compared to the de-noised spectrum via the analog low-pass filter . The result shows that the de-noising spectrum via the wavelet transformation keeps more information for the original signa1.So the detection sensitivity of the system will be improved with the aid of this method.
基于荧光的分析法具有简便、检测灵敏度高、易于实现在线测量等优点,这使其已成为当前水中微量矿物油浓度监测的一个研究热点。
本文对荧光测量法进行了详尽的研究,提出了一种在线测量系统的设计方法。
论文从荧光测量的基本原理出发,研究了石油荧光检测机理、分析了荧光法和全光纤实现水中油浓度测量的可行性以及荧光法相对于现有国标采用的红外法的优点,为在线测量系统的实现奠定了理论基础。
论文论述了吸收光谱、激发光谱、荧光光谱等荧光理论并通过实验的方法确定了矿物油的最佳激发波长和荧光波长。为激发光滤光片与荧光滤光片的选取提供了依据。
研究了光源的光谱特性、光源的驱动电路设计、光纤的传输特性、光电检测器件的选择等。设计了荧光测量仪器的系统原理图、信号检测系统控制电路图并勾画了在线测量系统的工程架构。从工程实践角度讲,该设计具有很强的可操作性。
通过对光纤荧光在线检测系统的噪声抑制方法进行分析,采用一种小波去噪方法——小波熵阈值去噪方法,进行小波阈值去噪,并将去噪后的荧光光谱图与用传统模拟低通滤波器去噪后的光谱图进行比较。结果表明,经小波去噪后的荧光光谱图更多地保留了原信号的信息,有助于提高系统的检测精度。
Oil contaminated to water is serious environment pollution and the water resource is very limit to human, so it is very important that the quality of water is monitored and polluted water is processed.
The analysis of oil in water base on the fluorescence is simpler and higher sensitive and easier in situ measurement. And because of this advantage, the fluorescence analysis became research hotspot in the concentration detection of oil in water.
This paper research the fluorescence measure way and given a new in situ measurement system.
Based on the fundamental theory of fluorescence measurement, this paper demonstrated the oil fluorescence detection principle and the feasibility of all optical fibers and fluorescence method in measuring oil concentration and also this paper describe the advantage of the fluorescence method compare with infrared method that was adopted by GB. All this can be used as the basis of theory and experiment for oil contamination measurement.
The paper describe the absorption spectra and excitation spectra and the fluorescence spectrum properties and also selected the best excitation wavelength and fluorescence wavelength. All these were done for selecting excitation light filter and fluorescence filter.
The paper studied the spectrum property of the excitation light, described the transmission property of fiber optic and selected photoelectric detector and so on. Described the blueprint of the fluorescence measuring instrument, design the control circuit of signal detection system and also described the system construction of the in situ measurement machine. It looked very suit for doing the real project.
Through analysis and research of noise control for in situ detection system, we get a new method for wavelet de-noising that based wavelet entropy. And the de-noised fluorescence spectrum via the wavelet transformation using this threshold method is compared to the de-noised spectrum via the analog low-pass filter . The result shows that the de-noising spectrum via the wavelet transformation keeps more information for the original signa1.So the detection sensitivity of the system will be improved with the aid of this method.
引文
1夏达英,张世魁.水中矿物油荧光特性实验研究.黄渤海海洋,2002,20(2):91-98
2王良均,吴孟周.石油化工废水处理设计手册.北京:中国石化出版社,838-839
3水质石油类和动植物油的测定-红外光度法.中华人民共和国国家标准GB/ 16488-1996国家环境保护局、国家技术监督局发布,1996-08-01发布
4 FLUORATO-02-3M荧光分析仪说明书.刘梅克斯公司,俄罗斯
5赵藻藩.周性尧,张悟铭,等.仪器分析.北京:高等教育出版社,1990
