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Since H2S is a corrosive and toxic gas pollutant, the accurate measurement of its concentration is significant. However, in the practical industrial processes, it is difficult to implement because of the disturbance caused by other emissions such as CO2 and CO. Therefore, in this work, the concentration of H2S, CO2 and CO are measured simultaneously based on cavity ring-down spectroscopy (CRDS) as a viable alternative to measure the concentration of H2S accurately when CO2 and CO exist. First, the wavelength of mixed gas within a range of 6336–6339 cm–1 is selected as the target region where the spectral line intensity of H2S is stronger than 10 times that of CO2 or CO and the water absorption is extremely weak. Second, the influence of the sampling length (Tm) on the accuracy of the ring-down time is analyzed by evaluating average (accuracy), standard deviation (precision) and consumption time (speed). Third, the experiments are carried out at different pressures in order to obtain the optimal pressure condition. Fourth, the concentration of trace H2S is measured when the disturbances caused by CO2 or CO are added, and the error of the measured concentration is analyzed. Finally, the detection limit of CRDS-based system is calculated to be 6.9 ppb by analyzing the SNR of four groups of low concentration H2S spectra, while the lower limit of detection of CRDS-based system is calculated to be 2 ppb by analyzing the Allan variance of long-term data. The measured concentration and its desired value show a good linearity at different dilution ratios. Both the high linearity and the low detection limit of H2S indicate the effectiveness of the CRDS-based measurement system to measure H2S when CO2 and CO exist. The successful application of the CRDS-based system to the measurement of H2S shows its promising prospect in gas concentration measurement for practical industrial processes.
[1] Glass D C, 1990 Ann. Occup. Hyg. 34 323
[2] Jappinen P, Vilkka V, Marttila O, Haahtela T 1990 Br. J. Ind. Med. 47 824
[3] Duong T X, Suruda A J, Maier L A 2001 Am. J. Ind. Med. 40 221
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[5] 杨建设, 尹爱国, 杨孝军, 钟丽霞 2005 水土保持研究 12 85
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[7] 许伟刚, 谭厚章, 刘原一, 魏博, 惠世恩 2018 中国电力 51 113
Xv W G, Tan H Z, Liu Y Y, Wei B, Hui S H 2018 Electric Power 51 113
[8] 王毅斌, 张思聪, 谭厚章, 林国辉, 王萌, 卢旭超, 杨浩 2021 中国电力 54 118
Wang Y B, Zhang S C, Tan H Z, Lin G H, Wang M, Lu X C, Yang H 2021 Electric Power 54 118
[9] Pandey S K, Kim K 2009 Environ. Sci. Technol. 43 3020
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[10] Kim K 2011 Atmos. Environ. 45 3366
Google Scholar
[11] Khan M A H, Whelan M E, Rhew R C 2012 Talanta 88 581
Google Scholar
[12] Brown M D, Hall J R, Schoenfisch M H 2019 Anal. Chim. Acta 1045 67
Google Scholar
[13] Mathieu O, Mulvihill C, Petersen E L 2017 P. Combust. Inst. 36 4019
Google Scholar
[14] 张杨, 范颖, 王哲, 陈文亮 2017 电子测量与仪器学报 31 1943
Zhang Y, Fan Y, Wang Z, Chen W L 2017 J. Electron. Measurem. Instrum. 31 1943
[15] 何岸, 陈雅茜, 郭敬远, 胡雪蛟, 江海峰 2022 矿业安全与环保 49 113
He A, Chen Y X, Guo J, Hu X J, Jiang H F 2022 Mining Safety Envir. Prot. 49 113
[16] Guo Y, Qiu X, Li N, Feng S, Cheng T, Liu Q, He Q, Kan R, Yang H, Li C 2020 Infrared Phys. Techn. 105 103153
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[17] 王振, 杜艳君, 丁艳军, 吕俊复, 彭志敏 2022 物理学报 71 184205
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Peng Z, He S L, Zhou P L, Wang Z, Du Y J, Ding Y J, Wu Y X, Lv J F 2022 Thermal Powergen. 51 145
[19] Keefe O A, Deacon D A G 1988 Rev. Sci. Instrum. 59 2544
Google Scholar
[20] Berden G, Engeln R 2009 Cavity Ring-Down Spectroscopy: Techniques and Applications (Wiltshire: Wiley-Blackwell) pp7–10
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Google Scholar
[22] Ball S M, Jones R L 2003 Chem. Rev. 103 5239
Google Scholar
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Wang Z, Du Y J, Ding Y J, Li Z, Peng Z M 2022 Acta Phys. Sin. 71 044205
Google Scholar
[24] Maity A, Pal M, Banik G D, Maithani S, Pradhan M 2017 Laser Phys. Lett. 14 115701
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Google Scholar
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Google Scholar
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Google Scholar
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图 1 腔衰荡光谱基本原理
Figure 1. Basic schematic of cavity ring-down spectroscopy.
