基于 10.4 μm 量子级联激光器及波长调制光谱技术的高温痕量氨检测

doi:10.3969/j.issn.1007-5461.2026.04.009

量子电子学报 ›› 2026, Vol. 43 ›› Issue (4): 601-611.doi: 10.3969/j.issn.1007-5461.2026.04.009

基于 10.4 μm 量子级联激光器及波长调制光谱技术的高温痕量氨检测

吴小广1, 马柳昊1*, 严永胜1, 李青 1, 王宇 1,2

1 武汉理工大学低碳燃烧与动力研究中心, 湖北武汉 430070; 2 国家能源氢能及氨氢融合新能源技术重点实验室, 佛山仙湖实验室, 广东佛山 528200

收稿日期:2024-12-09 修回日期:2025-02-24 出版日期:2026-07-28 发布日期:2026-07-27
通讯作者: E-mail: liuhaoma@whut.edu.cn E-mail:liuhaoma@whut.edu.cn
作者简介:吴小广 ( 2000 - ), 重庆垫江人, 研究生, 主要从事污染物监测方面的研究。E-mail: 333922@whut.edu.cn
基金资助:
国家自然科学基金 (52106221), 广东省基础与应用基础研究基金 (2023B1515120012), 佛山仙湖实验室重大科研项目 (XHD2024-21000000-03)

High‑temperature trace ammonia detection based on a 10.4 μm quantum cascade laser and wavelength modulation spectroscopy

WU Xiaoguang 1 , MA Liuhao 1*, YAN Yongsheng 1 , LI Qing 1 , WANG Yu 1,2

1 Low Carbon Combustion and Power Research Center, Wuhan University of Technology, Wuhan 430070, China;2 National Energy Key Laboratory for New Hydrogen-Ammonia Energy Technologies, Foshan Xianhu Laboratory, Foshan 528200, China

Received:2024-12-09 Revised:2025-02-24 Published:2026-07-28 Online:2026-07-27

摘要/Abstract

摘要： 氨作为典型的零碳富氢燃料, 其规模化应用有助于实现高温工业的源头脱碳。然而, 氨燃料反应活性低、稳燃范围窄, 在高通量来流条件下易发生脱火, 导致显著的氨逃逸。此外, 在选择性催化还原过程中, 过量喷氨也是氨逃逸的主要来源。本文利用中心波长为10.4 μm (962.15 cm−1 )的量子级联激光器和自研紧凑型单程高温气体池(T =120 ℃, P = 30 kPa), 开发了一套面向高温痕量氨逃逸检测的中红外光谱系统。首先, 基于直接吸收光谱技术测量了不同体积分数的氨气(NH3)标气在四种典型伴随气(N2、air、Ar、20%H2O)中的吸收特征, 并采用Voigt函数线型拟合获取目标气体吸收特征, 验证了光谱参数的可靠性。随后, 采用波长调制光谱技术测量低体积分数的NH3 , 利用一次谐波归一化二次谐波(2f /1f )的方法抑制非吸收因素及背景噪声引起的信号波动, 通过建立谐波信号峰值与气体体积分数的关系, 确定了系统的线性响应特性。实验结果表明, 通过直接吸收光谱技术测量体积分数为100 cm3 /m3 的NH3的测试误差≤2.1%; 波长调制光谱技术可实现最低体积分数为1 cm3 /m3 的NH3检测; 艾伦偏差分析显示, 在13 s积分时间下, 该系统对NH3的检测下限为0.02 cm3 /m3 。

