激光二极管波长调制技术用于氧气浓度检测的研究
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摘要
氧气是一种很重要的日常生活和工业用气体，探讨工业生产环境特别是锅炉尾气中氧气浓度检测的新的实用而准确的方法和装置对提高生产效率、燃烧利用率以及减少环境污染有很重要的实际意义。
文章全面调研了目前氧气浓度检测的现状，评述了各种方法和检测装置的优缺点。在分析比较的基础上，提出将激光二极管发射波长调制及谐波检测分析处理技术用于氧气浓度检测。
文章在介绍气体光谱吸收理论的基础上，着重对氧气的吸收光谱特点进行了分析研究，这对我们建立和实施我们提出的检测方案具有一定的指导意义。
文中着重对检测用光源激光二极管的特点，激光二极管波长的调制控制，氧气吸收光谱信息的探测，谐波检测相关线性及参数的设计和选择，如何提高信噪比，提高检测精度，简化实施装置的结构等进行了深入的分析研究。在现有实验条件下设计组建了检测氧气浓度的实验系统。为了便于检测控制和数据处理，我们将虚拟仪器技术用在我们的实验中。整个实验装置的联调、相关参数的调整均取得满意的结果。
用所建立的实验检测系统，我们对氧气的标定和浓度检测进行了多次实测。测量结果表明，所建实验装置运行良好，实验数据重复程度好，并且给出比较好的线性测量精度。这为该检测方法在国内的进一步深入研究和实用提供了满意的理论和实验基础。利用光谱吸收法实现氧气浓度检测，这在国内还是首次尝试。
Oxygen is an important gas in daily life and industry. Looking for a practical, accurate method and equipment for the detection of oxygen concentration in the industry surroundings, especially in the exhaust gas of boiler, has significant practical sense for improving the production efficiency and combustion utilization ratio, and reducing the environment pollution.
The state of oxygen concentration detection was comprehensively surveyed in this thesis. Merits and demerits of each method and equipment were commented. Then, the idea that detecting oxygen concentration by using laser diode wavelength modulation and harmonic signal treatment was proposed.
The characteristics of oxygen absorption spectrum were emphasized based on the theory of gas absorption spectrum. This work was helpful to set up and actualize detection scheme.
The followings were deeply and comprehensively discussed in this thesis: laser diode characteristics, controlling of the wavelength modulation of laser diode, detecting of the oxygen absorption, treatment of the harmonic signal and selection of the parameters, improvement of the signal to noise ratio and the test precision, etc. An experimental system has been set up based on the detection theory. The Virtual Instrument technology was introduced in the system, which is convenient for detection controlling and data processing.
The experiments for actual oxygen concentration detecting had been carried out repeatedly and the some satisfied results had been acquired. The experimental system runs well. The output data from the experimental system had a good repeatability and a good linear relation with the oxygen concentration. This work provided the theoretic and experimental basis for further research and practice in our future work. This is also the first time attempt to realizing oxygen concentration determination by using spectrum absorption method domestically.
文章全面调研了目前氧气浓度检测的现状，评述了各种方法和检测装置的优缺点。在分析比较的基础上，提出将激光二极管发射波长调制及谐波检测分析处理技术用于氧气浓度检测。
文章在介绍气体光谱吸收理论的基础上，着重对氧气的吸收光谱特点进行了分析研究，这对我们建立和实施我们提出的检测方案具有一定的指导意义。
文中着重对检测用光源激光二极管的特点，激光二极管波长的调制控制，氧气吸收光谱信息的探测，谐波检测相关线性及参数的设计和选择，如何提高信噪比，提高检测精度，简化实施装置的结构等进行了深入的分析研究。在现有实验条件下设计组建了检测氧气浓度的实验系统。为了便于检测控制和数据处理，我们将虚拟仪器技术用在我们的实验中。整个实验装置的联调、相关参数的调整均取得满意的结果。
用所建立的实验检测系统，我们对氧气的标定和浓度检测进行了多次实测。测量结果表明，所建实验装置运行良好，实验数据重复程度好，并且给出比较好的线性测量精度。这为该检测方法在国内的进一步深入研究和实用提供了满意的理论和实验基础。利用光谱吸收法实现氧气浓度检测，这在国内还是首次尝试。
Oxygen is an important gas in daily life and industry. Looking for a practical, accurate method and equipment for the detection of oxygen concentration in the industry surroundings, especially in the exhaust gas of boiler, has significant practical sense for improving the production efficiency and combustion utilization ratio, and reducing the environment pollution.