6陈素兰.红外光度法测定水中石油类.江苏地矿信息,2002,26(6):182-184
7杨俊衡.非分散红外法测定土壤中矿物油.仪器仪表与分析监测,2004,3:35-36
8钱达.水中矿物油的红外分光光度分析.交通环保,2000,3:31-34
9张丹丹.海面溢油的荧光光谱鉴别法述评.环境保护科学,2003,26(101):34-36
10 Uew Frank. Identification of petroleum oils by fluorescence spectroscopy. Conference on Prevention and Control of Oil Solution, 1979:11-16
11董献堆.水中矿物油的荧光分析.第八届青年分析测试会议论,2004,11(15):215
12郑健,周建光,陈焕文,等.水体和土壤中矿物油的常用测量方法与仪器[J].分析仪器.2004,3(3):1-9
13刘廷良,刘京,齐文启,等.水中石油分析方法的现状.环境科学研究,2002,13(5):58-60
14夏达英,张士魁.全光纤荧光水中矿物油浓度测量技术.国家科学进展,2002,20(2):91
15 Hill John, Lan Soutan. Identification of crude oils by synchronous excitations petrol fluoremetry. Analytical Chemistry, 1976,8(3):520-524
16 US Cost Guar, R and D Center Report. Oil spill identification system. National Technical Information Service CG-D-52-77, 1987,11-16
17 Scot H Fortier, Delay Stwood. Identification of fuel oils by low temperature luminescence spectrometry. Analytical Chemistry, 1998,50(2):334-338
18尚龙生.导数荧光技术在鉴别海面溢油方面的应用.海洋环境科学,1988,7(1):76
19马永安.气相色谱和荧光光谱多维线性指数模式识别法鉴别溢油.海洋环境科学,1990,9(2):76-82
20赵云英,马永安.荧光光谱法鉴别海面溢油的研究进展.海洋环境科,1997,16(2): 29-35
21马永安,赵云英.荧光光谱向量空间距离模式识别法鉴别海面溢油源.海洋学报,1998,2 (4):65-71
22何永安.三维荧光光谱技术简介.分析测试通报,1993,2(4):63-69
23许金钩,陈国珍.三维荧光光谱总体积积分法.科学通报,1997,42(7):714-716
24 Ndou Warner. Applications of multidimensional absorption and luminescence spectro scopies in analytical chemistry. Analytical Chemistry, 2000,91:493
25 Yong Kelan, Lu Jingei. Common and Diverse Characteristics of Three-dimensional Fluorescence Spectra of Crude oils. Spectroscopy letters, 2003,33(6):963-970
26夏达英,王振先,张士魁,等.海水荧光测量方法实验研究.海洋学,1999,3(1):104-109
27宋继梅,王凌峰.油气样品的固定波长同步荧光光谱特征研究.光谱学与光谱分析, 2003,22(5):803-805
28天然水,饮用水,污水中矿物油(石油类)总质量浓度的测定荧光分析法.俄罗斯国家环境保护总局PNDF10, 1:2:4.128-98.
29尚丽萍,史锦珊.全光纤荧光水中矿物油浓度测量技术研究.传感技术学报,2000.02: 132-136
30尚丽萍,史锦珊.地表水中矿物油浓度测量技术的研究.电子测量与仪器学报, 2000,14(3):13-16
31田广军.基于三维荧光谱参数化及模式识别的水中油类鉴别与测定.[燕山大学博士论文],2005:11
32郭德济,孙洪.光谱分析法.重庆:重庆大学出版社,1999:145,147,157-179
33王忠东.基于荧光机理的光纤农药残留测量系统的理论与实验研究.[燕山大学博士论文],2005,14-16
34尚丽萍.水中痕量矿物油污染荧光监测全光纤实现技术及应用基础.[燕山大学博士论文],2002:19
35 Yan Xu, Lin Ze. Study on to luminescence spectra-application of Monte-Carlo method to three-dimensional synchronous fluorescence spectrometry. Analytical Chemistry, 1995, 306:307
36 Tanco Hanalii, H. Junginger Bodd. Influence of phone the Intensity and Stability of the Fluorescence of pamino benzoic Acid in Aqueous solutions. European Journal of Chemistry Sciences,2003,5(1):31-35
37 MozoVillarias. Second Derivative Fluorescence Spectroscope of an Proteins. Journal of Biochemical and Biophysical Methods,2005,5(2-3):163-178
38 M Meroni, R Colombo. Leaf level detection of solar induced chlorophyll fluorescence by means of a subnanometer resolution spectro radiometer. Remote Sensing of Environment, 2006,(103):438-448
39王玉田.光电子学与光纤传感器技术.北京:国防工业出版社,2003:4-7
40 Zhang Yong sheng, Yu Ke, Xu Rong. Quartz Crystal Microbalance Coated with Carbon tube Films used as Humidity Sensor. Sensors and Actuators Physical,2005,1 20(1):142-146
41林坚,林永钟,谢树森.荧光分析系列滤光片.光电子·激光,2000,11(1):57-61
42郑龙江.光纤式海藻叶绿素a浓度的荧光测量理论与实践研究.[燕山大学博士论文文].2001:62-64
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2王良均,吴孟周.石油化工废水处理设计手册.北京:中国石化出版社,838-839
3水质石油类和动植物油的测定-红外光度法.中华人民共和国国家标准GB/ 16488-1996国家环境保护局、国家技术监督局发布,1996-08-01发布
