氨气高精度光谱检测装置的设计及实现 -

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氨气高精度光谱检测装置的设计及实现

doi:10.37188/CO.2023-0023

杨天悦^1,,
宫廷^1,,
郭古青^1,,
孙小聪^1,,
田亚莉^1,,
邱选兵^1,,
何秋生^2,,
高晓明^3,,
李传亮^1,,

1.
太原科技大学山西省精密测量与在线检测装备工程研究中心, 山西太原 030024
2.
太原科技大学环境与安全学院, 山西太原 030024
3.
中国科学院安徽光学精密机械研究所环, 安徽合肥 230031

基金项目:国家自然科学基金（No. U1810129，No. 52076145，No. 12304403）；山西省留学人员科技活动项目（No. 20230031）；山西省省筹资金资助回国留学人员科研资助项目（No. 2023-151）；山西省基础研究计划（No. 202203021222204）；太原科技大学科研启动基金（No. 20222008，No. 20222132）；山西省科技成果转化引导专项项目（No. 201904D131025）

详细信息

作者简介:
杨天悦（1997—），男，天津人，硕士研究生，2020年于太原科技大学获得学士学位，主要从事光谱学及应用等方面的研究。E-mail：1330944702@qq.com
宫　廷（1992—），女，山西忻州人，博士，讲师，硕士生导师，主要从事光谱学及应用等方面的研究。E-mail：gongting@tyust.edu.cn
郭古青（1986—），男，山西阳泉人，博士，副教授，硕士生导师，主要从事新型材料表征方法的研究。E-mail：2016035@tyust.edu.cn
孙小聪（1996—），女，山西运城人，博士，讲师，主要从事量子光学等方面的研究。E-mail：sunxiaocong@tyust.edu.cn
田亚莉（1991—），女，山西吕梁人，博士，讲师，主要从事原子与分子物理方面的研究。E-mail：tianyali@tyust.edu.cn
邱选兵（1980—），男，四川内江人，博士，教授，博士生导师，主要从事光谱技术、嵌入式系统的研究。E-mail：qiuxb@tyust.edu.cn
何秋生（1977—），男，山西介休人，博士，教授，博士生导师，主要从事有机污染物相关的大气环境、大气化学和污染修复研究。E-mail：heqs@tyust.edu.cn
高晓明（1965—），男，安徽南陵人，博士，研究员，博士生导师，主要从事高灵敏度光谱检测技术及应用的研究。E-mail：xmgao@aiofm.ac.cn
李传亮（1983—），男，山东沂源人，博士，教授，博士生导师，2011年于华东师范大学获得博士学位，主要从事光谱学及应用、光电传感装备的研究。E-mail：clli@tyust.edu.cn

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出版历程
- 收稿日期:2023-02-04
- 录用日期:2023-04-13
- 修回日期:2023-02-24
- 网络出版日期:2023-04-13

Design and achievement of a device for high-precision ammonia gas detection based on laser spectroscopy

1.
Shanxi Engineering Research Center of Precision Measurement and Online Detection Equipment, Taiyuan 030024, China
2.
School of Environment and Safety, Taiyuan University of Science and Technology, Taiyuan 030024, China
3.
Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China

Funds:Supported by National Natural Science Foundation of China (No. U1810129, No. 52076145, No. 12304403); Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province (No. 20230031); Shanxi Scholarship Council of China (No.2023-151); Fundamental Research Program of Shanxi Province (No. 202203021222204); Taiyuan University of Science and Technology Scientific Research Initial Funding (No. 20222008, No. 20222132); Transformation of Scientific and Technological Achievements Fund of Shanxi Province (No. 201904D131025)

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Corresponding author:clli@tyust.edu.cn