图 2 腔衰荡光谱测量系统(PC: 计算机, LC: 激光器控制器, DFB: 激光器, ISO: 光纤隔离器, AOM: 声光调制器, RDC: 衰荡腔, PZT: 压电陶瓷, APD: 雪崩式光电探测器, PG: 脉冲信号发生器, RF: 射频发生器, DAQ: 数据采集系统, RD: 衰荡信号, Trig: 触发信号)
Figure 2. Cavity ring-down spectroscopy measurement system (PC: personal computer, LC: laser controller, DFB: DFB laser, ISO: fiber isolator, AOM: acousto-optic modulator, RDC: ring-down cavity, PZT: piezoceramics, APD: avalanche photodiode, PG: pulse generator, RF: radio frequency generator, DAQ: digital acquisition, RD: ring-down signal, Trig: trigger)
图 3 不同衰荡信号采样长度
Figure 3. Different sampling length of ring-down signal.
图 4 不同采样长度下, 衰荡时间提取效果
Figure 4. The result of ring-down time extraction in different sampling length.
图 5 待测区域谱线展示与不同压力测量结果
Figure 5. Display of spectral lines in measured region and the measured spectra in different pressures.
图 6 仅改变H2S浓度测量结果
Figure 6. the spectra in only H2S concentration changed.
图 7 变物质浓度测量光谱与线性度分析
Figure 7. The spectra of changing concentration and analysis of linearity.
图 8 低浓度H2S测量结果
Figure 8. The spectra of H2S in low concentration.
图 9 吸收系数Allan方差
Figure 9. Allan variance of absorption coefficient.
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[1] Glass D C, 1990 Ann. Occup. Hyg. 34 323
[2] Jappinen P, Vilkka V, Marttila O, Haahtela T 1990 Br. J. Ind. Med. 47 824
[3] Duong T X, Suruda A J, Maier L A 2001 Am. J. Ind. Med. 40 221
Google Scholar
[4] Steinsmo. U, Rogne. T, Drugli. J 1997 Corrosion 53 955
Google Scholar
[5] 杨建设, 尹爱国, 杨孝军, 钟丽霞 2005 水土保持研究 12 85
Google Scholar
Yang J S, Yin A G, Yang X J, Zhong L X 2005 Res. Soil. Water. Conserv. 12 85
Google Scholar
[6] Wang Y, Wang B, He S, Zhang L, Xing X, Li H, Lu M 2022 J. Nat. Gas Sci. Eng. 100 104477
Google Scholar
[7] 许伟刚, 谭厚章, 刘原一, 魏博, 惠世恩 2018 中国电力 51 113
Xv W G, Tan H Z, Liu Y Y, Wei B, Hui S H 2018 Electric Power 51 113
[8] 王毅斌, 张思聪, 谭厚章, 林国辉, 王萌, 卢旭超, 杨浩 2021 中国电力 54 118
Wang Y B, Zhang S C, Tan H Z, Lin G H, Wang M, Lu X C, Yang H 2021 Electric Power 54 118
[9] Pandey S K, Kim K 2009 Environ. Sci. Technol. 43 3020
Google Scholar
[10] Kim K 2011 Atmos. Environ. 45 3366
Google Scholar
[11] Khan M A H, Whelan M E, Rhew R C 2012 Talanta 88 581
Google Scholar
[12] Brown M D, Hall J R, Schoenfisch M H 2019 Anal. Chim. Acta 1045 67
Google Scholar
[13] Mathieu O, Mulvihill C, Petersen E L 2017 P. Combust. Inst. 36 4019
Google Scholar
[14] 张杨, 范颖, 王哲, 陈文亮 2017 电子测量与仪器学报 31 1943
Zhang Y, Fan Y, Wang Z, Chen W L 2017 J. Electron. Measurem. Instrum. 31 1943
[15] 何岸, 陈雅茜, 郭敬远, 胡雪蛟, 江海峰 2022 矿业安全与环保 49 113
He A, Chen Y X, Guo J, Hu X J, Jiang H F 2022 Mining Safety Envir. Prot. 49 113
[16] Guo Y, Qiu X, Li N, Feng S, Cheng T, Liu Q, He Q, Kan R, Yang H, Li C 2020 Infrared Phys. Techn. 105 103153