The state of oxygen concentration detection was comprehensively surveyed in this thesis. Merits and demerits of each method and equipment were commented. Then, the idea that detecting oxygen concentration by using laser diode wavelength modulation and harmonic signal treatment was proposed.
The characteristics of oxygen absorption spectrum were emphasized based on the theory of gas absorption spectrum. This work was helpful to set up and actualize detection scheme.
The followings were deeply and comprehensively discussed in this thesis: laser diode characteristics, controlling of the wavelength modulation of laser diode, detecting of the oxygen absorption, treatment of the harmonic signal and selection of the parameters, improvement of the signal to noise ratio and the test precision, etc. An experimental system has been set up based on the detection theory. The Virtual Instrument technology was introduced in the system, which is convenient for detection controlling and data processing.
The experiments for actual oxygen concentration detecting had been carried out repeatedly and the some satisfied results had been acquired. The experimental system runs well. The output data from the experimental system had a good repeatability and a good linear relation with the oxygen concentration. This work provided the theoretic and experimental basis for further research and practice in our future work. This is also the first time attempt to realizing oxygen concentration determination by using spectrum absorption method domestically.
引文
[1] 邱安平，苑立波，钟辉．氧量含量的光纤检测方法研究，哈尔滨理工大学学报，1994，4(2)：42-44
[2] 王家桢，王俊杰．传感器与变送器，北京：清华大学出版社，1996：204
[3] Michael E.Webber, Suhong Kim, Scott T.Sanders. In situ combustion measurements of CO_2 by use of a distributed-feedback diode-laser sensor near 2.0mm, Appl.Opt., 2001, 40(6): 821-828
[4] R.R.Skaggs, R.G.Daniel, A.W.Miziolek. Diode laser measurements of HF concentrations produced from heptane-air pan fires extinguished by FE-36, FM-200,FE-36 plus APP, or FM-200 plus APP, Appl.Spectrosc., 1999, 53: 1143-1148
[5] J.Reid, M.El-Sherbiny, B.K.Garside. Sensitivity limit of a tunable diode laser spectrometer, with application to the detection of NO at the 100-ppt level, Appl.Opt., 1980, 19:3349-3354
[6] J.Wang, S.T.Sanders, J.B.Jeffries. Oxygen measurements at high pressures with vertical cavity surface-emitting lasers, Appl.Phys.B, 2001, 72(7): 865-872
[7] H.P.Zappe, M.Hess, M.Moser. Narrow-linewidth vertical-cavity surface-emitting lasers for oxygen detection, Applied Optics, 2000, 39:2475-2479
[8] D.M.Bruce, D.T.Cassidy. Detection of oxygen using short external cavity GaAs semiconductor diode laser, Appl.Opt., 1990, 29:1327-1332
[9] E.Vander Donckt, B.Camerman, R.Herne. Fibre-optic oxygen sensor based on luminescence quenching of a Pt(Ⅱ) complex embedded in polymer matrices, Sensors and Actuators B, 1996, 32:121-127