摘要

摘要:
氨气排放会对环境以及人体健康造成危害，因此对环境中氨气浓度的高精度监测显得尤为重要。本文基于具有高灵敏度、高响应速度等优点的离轴积分腔输出光谱技术(OA-ICOS)对氨气高精度检测装置进行设计。使用基长30 cm装有反射率为99.99%的高反镜的光学谐振腔作为气体吸收池，实现了近3000 m的光程，将中心波长为1528 nm的分布反馈式器（DFB）调谐至6548.611 cm⁻¹和6548.798 cm⁻¹附近，在常温18.6 kPa的气压下对1×10⁻⁵~5×10⁻⁵范围内NH₃进行了检测。测量结果表明NH₃浓度与信号幅值的线性拟合度 R ²可达0.99979。使用Allan方差对实验数据进行分析得到13 s后系统的平均检测极限为9.8×10⁻⁹，在103 s时系统的最低检测极限可达7×10⁻⁹（ S / N ~1）。实验结果表明，该检测装置具有良好的稳定性与高灵敏度，满足对氨气高精度检测的需求，本文研究为国内自主研发痕量气体高精度检测设备提供了技术经验。
- 离轴积分腔输出光谱/
- 氨气/
- 高精度检测
Abstract:
Ammonia emission will cause harm to the environment and human health, so it is particularly important that the ammonia concentrations are measured with high precision. Off-Axis Integrating Cavity Output Spectroscopy (OA-ICOS), which has the advantages of high sensitivity and high response speed, is used to design a high-precision ammonia detection device. The gas absorption cell is composed of two high reflection mirrors with a reflectivity of 99.99%, and the base length of the optical resonator is 30 cm. Finally, an optical path of nearly 3000 m was realized. The Distributed Feedback Laser (DFB) with a central wavelength of 1528 nm is tuned to 6548.611 cm⁻¹and 6548.798 cm⁻¹. The concentration of NH₃is changed from 1×10⁻⁵to 5×10⁻⁵and is detected under an atmospheric pressure of 18.6 kPa at room temperature. The measurement results show that the linear fit R ²between NH₃concentration and signal amplitude can reach 0.99979. The Allan variance is used to analyze the experimental data, and the minimum detection limit of the system can reach 7×10⁻⁹at 103 s. The experimental results show that the detection device has good stability and high sensitivity, meets the demand for the high-precision detection of ammonia gas, and also provides technical experience for the domestic independent research and development of high-precision detection equipment for trace gases.
- Off-axis integrated cavity output spectroscopy/
- NH₃/
- High-precision detection

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图 1（a）检测装置原理图及（b）谐振腔结构示意图

Figure 1.(a) Schematic diagram of detection device and (b) schematic diagram of resonator structure

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图 2检测装置实物图

Figure 2.Detection device diagram

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图 3（a）体积分数为1×10⁻⁵NH₃吸收信号及（b）去除背景信号后的NH₃吸收信号

Figure 3.(a)NH₃absorption signal with volume fraction of 1×10⁻⁵; (b) NH₃absorption signal after removing background signal

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图 4不同浓度下的NH₃测量信号

Figure 4.Measured NH₃signals at different concentrations

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图 5NH₃浓度与NH₃吸收信号幅度间的线性关系

Figure 5.Linear relationship between the real concentrations and the fitted ones of NH₃absorption signal

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图 6（a）体积分数为1×10⁻⁵的NH₃测量2000 s的原始数据及（b）Allan方差分析图

Figure 6.(a) Row data of NH₃with concentration of 1×10⁻⁵over 2000 s; (b) Allan variance as a function of integration time

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图 7体积分数为1×10⁻⁵NH₃标准气体的检测浓度分布图，红线为高斯函数拟合结果

Figure 7.Detection concentration distribution diagram of NH₃standard gas with concentration of 1×10⁻⁵. The red line is a Gaussian profile fitting

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表 1各检测方法对比表

Table 1.Comparison table of various detection methods

序号	研究者	检测方法	吸收线位置 (cm⁻¹)	吸收线强 (cm/mol)	光程 (m)	检测极限（1×10⁻⁶）
1	Claps^[11]	VOAS	6528.76	1.1741×10⁻²¹	36	0.7
2	Miller^[12]	WMS	1103.44	1.5141×10⁻¹⁹	60	0.0002
3	Guo^[13]	WMS 2f/1f	6599.9	1.3871×10⁻²¹	15	0.16
4	Baer^[15]	OA-ICOS	6528.9	1.350×10⁻²¹	5035	0.002
5	Jia^[16]	OA-ICOS& WMS	6528.76	1.174×10⁻²¹	115.4	0.274
6	Our work	OA-ICOS	6548.61	1.879×10⁻²¹	3000	0.007
6	Our work	OA-ICOS	6548.79	1.847×10⁻²¹	3000	0.007
注：VOAS (Vibrational overtone absorption spectroscopy); WMS (Wavelength modulation spectroscopy); OA-ICOS (Off-axis integrated cavity output spectroscopy).

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