紫外荧光SO_2分析仪关键技术研究
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摘要
各种污染气体的排放导致大气环境质量下降。二氧化硫是其中第一大污染物,也是酸雨的根源,影响到人们的身体健康和工农业的生产。要通过有效的手段控制环境污染,其浓度监测是必须的。在各大、中城市建立一个合理的、及时反应大气环境质量的监测网络是防治大气污染的保证。
而我国现在使用的大气质量监测仪器依靠国外进口,价格昂贵,维护不便,严重制约了我国大气污染防治工作的进行。为此,在广州市环保局支持下,以华南师范大学物理与电信工程学院杨冠玲教授为首的课题组开展“大气自动监测系统国产化样机的研制”项目的研究,“大气二氧化硫浓度分析仪样机研制”是该项目的一部分。
论文是在课题组的其它同志的工作基础上继续进行的,在他们的努力下,已完成基本理论研究和仪器样机的组建,取得大量真实可靠的实验数据。
在此基础上,本论文进一步分析、比较各种测量二氧化硫浓度的理论和方法,分析了仪器各个组成部分的设计,并进行了研究性实验,不断探索研究分析仪的运行参数,取得监测大气二氧化硫浓度的各项性能指标。分析仪是基于二氧化硫紫外荧光检测理论,采用了虚拟仪器和光子计数技术,本文重点在于分析仪的几个关键性技术研究:
1、研究了紫外荧光的理论和基于此理论的大气二氧化硫浓度的监测机理,推导出激发荧光与二氧化硫浓度及激发光强度的关系式,荧光强度与二者成正比。式中,l、c分别为样品池的长度和样品的浓度,ε为单位长度和单位浓度介质的吸收系数,εlc是个无单位的数。将Lambert—Beer定律按级数展开,只有在εlc的值很小的情况下才能导出上式。
2、将仪器样机智能化、系统化,开发出完全脱离虚拟仪器平台的、独立的仪器测控系统。进一步降低仪器本底,仪器面板的设计,光信
The atmosphere is very much polluted by various gases, among which sulfur dioxide is the most outrageous. It is known to all that sulfur dioxide produces acid rain of negative influence upon people's health, industry and agriculture. To put environmental pollution under control requires a constant keenness to concentration of sulfur dioxide in the atmosphere. Appropriate detection systems, that inform researchers of atmosphere quality in time, are supposed to established up in big cities. This is proved to be an effective way for the very purpose.Today, expensive as well as hard to maintain, instruments for detecting atmosphere quality are imported, which strains the proceeding of our research in this field. Prof. Yang Guanling, from Physic and telecom engineering school, South China Normal University, lead the project group to develop a project named "Domestic Research and Production of Atmosphere Auto-monitoring System". "Concentration Detection System of Sulfur Dioxide in the Atmosphere", is a part of the project. And Guang zhou Bureau of Environmental Protection supports the item.The thesis is based on other members' achievements in basic theories as well as fabrication of sample instruments for its smooth composition. A lot of helpful data really help a lot in the present work.Based on all work done by our members, the thesis makes a contrastive analysis of various principles and methods employed in detecting concentration of sulfur dioxide. Based on that ultra-violet fluorescence, theoretically, is able to function effectively in the detection, the invention of the monitoring instrument adopts virtual instruments and optic counting. The designing of all parts of the monitoring instrument is analyzed; running parameters are constantly in our mastery; all performance indexes of the instrument employed in the detection get ready for our research. The thesis emphasizes the key technologies. 1, In this paper, special attention is given to the theory of ultra-violet
fluorescence and the detection of sulfur dioxide concentration in the atmosphere led by the former. The following formula is induced:Based on Lambert—Beer Law, the value of sic is small.2, Perfect the intelligent sample instrument and develop instrumental detection system that can run properly without the involvement of any virtual instrumental platform. The last system includes: the proposition of the best absorption spectrum; the designing of exciting light source; the further lowering of instrumental background counts; the designing of plate; the self detection of signals; the refrigeration of counting system and the display of temperature. Owning to the last list, the user can enjoy simple operation platform and the interaction between man and machine. As a part of the detection system of atmosphere quality, it takes into consideration systematization and the choice of instrumental network interface.3, The thesis completes the designing as well as debugging of software and hardware concerning light, machines, electricity and computation, figures out instrumental operation parameters.4, Acquire a lot of function parameter based on the instrument:(1) When the room temperature is 22°C ,the temperature of photon counter lowers to 5°C after 25 minutes.(2) The dark counter and background counter are stability. At the same time, the concentration of sample gas is constant, The response value is also bigger when the flow increases.(3) The concentration of sulfur dioxide is linear to photon counter when the counter gate is 1 second, the response value is 0.24counts/ppb · s. When the gate is 2s and 5s, the values increase to 0.51counts/ppb · s and 1.31counts/ppb · s.
