基于光声光谱的乙烯探测技术
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摘要
乙烯(C2H4)是石油化工产业中的基本化工原料,具有爆炸性,也常被作为煤层自燃的标识性气体。为实现对低浓度乙烯的检测,搭建了基于近红外可调谐二极管激光器的低成本光声光谱测量系统。通过对乙烯近红外波段吸收谱线的分析,选择了乙烯位于1620.44nm处的吸收谱线作为测量对象,并结合波长调制吸收技术,使用光声池的共振频率作为激光器的调制频率,利用吸收谱线的二次谐波信号实现了对乙烯浓度的反演。实验结果表明系统对于乙烯的测量准确度为0.688%,探测极限达到了1.16×10-5,对同一样品在30min之内的连续测量验证了系统良好的稳定性,所有实验结果均显示了该套系统在乙烯痕量探测方面的应用价值。
Ethylene(C2H4)is a common chemical material in the petroleum and chemical industry.It is explosive and often used as identifier for coal spontaneous combustion.An inexpensive photoacoustic spectrometry based on near infrared tunable diode laser is developed to detect the ethylene with low concentration.By analyzing the nearinfrared absorption line of ethylene,we choose absorption line of ethylene at 1620.44 nm as measuring object.By combining wavelength modulation absorption technique,resonant frequency of photoacoustic cell is used as modulation frequency,and the second harmonic signal of absorption line is used to realize inversion of ethylene gas concentration.The results show that the measurement accuracy of ethylene by the system is 0.688%.The detection limit of the system is up to be about 1.16×10~(-5).A continuous measurement for a gas sample in half an hour shows the stability of the system.All the results represent the application value of the system for trace detection of ethylene.
Ethylene(C2H4)is a common chemical material in the petroleum and chemical industry.It is explosive and often used as identifier for coal spontaneous combustion.An inexpensive photoacoustic spectrometry based on near infrared tunable diode laser is developed to detect the ethylene with low concentration.By analyzing the nearinfrared absorption line of ethylene,we choose absorption line of ethylene at 1620.44 nm as measuring object.By combining wavelength modulation absorption technique,resonant frequency of photoacoustic cell is used as modulation frequency,and the second harmonic signal of absorption line is used to realize inversion of ethylene gas concentration.The results show that the measurement accuracy of ethylene by the system is 0.688%.The detection limit of the system is up to be about 1.16×10~(-5).A continuous measurement for a gas sample in half an hour shows the stability of the system.All the results represent the application value of the system for trace detection of ethylene.
引文
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[2]Persson L,Gao H,Sj9holm M,et al.Diode laser absorption spectroscopy for studies of gas exchange in fruits[J].Opt Laser Eng,2006,44(7):687-698.
[3]Bell A J.Upon the production and reproduction of sound by light[J].Journal of the Society of Telegraph Engineers,2010,9(34):404-426.
[4]Kerr E L,Atwood J G.The laser illuminated absorptivity spectrophone:A method for measurement of weak absoptivity in gases at laser wavelengths[J].Appl Optics,1968,7(5):915-921.
[5]Kreuzer L B,Kenyon N D,Patel C K.Air pollution:Sensitive detection of ten pollutant gases by carbon monoxide and carbon dioxide lasers[J].Science,1972,177(4046):347-349.
[6]Meyer P L,Sigrist M W.Atmospheric pollution monitoring using CO2-laser photoacoustic spectroscopy and other techniques[J].Rev Sci Instrum,1990,61(7):1779-1807.
[7]Narasimhan L R,Goodman W,Patel C K N.Correlation of breath ammonia with blood urea nitrogen and creatinine during hemodialysis[C].Proc Natl Acad Sci U S A,2001,98(8):4617-4621.
[8]Gyawali M,Arnott W P,Zaveri R A,et al.Photoacoustic optical properties at UV,VIS,and near IR wavelengths for laboratory generated and winter time ambient urban aerosols[J].Atmos Chem Phys,2012,12(5):2587-2601.
[9]Webber M E,MacDonald T,Pushkarsky M B,et al.Agricultural ammonia sensor using diode lasers and photoacoustic spectroscopy[J].Meas Sci Technol,2005,16(8):1547-1553.
[10]Bakhirkin Y A,Kosterev A A,Curl R F,et al.Sub-ppbv nitric oxide concentration measurements using cw thermoelectrically cooled quantum cascade laser-based integrated cavity output spectroscopy[J].Appl Phy B-Lasers O,2006,82(1):149-154.
[11]Besson J P,Schilt S,Sauser F,et al.Multi-hydrogenated compounds monitoring in optical fibre manufacturing process by photoacoustic spectroscopy[J].Appl Phys B-Lasers O,2006,85(2):343-348.
[12]Slowik J G,Cross E S,Han J H,et al.An inter-comparison of instruments measuring black carbon content of soot particles[J].Aerosol Sci Tech,2007,41(3):295-314.
[13]Curl R F,Tittel F K.Tunable infrared laser spectroscopy[J].Annu Rep Prog Chem,Sect C,2002,98(4050):219-272.
[14]Li J S,Gao X M,Fang L,et al.Resonant photoacoustic detection of trace gas with DFB diode laser[J].Opt Laser Technol,2007,39(6):1144-1149.
[15]Wu H P,Dong L,Zheng H D,et al.Enhanced near-infrared QEPAS sensor for sub-ppm level H2S detection by means of a fiber amplified 1582nm DFB laser[J].Sensor Actuat B-Chem,2015,221:666-672.
[16]Hu Libin,Liu Kun,Wang Guishi,et al.Research on detecting CO with quartz enhanced photoacoustic spectroscopy based on 2.33μm distributed feed back laser[J].Laser&Optoelectronics Progress,2015,52(5):053002.胡立兵,刘锟,王贵师,等.基于2.33μm可调谐激光的石英音叉增强型光声光谱测量CO研究[J].激光与光电子学进展,2015,52(5):053002.
[17]Yao Lu,Liu Wenqin,Liu Jianguo,et al.Research on open-path detection for atmospheric trace gas CO based on TDLAS[J].Chinese J Lasers,2015,42(2):0215003.姚路,刘文清,刘建国,等.基于TDLAS的长光程环境大气痕量CO监测方法研究[J].中国激光,2015,42(2):0215003.
[18]Gao Guangzhen,Cai Tingdong.Multi-mode absorption spectroscopy for carbon monoxide detection using diode laser near 1570nm[J].Acta Optica Sinica,2016,36(5):0530002.高光珍,蔡廷栋.1570nm附近多模二极管激光吸收光谱CO浓度测量[J].光学学报,2016,36(5):0530002.
[19]Schmid T.Photoacoustic spectroscopy for process analysis[J].Anal Bioanal Chem,2006,384(5):1071-1086.
[20]Sigrist M W.Trace gas monitoring by laser-photoacoustic spectroscopy[J].Infrared Phys Techn,1995,36(1):415-425.
[21]Kapitanov V,Ponomarev Y N.High resolution ethylene absorption spectrum between 6035and 6210cm-1[J].Appl Phys B-Lasers O,2008,90(2):235-241.