[10] M.A.Chan, J.L.Lawless, S.K.Lam. Fiber optic oxygen sensor based on phosphorescence quenching of erythrosin B trapped in silica-gel glasses, Analytica Chimica Acta, 2000, 408:33-37
[11] Kerry.P.McNamara, Xueping Li, Angela D.Stull. Fiber-optic oxygen sensor based on the fouorescence quenching of tris(5-acrylamido, 1,10 phenanthroline) ruthenium chloride, Analytica Chimica Acta, 1998, 361:73-83
[12] 朱明华．仪器分析，北京：高等教育出版社，2000
[13] 刘崇进，郑大昉．气体传感器的发展概况和发展方向，计算机自动测量与控制，1999，7(2)：54-56
[14] 刘威．气体传感器的研究与发展，化工时刊，2000(9)：1-5
[15] G.Sberveglieri. Recent developments in semiconducting thin-film gas sensors, Sensors and Actuators B, 1995, 23:103-105
[16] V.M.Aroutiounian, G.S.Aghababian. To the theory of semiconductor gas sensors, Sensors and Actuators B, 1998, 50:80-84
[17] 崔熙钟．气体传感器及其应用，有色金属分析通讯，1992(3)：26-31
[18] 杨邦朝，张益康．气体传感器研究动向，传感器世界，1997(9)：1-8
[19] Yongfa Zhu, Jinjun Shi, Zhenyu Zhang. Development of a Gas Sensor Utilizing Chemiluminescence on Nanosized Titanium Dioxide, Anal.Chem., 2002, 74:120-124
[20] Yang Qingbai, Li Peng. Oxygen sensor and its application in thermal power plant, Sensor world(Chinese), 2001 (9): 19-21
[21] Jacob Y.Wong, Santa Barbara. Oxygen measurement using visible radiation, United States Patent:4730112, 1988
[22] 喻洪波，廖延彪，靳伟．光纤化的气体传感技术，激光与红外，2002，32(3)：193-196
[23] Xueping Li, Zeev Rosenzweig. A fiber optic sensor for rapid analysis of bilirubin in serum, Analytica Chimica Acta, 1997, 353:263-273
[24] Ming Fat Choi, Peter Hawkins. A fiber-optic oxygen sensor based on contact charge-transfer absorption, Sensors and Actuators B, 1996, 30:167-171
[25] C.Kolle, W.Gruber, W.Trettnak. Fast optochemical sensor for continuous monitoring of oxygen in breath-gas analysis, Sensors and Actuators B, 1997, 38: 141-149
[26] M.Tservistas, R.Koneke, A.Comte. Oxygen monitoring in supercritical carbon dioxide using a fibre optic sensor, Enzyme and Microbial Technology, 2001, 28: 637-641
[27] Wolfgang Trettnak, Wolfgang Gruber, Franz Reininger. Recent progress in optical oxygen sensor instrumentation, Sensors and Actuators B, 1995, 29:219-225
[28] A.K.Demin, B.V.Zhuravlev, S.I.Somov. Sensor for measuring the oxygen concentration in gas mixtures with unsteady pressure, Solid State Ionics, 1998, 112: 355-359
[29] O.Kohls a, Th.Scheper. Setup of a fiber optical oxygen multisensor-system and its applications in biotechnology, Sensors and Actuators B, 2000, 70:121-130
[30] V.Weldon, J.J.Perez-Camacho, D.McDonaid. Laser diode based oxygen sensing: A comparison of VCSEL and DFB laser diodes emitting in the 762nm region, Infrared Physics & Technology, 1997, 38:325-329
[31] 吴国祯．分子振动光谱学基础，北京：化学工业出版社，1990
[32] 钟立晨，丁海曙．分子光谱及激光，北京：电子工业出版社，1987
[33] 夏慧荣，王祖赓．分子光谱学和激光光谱学导论，上海：华东师范大学出版社，1989