关键词: 光谱学, 痕量氨检测, 中红外吸收光谱, 直接吸收光谱技术, 波长调制光谱技术

Abstract: Ammonia is a typical zero-carbon, hydrogen-rich fuel. Its large-scale application can achieve decarbonization at the source of high-temperature industry. However, ammonia fuel has low reactivity and a narrow stable combustion range, making it prone to significant ammonia escape due to misfiring under high-throughput fuel flow conditions. In addition, excessive ammonia injection also constitutes a major source of ammonia escape during the selective catalytic reduction stage. This study employs a quantum cascade laser with a center wavelength of 10.4 μm (962.15 cm−1 ) and a self-developed compact single-pass high-temperature gas cell (T = 120 ℃, P = 30 kPa) to develop a mid-infrared spectroscopic gas detection system for high-temperature trace ammonia escape. Firstly, based on direct absorption spectroscopy (DAS), the absorption characteristics of ammonia (NH3) standard gases with various volume fractions in four typical background gases (N2, air, Ar, and 20%H2O) are measured, and the Voigt line fitting method is applied to extract absorption information correlated with gas concentration, thereby verifying the feasibility of the spectral parameters. Subsequently, wavelength modulation spectroscopy (WMS) is adopted for low-volume-fraction NH3 measurement, with the second-harmonic-normalized-by-first-harmonic (2f /1f) method used to suppress signal fluctuations induced by non-absorption effects and background noise. The linear response characteristics of the system are then determined by establishing the correlation between the harmonic signal peak and the gas volume fraction. The experimental results show that, using DAS to measure NH3 with a volume fraction of 100 cm3 /m3 in different background gases, the measurement error is ≤ 2.1%, and using WMS technology enables NH3 detection with a minimum volume fraction of 1 cm3 /m3 . And Allan deviation analysis indicates that the detection limit of the system for NH3 is 0.02 cm3 /m3 at an integration time of 13 s.

Key words: spectroscopy, trace ammonia detection, mid-infrared absorption spectroscopy, direct absorption spectroscopy technology, wavelength modulation spectroscopy technology

中图分类号:

0433.54

吴小广, 马柳昊, 严永胜, 李青, 王宇, . 基于 10.4 μm 量子级联激光器及波长调制光谱技术的高温痕量氨检测[J]. 量子电子学报, 2026, 43(4): 601-611.

WU Xiaoguang , MA Liuhao , YAN Yongsheng , LI Qing , WANG Yu , . High‑temperature trace ammonia detection based on a 10.4 μm quantum cascade laser and wavelength modulation spectroscopy[J]. Chinese Journal of Quantum Electronics, 2026, 43(4): 601-611.