而我国现在使用的大气质量监测仪器依靠国外进口,价格昂贵,维护不便,严重制约了我国大气污染防治工作的进行。为此,在广州市环保局支持下,以华南师范大学物理与电信工程学院杨冠玲教授为首的课题组开展“大气自动监测系统国产化样机的研制”项目的研究,“大气二氧化硫浓度分析仪样机研制”是该项目的一部分。
论文是在课题组的其它同志的工作基础上继续进行的,在他们的努力下,已完成基本理论研究和仪器样机的组建,取得大量真实可靠的实验数据。
在此基础上,本论文进一步分析、比较各种测量二氧化硫浓度的理论和方法,分析了仪器各个组成部分的设计,并进行了研究性实验,不断探索研究分析仪的运行参数,取得监测大气二氧化硫浓度的各项性能指标。分析仪是基于二氧化硫紫外荧光检测理论,采用了虚拟仪器和光子计数技术,本文重点在于分析仪的几个关键性技术研究:
1、研究了紫外荧光的理论和基于此理论的大气二氧化硫浓度的监测机理,推导出激发荧光与二氧化硫浓度及激发光强度的关系式,荧光强度与二者成正比。式中,l、c分别为样品池的长度和样品的浓度,ε为单位长度和单位浓度介质的吸收系数,εlc是个无单位的数。将Lambert—Beer定律按级数展开,只有在εlc的值很小的情况下才能导出上式。
2、将仪器样机智能化、系统化,开发出完全脱离虚拟仪器平台的、独立的仪器测控系统。进一步降低仪器本底,仪器面板的设计,光信
The atmosphere is very much polluted by various gases, among which sulfur dioxide is the most outrageous. It is known to all that sulfur dioxide produces acid rain of negative influence upon people's health, industry and agriculture. To put environmental pollution under control requires a constant keenness to concentration of sulfur dioxide in the atmosphere. Appropriate detection systems, that inform researchers of atmosphere quality in time, are supposed to established up in big cities. This is proved to be an effective way for the very purpose.Today, expensive as well as hard to maintain, instruments for detecting atmosphere quality are imported, which strains the proceeding of our research in this field. Prof. Yang Guanling, from Physic and telecom engineering school, South China Normal University, lead the project group to develop a project named "Domestic Research and Production of Atmosphere Auto-monitoring System". "Concentration Detection System of Sulfur Dioxide in the Atmosphere", is a part of the project. And Guang zhou Bureau of Environmental Protection supports the item.The thesis is based on other members' achievements in basic theories as well as fabrication of sample instruments for its smooth composition. A lot of helpful data really help a lot in the present work.Based on all work done by our members, the thesis makes a contrastive analysis of various principles and methods employed in detecting concentration of sulfur dioxide. Based on that ultra-violet fluorescence, theoretically, is able to function effectively in the detection, the invention of the monitoring instrument adopts virtual instruments and optic counting. The designing of all parts of the monitoring instrument is analyzed; running parameters are constantly in our mastery; all performance indexes of the instrument employed in the detection get ready for our research. The thesis emphasizes the key technologies. 1, In this paper, special attention is given to the theory of ultra-violet
fluorescence and the detection of sulfur dioxide concentration in the atmosphere led by the former. The following formula is induced:Based on Lambert—Beer Law, the value of sic is small.2, Perfect the intelligent sample instrument and develop instrumental detection system that can run properly without the involvement of any virtual instrumental platform. The last system includes: the proposition of the best absorption spectrum; the designing of exciting light source; the further lowering of instrumental background counts; the designing of plate; the self detection of signals; the refrigeration of counting system and the display of temperature. Owning to the last list, the user can enjoy simple operation platform and the interaction between man and machine. As a part of the detection system of atmosphere quality, it takes into consideration systematization and the choice of instrumental network interface.3, The thesis completes the designing as well as debugging of software and hardware concerning light, machines, electricity and computation, figures out instrumental operation parameters.4, Acquire a lot of function parameter based on the instrument:(1) When the room temperature is 22°C ,the temperature of photon counter lowers to 5°C after 25 minutes.(2) The dark counter and background counter are stability. At the same time, the concentration of sample gas is constant, The response value is also bigger when the flow increases.(3) The concentration of sulfur dioxide is linear to photon counter when the counter gate is 1 second, the response value is 0.24counts/ppb · s. When the gate is 2s and 5s, the values increase to 0.51counts/ppb · s and 1.31counts/ppb · s.