[34] Rothman, L. S., Barbe, A., Chris Benner, D. The HITRAN molecular spectroscopic database: edition of 2000 including updates through 2001, Journal of Quantitative Spectroscopy and Radiative Transfer, 2003, 82(1-4): 5-44
[35] K.J.Ritter, T.D.Wilkerson. High-resolution spectroscopy of the oxygen A band, J.Mol.Spectrosc., 1987, 121:1-19
[36] Wang Yutian, Guo Tingrong, Wang Litian. A methane optic fiber sensor of differential absorption, Journal of Transducer Technology (Chinese), 2000, 19(5): 42-43
[37] Chen Juan, Feng Xiyu, Ma Ying. A CH_4 gas sensing system using infrared absorption type optic fibre, Journal of JiLin Institute of Technology (Chinese), 1997, 18(2): 57-60
[38] 雷玉堂，王庆有，何加铭．光电检测技术，北京：中国计量出版社，1997
[39] 张志鹏．光纤传感器原理，北京：中国计量出版社，1991
[40] Xie Jianping, Wang Pei, Xu Lixin. Wavelength tuning and stabilizing techniques of
semiconductor lasers, Chinese journal of quantum electronics, 2002, 19(2): 97-103
[41] Stephen D.Walker, Robert A.Nichols, William A.Cuman. Method and apparatus for measuring gas concentration using a semiconductor laser, United States Patent: 6091504, 2000
[42] P.Werle, R.Mucke, F.D'Amato. Near-infrared trace-gas sensors based on room-temperature diode lasers, Appl.Phys.B, 1998, 67:307-315
[43] 黄德修，刘雪峰．半导体激光器及其应用，北京：国防工业出版社，2004
[44] 黄章勇．光纤通信用光电子器件和组件，北京：北京邮电大学出版社，2001
[45] 张培林．半导体激光器在光谱研究中的应用，物理，1993，22(10)：596-601
[46] M.Kroil, J.A.McClintock, O.Ollinger. Measurement of gaseous oxygen using diode laser spectroscopy, Appl.Phys.Lett., 1987, 51 (18): 1465-1467
[47] 张靖，刘少强．检测技术与系统设计，北京：中国电力出版社，2002：383-385
[48] 王仲生．智能检测与控制技术，西安：西北工业大学出版社，2002：226-230
[49] Model 7260 DSP Lock-in Amplifier Instrument Manual, EG&G INSTRUMENTS CORPORATION, 1996
[50] 陆同兴，路轶群．激光光谱技术原理及应用，合肥：中国科学技术大学出版社，1999
[51] A N Dharamsi. A theory of modulation spectroscopy with applications of higher harmonic detection, J.Phys.D:Appl.Phys., 1996, 29:540-549
[52] P.Kluczynski, O.Axner. Theoretical description based upon Fourier analysis of wavelength-modulation spectrometry in terms of analytical and background signals, Appl.Opt., 1999, 38:5803-5815
[53] X.Zhu, D.T.Cassidy. Modulation spectroscopy with a semiconductor diode laser by injection-current modulation, J.Opt.Soc.Am.B, 1997, 14:1945-1950
[54] 张国威，王兆民．激光光谱学原理与技术，北京：北京理工大学出版社，2004
[55] 杨乐平，李海涛等．虚拟仪器技术概论，北京：电子工业出版社，2003
[56] 汪敏生．LabVIEW基础教程，北京：电子工业出版社，2002
[2] 王家桢，王俊杰．传感器与变送器，北京：清华大学出版社，1996：204
[3] Michael E.Webber, Suhong Kim, Scott T.Sanders. In situ combustion measurements of CO_2 by use of a distributed-feedback diode-laser sensor near 2.0mm, Appl.Opt., 2001, 40(6): 821-828
[4] R.R.Skaggs, R.G.Daniel, A.W.Miziolek. Diode laser measurements of HF concentrations produced from heptane-air pan fires extinguished by FE-36, FM-200,FE-36 plus APP, or FM-200 plus APP, Appl.Spectrosc., 1999, 53: 1143-1148
[5] J.Reid, M.El-Sherbiny, B.K.Garside. Sensitivity limit of a tunable diode laser spectrometer, with application to the detection of NO at the 100-ppt level, Appl.Opt., 1980, 19:3349-3354