Google Scholar
[17] 王振, 杜艳君, 丁艳军, 吕俊复, 彭志敏 2022 物理学报 71 184205
Google Scholar
Wang Z, Du Y J, Ding Y J, Lu J F, Peng Z M 2022 Acta Phys. Sin. 71 184205
Google Scholar
[18] 彭志敏, 贺拴玲, 周佩丽, 杜艳君, 王振, 丁艳军, 吴玉新, 吕俊复 2022 热力发电 51 145
Peng Z, He S L, Zhou P L, Wang Z, Du Y J, Ding Y J, Wu Y X, Lv J F 2022 Thermal Powergen. 51 145
[19] Keefe O A, Deacon D A G 1988 Rev. Sci. Instrum. 59 2544
Google Scholar
[20] Berden G, Engeln R 2009 Cavity Ring-Down Spectroscopy: Techniques and Applications (Wiltshire: Wiley-Blackwell) pp7–10
[21] Maity A, Maithani S, Pradhan M 2021 Anal. Chem. 93 388
Google Scholar
[22] Ball S M, Jones R L 2003 Chem. Rev. 103 5239
Google Scholar
[23] 王振, 杜艳君, 丁艳军, 李政, 彭志敏 2022 物理学报 71 044205
Google Scholar
Wang Z, Du Y J, Ding Y J, Li Z, Peng Z M 2022 Acta Phys. Sin. 71 044205
Google Scholar
[24] Maity A, Pal M, Banik G D, Maithani S, Pradhan M 2017 Laser Phys. Lett. 14 115701
Google Scholar
[25] Pandaa B, Maithania S, Pradhana M 2020 Chem. Phys. 535 110769
[26] Matheson I B C 1987 Instrum. Sci. Technol. 16 345
Google Scholar
[27] Halmer D, von Basum G, Hering P, Mürtz M 2004 Rev. Sci. Instrum. 75 2187
Google Scholar
[28] Galatry L 1961 Phys. Rev. 122 1218
Google Scholar
[29] Dicke R H 1953 Phy. Rev. 89 472
Google Scholar
[30] Boone C D, Walker K A, Bernath P F 2007 J. Quant. Spectrosc. Ra. 105 525
Google Scholar
[31] Lan L J, Ding Y J, Peng Z M, Du Y J, Liu Y F, Li Z 2014 Appl. Phys. B 117 543
Google Scholar
[32] Gordon I E, Rothman L S, Hargreaves R J, Hashemi R, Karlovets E V, Skinner F M, Conway E K, Hill C, Kochanov R V, Tan Y, Wcisło P, Finenko A A, Nelson K, Bernath P F, Birk M, Boudon V, Campargue A, Chance K V, Coustenis A, Drouin B J, Flaud J M, Gamache R R, Hodges J T, Jacquemart D, Mlawer E J, Nikitin A V, Perevalov V I, Rotger M, Tennyson J, Toon G C, Tran H, Tyuterev V G, Adkins E M, Baker A, Barbe A, Canè E, Császár A G, Dudaryonok A, Egorov O, Fleisher A J, Fleurbaey H, Foltynowicz A, Furtenbacher T, Harrison J J, Hartmann J M, Horneman V M, Huang X, Karman T, Karns J, Kassi S, Kleiner I, Kofman V, Kwabia Tchana F, Lavrentieva N N, Lee T J, Long D A, Lukashevskaya A A, Lyulin O M, Makhnev V Y, Matt W, Massie S T, Melosso M, Mikhailenko S N, Mondelain D, Müller H S P, Naumenko O V, Perrin A, Polyansky O L, Raddaoui E, Raston P L, Reed Z D, Rey M, Richard C, Tóbiás R, Sadiek I, Schwenke D W, Starikova E, Sung K, Tamassia F, Tashkun S A, Vander Auwera J, Vasilenko I A, Vigasin A A, Villanueva G L, Vispoel B, Wagner G, Yachmenev A, Yurchenko S N 2022 J. Quant. Spectrosc. Ra. 277 107949
Google Scholar
[33] Allan D W 1966 P. IEEE 54 221
Google Scholar
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