引文
[1] 冯玲,杨景玲,蔡树中。烟气脱硫技术的发展及应用状况。环境工程,1997,15(2)19-24。
[2] 徐明,烟气二氧化硫污染控制技术发展及现状,安徽师范大学学报自然科学版,2001,24(2):187-189
[3] 彭定一,林少宁编著。《大气污染及其控制》。北京,中国环境科学出版社,1991,298-300
[4] 吴风武,何治柯等,二氧化硫分析研究进展,分析科学学报,2000,16(3)248-250
[5] West P W, Gaeke G C. Anel chem., 1956;(28)12:1816
[6] 陈玲 赵建夫等,环境监测,北京:化学工业出版社,2004,177
[7] 张文德。二氧化硫光度分析的研究进展,理化检验—化学分册1997 (33)39-41
[8] Ibrahm I, Cemal Y AND Humeyra B, Analyst, 1996, 121:1873
[9] Ekkad N and Huber C O, Anal. Chem. Acta, 1996, 332:155
[10] Xu Y J, Lu C Y, Chen K, Nie L H, Yao S Z, Talanta, 1996, 43(8):1297
[11] Yang J H, Yang P H, Meng G Y, Sens. Actuators, 1996, 31B(3):209
[12] Chiou C. Y., and Chou T-C, Electronalysis, 1996, 8:1179
[13] Wei H M, Wang L S Xing W L, Zhnag B G, Liu C J, Feng J X, Anal. Chem., 1997, 69(4):699
[14] 张荣坤,周晓宾.罗颖华,化学传感器,1994,14(3):195.
[15] 鲜跃仲,薛建等,高等学校化学学报,2000,21(9):1375-1376
[16] 许汉英 王柯敏等 高灵敏度二氧化硫光纤传感器的研究,高等学校化学学报 1998,(19)1401-1404
[17] 齐怀琴,李春林,王仲杰,红外传感器在二氧化硫监测中的应用,齐齐哈尔大学学学报,2002,18(2):89-91
[18] 黄维,我国SO_2总量控制监测技术的进展,甘肃环境研究与监测1999(3)167-168;
[19] 龙绮云,离子色谱法测定大气中二氧化硫方法的探讨,铁道劳动安全卫生与环保,2001,28(2):128-130
[20] W L Crider, Anal. Chem.,1965,37:1770-1773
[21] 王雄,蒋坚毅,胡汉祥。Procal插入式红外气体自动分析仪,环境工程,1996,14(4):55-56
[22] Robert F. Adamowicz and Kee P. Koo, Applied Optics, 1979, 18(17): 2938
[23] P. Vujkovie Cvijin, D.A. Gilmore, M.A. Leugers, and G.H.Atkinson, Anal. Chem., 1987, 59:300-304
[24] 饶明辉,大气二氧化硫浓度紫外荧光分析仪的研制及优化,华南师范大学硕士研究生学位论文,2004
[25] JULES DUCHESNE and B. ROSEN, Journal of Chemical physics, 1947, 15(9):631-644
[26] H Okade, the Journal of the American Chemical Society, 1971, 93:7095-7097
[27] Hideo Okabe, Paul L Splitstone, and Joseph J Ball, Journal of The Air Pollution Control Association, 1973, 23:514-516
[28] 张需芳,吴佛运等,用晶体作传感器的二氧化硫测试仪,仪器仪表学报,1995,16(1),32
[29] 陈九江,张心等,二氧化硫浓度的双光路紫外吸收测量法,电测与仪表,2000,26(5):462
[30] 王式民,徐益谦,测量NO和SO_2浓度的荧光光学分析仪,燃烧科学与技术,1997,3(3):253
[31] 杨初平,ppb级大气二氧化硫紫外荧光检测理论与实现技术研究,华南师范大学博士研究生学位论文,2002,8