[6] J.Wang, S.T.Sanders, J.B.Jeffries. Oxygen measurements at high pressures with vertical cavity surface-emitting lasers, Appl.Phys.B, 2001, 72(7): 865-872
[7] H.P.Zappe, M.Hess, M.Moser. Narrow-linewidth vertical-cavity surface-emitting lasers for oxygen detection, Applied Optics, 2000, 39:2475-2479
[8] D.M.Bruce, D.T.Cassidy. Detection of oxygen using short external cavity GaAs semiconductor diode laser, Appl.Opt., 1990, 29:1327-1332
[9] E.Vander Donckt, B.Camerman, R.Herne. Fibre-optic oxygen sensor based on luminescence quenching of a Pt(Ⅱ) complex embedded in polymer matrices, Sensors and Actuators B, 1996, 32:121-127
[10] M.A.Chan, J.L.Lawless, S.K.Lam. Fiber optic oxygen sensor based on phosphorescence quenching of erythrosin B trapped in silica-gel glasses, Analytica Chimica Acta, 2000, 408:33-37
[11] Kerry.P.McNamara, Xueping Li, Angela D.Stull. Fiber-optic oxygen sensor based on the fouorescence quenching of tris(5-acrylamido, 1,10 phenanthroline) ruthenium chloride, Analytica Chimica Acta, 1998, 361:73-83
[12] 朱明华．仪器分析，北京：高等教育出版社，2000
[13] 刘崇进，郑大昉．气体传感器的发展概况和发展方向，计算机自动测量与控制，1999，7(2)：54-56
[14] 刘威．气体传感器的研究与发展，化工时刊，2000(9)：1-5
[15] G.Sberveglieri. Recent developments in semiconducting thin-film gas sensors, Sensors and Actuators B, 1995, 23:103-105
[16] V.M.Aroutiounian, G.S.Aghababian. To the theory of semiconductor gas sensors, Sensors and Actuators B, 1998, 50:80-84
[17] 崔熙钟．气体传感器及其应用，有色金属分析通讯，1992(3)：26-31
[18] 杨邦朝，张益康．气体传感器研究动向，传感器世界，1997(9)：1-8
[19] Yongfa Zhu, Jinjun Shi, Zhenyu Zhang. Development of a Gas Sensor Utilizing Chemiluminescence on Nanosized Titanium Dioxide, Anal.Chem., 2002, 74:120-124
[20] Yang Qingbai, Li Peng. Oxygen sensor and its application in thermal power plant, Sensor world(Chinese), 2001 (9): 19-21
[21] Jacob Y.Wong, Santa Barbara. Oxygen measurement using visible radiation, United States Patent:4730112, 1988
[22] 喻洪波，廖延彪，靳伟．光纤化的气体传感技术，激光与红外，2002，32(3)：193-196
[23] Xueping Li, Zeev Rosenzweig. A fiber optic sensor for rapid analysis of bilirubin in serum, Analytica Chimica Acta, 1997, 353:263-273
[24] Ming Fat Choi, Peter Hawkins. A fiber-optic oxygen sensor based on contact charge-transfer absorption, Sensors and Actuators B, 1996, 30:167-171
[25] C.Kolle, W.Gruber, W.Trettnak. Fast optochemical sensor for continuous monitoring of oxygen in breath-gas analysis, Sensors and Actuators B, 1997, 38: 141-149
[26] M.Tservistas, R.Koneke, A.Comte. Oxygen monitoring in supercritical carbon dioxide using a fibre optic sensor, Enzyme and Microbial Technology, 2001, 28: 637-641
[27] Wolfgang Trettnak, Wolfgang Gruber, Franz Reininger. Recent progress in optical oxygen sensor instrumentation, Sensors and Actuators B, 1995, 29:219-225
[28] A.K.Demin, B.V.Zhuravlev, S.I.Somov. Sensor for measuring the oxygen concentration in gas mixtures with unsteady pressure, Solid State Ionics, 1998, 112: 355-359