4 FLUORATO-02-3M荧光分析仪说明书.刘梅克斯公司,俄罗斯
5赵藻藩.周性尧,张悟铭,等.仪器分析.北京:高等教育出版社,1990
6陈素兰.红外光度法测定水中石油类.江苏地矿信息,2002,26(6):182-184
7杨俊衡.非分散红外法测定土壤中矿物油.仪器仪表与分析监测,2004,3:35-36
8钱达.水中矿物油的红外分光光度分析.交通环保,2000,3:31-34
9张丹丹.海面溢油的荧光光谱鉴别法述评.环境保护科学,2003,26(101):34-36
10 Uew Frank. Identification of petroleum oils by fluorescence spectroscopy. Conference on Prevention and Control of Oil Solution, 1979:11-16
11董献堆.水中矿物油的荧光分析.第八届青年分析测试会议论,2004,11(15):215
12郑健,周建光,陈焕文,等.水体和土壤中矿物油的常用测量方法与仪器[J].分析仪器.2004,3(3):1-9
13刘廷良,刘京,齐文启,等.水中石油分析方法的现状.环境科学研究,2002,13(5):58-60
14夏达英,张士魁.全光纤荧光水中矿物油浓度测量技术.国家科学进展,2002,20(2):91
15 Hill John, Lan Soutan. Identification of crude oils by synchronous excitations petrol fluoremetry. Analytical Chemistry, 1976,8(3):520-524
16 US Cost Guar, R and D Center Report. Oil spill identification system. National Technical Information Service CG-D-52-77, 1987,11-16
17 Scot H Fortier, Delay Stwood. Identification of fuel oils by low temperature luminescence spectrometry. Analytical Chemistry, 1998,50(2):334-338
18尚龙生.导数荧光技术在鉴别海面溢油方面的应用.海洋环境科学,1988,7(1):76
19马永安.气相色谱和荧光光谱多维线性指数模式识别法鉴别溢油.海洋环境科学,1990,9(2):76-82
20赵云英,马永安.荧光光谱法鉴别海面溢油的研究进展.海洋环境科,1997,16(2): 29-35
21马永安,赵云英.荧光光谱向量空间距离模式识别法鉴别海面溢油源.海洋学报,1998,2 (4):65-71
22何永安.三维荧光光谱技术简介.分析测试通报,1993,2(4):63-69
23许金钩,陈国珍.三维荧光光谱总体积积分法.科学通报,1997,42(7):714-716
24 Ndou Warner. Applications of multidimensional absorption and luminescence spectro scopies in analytical chemistry. Analytical Chemistry, 2000,91:493
25 Yong Kelan, Lu Jingei. Common and Diverse Characteristics of Three-dimensional Fluorescence Spectra of Crude oils. Spectroscopy letters, 2003,33(6):963-970
26夏达英,王振先,张士魁,等.海水荧光测量方法实验研究.海洋学,1999,3(1):104-109
27宋继梅,王凌峰.油气样品的固定波长同步荧光光谱特征研究.光谱学与光谱分析, 2003,22(5):803-805
28天然水,饮用水,污水中矿物油(石油类)总质量浓度的测定荧光分析法.俄罗斯国家环境保护总局PNDF10, 1:2:4.128-98.
29尚丽萍,史锦珊.全光纤荧光水中矿物油浓度测量技术研究.传感技术学报,2000.02: 132-136
30尚丽萍,史锦珊.地表水中矿物油浓度测量技术的研究.电子测量与仪器学报, 2000,14(3):13-16
31田广军.基于三维荧光谱参数化及模式识别的水中油类鉴别与测定.[燕山大学博士论文],2005:11
32郭德济,孙洪.光谱分析法.重庆:重庆大学出版社,1999:145,147,157-179
33王忠东.基于荧光机理的光纤农药残留测量系统的理论与实验研究.[燕山大学博士论文],2005,14-16
34尚丽萍.水中痕量矿物油污染荧光监测全光纤实现技术及应用基础.[燕山大学博士论文],2002:19
35 Yan Xu, Lin Ze. Study on to luminescence spectra-application of Monte-Carlo method to three-dimensional synchronous fluorescence spectrometry. Analytical Chemistry, 1995, 306:307
36 Tanco Hanalii, H. Junginger Bodd. Influence of phone the Intensity and Stability of the Fluorescence of pamino benzoic Acid in Aqueous solutions. European Journal of Chemistry Sciences,2003,5(1):31-35
37 MozoVillarias. Second Derivative Fluorescence Spectroscope of an Proteins. Journal of Biochemical and Biophysical Methods,2005,5(2-3):163-178
38 M Meroni, R Colombo. Leaf level detection of solar induced chlorophyll fluorescence by means of a subnanometer resolution spectro radiometer. Remote Sensing of Environment, 2006,(103):438-448
39王玉田.光电子学与光纤传感器技术.北京:国防工业出版社,2003:4-7
40 Zhang Yong sheng, Yu Ke, Xu Rong. Quartz Crystal Microbalance Coated with Carbon tube Films used as Humidity Sensor. Sensors and Actuators Physical,2005,1 20(1):142-146
41林坚,林永钟,谢树森.荧光分析系列滤光片.光电子·激光,2000,11(1):57-61
42郑龙江.光纤式海藻叶绿素a浓度的荧光测量理论与实践研究.[燕山大学博士论文文].2001:62-64
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