[32] 方惠群,于俊生,史坚著,仪器分析,科学出版社,2001.2,309-311
[33] 方禹之主编,仪器分析,华东师范大学出版社,1990:235
[34] 夏锦尧编著,实用荧光分析法,中国人民公安大学出版社,1991:11
[35] G.W.尤因著,华东化工学院分析化学教研组译,《化学分析的仪器方法》,北京,高等教育出版社,1986,292-293
[36] D. Golomb, K. Watanabe, and F.F. Marmo, Journal of Chemical Physics, 1962, 36(4):958-960
[37] S.S Colier, Akira Morikawa, D H Slater, J G Calvert, G Reinhardt, and E Damon, the Journal of the Americn Chemical Society, 197092: 217-218
[38] K F Green, and A B F Dancan, J Amer, Chem. Soc, 1962, 83: 555
[39] H. Okade, Paul L. Splitstone, Joseph J. Ambient and source SO_2 Detector Based on a Fluorescence Method, Journal of the air pollution control association, 1973, 23 (6): 514
[40] P. Warneck, F.F.Marmo, and J.O. Sullivan, Journal of Chemical physics 1964, 40(4): 1132-1136
[41] FrederickPSchwarz, HideoOkabe, and JulianK. Whittakr, Anal. chem.,1974, 46:1024-1028
[42] 钟旭滨编著,光电探测技术,华南理工大学出版社,1994:228
[43] 郭永康等,光学教程,四川大学出版社,2001:374
[44] 刘振玉,光电技术,北京理工大学出版社,1990:98
[45] 罗先和 张广军,骆飞,宋育东,光电检测技术,北京航空航天大学出版社,1995,95
[46] 马正先 UV荧光法测量SO_2浓度研究,华南师范大学研究生学位论文,1997:15-16
[47] 张伟平,李沸,杨轶颖,论大气监测系统SO_2零点漂移的控制,辽宁城乡环境科技,17(2):66-67
[48] 江东林等,高选择性透过二氧化硫气体分离膜的研究,高等学校化学学报,1994,15(1):150
[2] 徐明,烟气二氧化硫污染控制技术发展及现状,安徽师范大学学报自然科学版,2001,24(2):187-189
[3] 彭定一,林少宁编著。《大气污染及其控制》。北京,中国环境科学出版社,1991,298-300
[4] 吴风武,何治柯等,二氧化硫分析研究进展,分析科学学报,2000,16(3)248-250
[5] West P W, Gaeke G C. Anel chem., 1956;(28)12:1816
[6] 陈玲 赵建夫等,环境监测,北京:化学工业出版社,2004,177
[7] 张文德。二氧化硫光度分析的研究进展,理化检验—化学分册1997 (33)39-41
[8] Ibrahm I, Cemal Y AND Humeyra B, Analyst, 1996, 121:1873
[9] Ekkad N and Huber C O, Anal. Chem. Acta, 1996, 332:155
[10] Xu Y J, Lu C Y, Chen K, Nie L H, Yao S Z, Talanta, 1996, 43(8):1297
[11] Yang J H, Yang P H, Meng G Y, Sens. Actuators, 1996, 31B(3):209
[12] Chiou C. Y., and Chou T-C, Electronalysis, 1996, 8:1179
[13] Wei H M, Wang L S Xing W L, Zhnag B G, Liu C J, Feng J X, Anal. Chem., 1997, 69(4):699
[14] 张荣坤,周晓宾.罗颖华,化学传感器,1994,14(3):195.