[29] O.Kohls a, Th.Scheper. Setup of a fiber optical oxygen multisensor-system and its applications in biotechnology, Sensors and Actuators B, 2000, 70:121-130
[30] V.Weldon, J.J.Perez-Camacho, D.McDonaid. Laser diode based oxygen sensing: A comparison of VCSEL and DFB laser diodes emitting in the 762nm region, Infrared Physics & Technology, 1997, 38:325-329
[31] 吴国祯．分子振动光谱学基础，北京：化学工业出版社，1990
[32] 钟立晨，丁海曙．分子光谱及激光，北京：电子工业出版社，1987
[33] 夏慧荣，王祖赓．分子光谱学和激光光谱学导论，上海：华东师范大学出版社，1989
[34] Rothman, L. S., Barbe, A., Chris Benner, D. The HITRAN molecular spectroscopic database: edition of 2000 including updates through 2001, Journal of Quantitative Spectroscopy and Radiative Transfer, 2003, 82(1-4): 5-44
[35] K.J.Ritter, T.D.Wilkerson. High-resolution spectroscopy of the oxygen A band, J.Mol.Spectrosc., 1987, 121:1-19
[36] Wang Yutian, Guo Tingrong, Wang Litian. A methane optic fiber sensor of differential absorption, Journal of Transducer Technology (Chinese), 2000, 19(5): 42-43
[37] Chen Juan, Feng Xiyu, Ma Ying. A CH_4 gas sensing system using infrared absorption type optic fibre, Journal of JiLin Institute of Technology (Chinese), 1997, 18(2): 57-60
[38] 雷玉堂，王庆有，何加铭．光电检测技术，北京：中国计量出版社，1997
[39] 张志鹏．光纤传感器原理，北京：中国计量出版社，1991
[40] Xie Jianping, Wang Pei, Xu Lixin. Wavelength tuning and stabilizing techniques of
semiconductor lasers, Chinese journal of quantum electronics, 2002, 19(2): 97-103
[41] Stephen D.Walker, Robert A.Nichols, William A.Cuman. Method and apparatus for measuring gas concentration using a semiconductor laser, United States Patent: 6091504, 2000
[42] P.Werle, R.Mucke, F.D'Amato. Near-infrared trace-gas sensors based on room-temperature diode lasers, Appl.Phys.B, 1998, 67:307-315
[43] 黄德修，刘雪峰．半导体激光器及其应用，北京：国防工业出版社，2004
[44] 黄章勇．光纤通信用光电子器件和组件，北京：北京邮电大学出版社，2001
[45] 张培林．半导体激光器在光谱研究中的应用，物理，1993，22(10)：596-601
[46] M.Kroil, J.A.McClintock, O.Ollinger. Measurement of gaseous oxygen using diode laser spectroscopy, Appl.Phys.Lett., 1987, 51 (18): 1465-1467
[47] 张靖，刘少强．检测技术与系统设计，北京：中国电力出版社，2002：383-385
[48] 王仲生．智能检测与控制技术，西安：西北工业大学出版社，2002：226-230
[49] Model 7260 DSP Lock-in Amplifier Instrument Manual, EG&G INSTRUMENTS CORPORATION, 1996
[50] 陆同兴，路轶群．激光光谱技术原理及应用，合肥：中国科学技术大学出版社，1999
[51] A N Dharamsi. A theory of modulation spectroscopy with applications of higher harmonic detection, J.Phys.D:Appl.Phys., 1996, 29:540-549
[52] P.Kluczynski, O.Axner. Theoretical description based upon Fourier analysis of wavelength-modulation spectrometry in terms of analytical and background signals, Appl.Opt., 1999, 38:5803-5815
[53] X.Zhu, D.T.Cassidy. Modulation spectroscopy with a semiconductor diode laser by injection-current modulation, J.Opt.Soc.Am.B, 1997, 14:1945-1950
[54] 张国威，王兆民．激光光谱学原理与技术，北京：北京理工大学出版社，2004
[55] 杨乐平，李海涛等．虚拟仪器技术概论，北京：电子工业出版社，2003
[56] 汪敏生．LabVIEW基础教程，北京：电子工业出版社，2002