[15] 鲜跃仲,薛建等,高等学校化学学报,2000,21(9):1375-1376
[16] 许汉英 王柯敏等 高灵敏度二氧化硫光纤传感器的研究,高等学校化学学报 1998,(19)1401-1404
[17] 齐怀琴,李春林,王仲杰,红外传感器在二氧化硫监测中的应用,齐齐哈尔大学学学报,2002,18(2):89-91
[18] 黄维,我国SO_2总量控制监测技术的进展,甘肃环境研究与监测1999(3)167-168;
[19] 龙绮云,离子色谱法测定大气中二氧化硫方法的探讨,铁道劳动安全卫生与环保,2001,28(2):128-130
[20] W L Crider, Anal. Chem.,1965,37:1770-1773
[21] 王雄,蒋坚毅,胡汉祥。Procal插入式红外气体自动分析仪,环境工程,1996,14(4):55-56
[22] Robert F. Adamowicz and Kee P. Koo, Applied Optics, 1979, 18(17): 2938
[23] P. Vujkovie Cvijin, D.A. Gilmore, M.A. Leugers, and G.H.Atkinson, Anal. Chem., 1987, 59:300-304
[24] 饶明辉,大气二氧化硫浓度紫外荧光分析仪的研制及优化,华南师范大学硕士研究生学位论文,2004
[25] JULES DUCHESNE and B. ROSEN, Journal of Chemical physics, 1947, 15(9):631-644
[26] H Okade, the Journal of the American Chemical Society, 1971, 93:7095-7097
[27] Hideo Okabe, Paul L Splitstone, and Joseph J Ball, Journal of The Air Pollution Control Association, 1973, 23:514-516
[28] 张需芳,吴佛运等,用晶体作传感器的二氧化硫测试仪,仪器仪表学报,1995,16(1),32
[29] 陈九江,张心等,二氧化硫浓度的双光路紫外吸收测量法,电测与仪表,2000,26(5):462
[30] 王式民,徐益谦,测量NO和SO_2浓度的荧光光学分析仪,燃烧科学与技术,1997,3(3):253
[31] 杨初平,ppb级大气二氧化硫紫外荧光检测理论与实现技术研究,华南师范大学博士研究生学位论文,2002,8
[32] 方惠群,于俊生,史坚著,仪器分析,科学出版社,2001.2,309-311
[33] 方禹之主编,仪器分析,华东师范大学出版社,1990:235
[34] 夏锦尧编著,实用荧光分析法,中国人民公安大学出版社,1991:11
[35] G.W.尤因著,华东化工学院分析化学教研组译,《化学分析的仪器方法》,北京,高等教育出版社,1986,292-293
[36] D. Golomb, K. Watanabe, and F.F. Marmo, Journal of Chemical Physics, 1962, 36(4):958-960
[37] S.S Colier, Akira Morikawa, D H Slater, J G Calvert, G Reinhardt, and E Damon, the Journal of the Americn Chemical Society, 197092: 217-218
[38] K F Green, and A B F Dancan, J Amer, Chem. Soc, 1962, 83: 555
[39] H. Okade, Paul L. Splitstone, Joseph J. Ambient and source SO_2 Detector Based on a Fluorescence Method, Journal of the air pollution control association, 1973, 23 (6): 514
[40] P. Warneck, F.F.Marmo, and J.O. Sullivan, Journal of Chemical physics 1964, 40(4): 1132-1136
[41] FrederickPSchwarz, HideoOkabe, and JulianK. Whittakr, Anal. chem.,1974, 46:1024-1028
[42] 钟旭滨编著,光电探测技术,华南理工大学出版社,1994:228
[43] 郭永康等,光学教程,四川大学出版社,2001:374
[44] 刘振玉,光电技术,北京理工大学出版社,1990:98
[45] 罗先和 张广军,骆飞,宋育东,光电检测技术,北京航空航天大学出版社,1995,95
[46] 马正先 UV荧光法测量SO_2浓度研究,华南师范大学研究生学位论文,1997:15-16
[47] 张伟平,李沸,杨轶颖,论大气监测系统SO_2零点漂移的控制,辽宁城乡环境科技,17(2):66-67
[48] 江东林等,高选择性透过二氧化硫气体分离膜的研究,高等学校化学学报,1994,15(1):150