参考文献

[1]Zhang Shu, Ma Yubo, Zheng Xinzhu, etc Recons-truction and Enlightenment of Energy Security Asses-sment System under the Background of Green and L-ow Carbon Transformation [J] Chinese Engineering Science, 2024, 26 (04): 28-39.
章姝, 马堉博, 郑馨竺, 等. 绿色低碳转型背景下能源安全评估体系重构与启示[J]. 中国工程科学，2024，26(04): 28-39.
[2]Dimitriou P, Javaid R. A review of ammonia as a compression ignition engine fuel[J]. International Journal of Hydrogen Energy, 2020, 45(11): 7098-7118.
[3]Valera-Medina A, Vigueras-Zuniga M O, et al. Amm-onia combustion in furnaces: A review[J]. Internation-al Journal of Hydrogen Energy, 2023,49:1597-1618.
[4]Thomas D E, Wadkar C, Goertemiller C F W, et al. Structure and nitric oxide formation in laminar diffusion flames of ammonia–hydrogen and air[J]. Fuel, 2024, 362: 130764.
[5]Bathrinath S, Devaganesh J, Santhi B, et al. The Adverse Human Health Effects Due To Ammonia, Hydrogen Sulphide and Chlorine in Process Industry: A Review[J]. Int. J. Mech. Prod, 2018, 8: 394-402.
[6]Zhao S, Peng J, Ge R, et al. Research progress on selective catalytic reduction (SCR) catalysts for NOx removal from coal-fired flue gas[J]. Fuel Processing Technology, 2022, 236: 107432.
[7]LI Zishang, ZHU Renhan, DU Zhen. Analysis on the Optimization Technology of Precise Ammonia Injection in SCR Denitration System[J]. Power Generation Technology, 2021, 42(5): 630.
[8]Zhu X, Du J, Yu Z, et al. NOx Emission and Con-trol in Ammonia Combustion: State-of-the-Art Review and Future Perspectives[J]. Energy & Fuels, 2023, 38(1): 43-60.
[9]An T, Wei B, Ma R, et al. Study on the high-temperature corrosion mechanism of boiler steel 15CrMoG in ammonia-coal co-firing environment[J]. Fuel, 2024, 378: 132892.
[10]Yin Jiaqi, Shen Wenfeng, Lv Dawu, etc Research progress on metal oxide semiconductor MEMS gas sensors [J] Material Review, 2024, 38 (01): 34-47
尹嘉琦, 沈文锋, 吕大伍, 等. 金属氧化物半导体MEMS气体传感器研究进展[J]. 材料导报, 2024, 38(01)： 34-47.
[11]Molleman B, Alessi E, Krol D, et al. Application of metal oxide semiconductor for detection of ammonia emissions from agricultural sources[J]. Sensing and Bio-Sensing Research, 2022, 38: 100541.
[12]Mashruk S, Zhu X, Roberts W L, et al. Chemiluminescent footprint of premixed ammonia-methane-air swirling flames[J]. Proceedings of the Combustion Institute, 2023, 39(1): 1415-1423.
[13]Guth U, Zosel J. Electrochemical solid electrolyte gas sensors—Hydrocarbon and NOx analysis in exhaust gases[J]. Ionics, 2004, 10: 366-377.
[14]Lackner M. Tunable diode laser absorption spectroscopy (TDLAS) in the process industries–a review[J]. Reviews in Chemical Engineering, 2007, 23(2): 65-147.
[15]Xing Kunming, Yang Ke, Zhang Long, et al. Simultaneous detection of CO and CO2 in mainstream cigarette smoke using TDLAS technology [J]. Journal of Quantum Electronics, 2017,34 (01): 81-87.
邢昆明，杨柯，张龙，等.基于TDLAS技术同时检测卷烟主流烟气中的CO和CO_2[J].量子电子学报,2017,34(01):81-87
[16]Liu Qinghui, Huang Wenjian, Gao Guangzhen, Zhang Mingke, Wang Xuan, Yang Yubing, Cai Tingdong. Simultaneous detection of acetylene concentration and temperature based on TDLAS under high temperature and pressure [J]. Journal of Quantum Electronics, 1-13.
刘庆辉，黄文健，高光珍，张铭珂，王宣，杨玉冰，蔡廷栋.高温高压下基于TDLAS的乙炔浓度和温度同时探测[J].量子电子学报,1-13.
[17]Yao Shunchun, Guo Songjie, Yang Yan, etc Research and application of flue gas ammonia escape detection based on tunable diode laser absorption spectroscopy technology (invited) [J] Acta Photonica Sinica, 2023, 52 (03): 11-24.
姚顺春 ,郭松杰, 杨言, 等. 基于可调谐二极管激光吸收光谱技术的烟气氨逃逸检测研究及应用（特邀）[J]. 光子学报, 2023, 52(03): 11-24.
[18]Ma L, Wang W, Zhou C, et al. A laser absorption sensor for fuel slip monitoring in high-humidity flue gases from ammonia combustion[J]. Measurement Science and Technology, 2023, 34(9): 094005.
[19]Guo X, Zheng F, Li C, et al. A portable sensor for in-situ measurement of ammonia based on near-infrared laser absorption spectroscopy[J]. Optics and Lasers in Engineering, 2019, 115: 243-248.
[20]Guo S, Li Z, Liu Z, et al. Simultaneous measurement of NH3 and NO by mid-infrared tunable diode laser absorption spectroscopy based on machine-learning algorithms[J]. Measurement, 2024, 234: 114858.
[21]陈晨. 基于调频连续波的多通池气体传感技术研究[D]. 哈尔滨: 哈尔滨工业大学, 2018: 37-47.
[22]Razeghi M, Lu Q Y, Bandyopadhyay N, et al. Quantum cascade lasers: from tool to product[J]. Optics express, 2015, 23(7): 8462-8475.
[23]Vitiello M S, Scalari G, Williams B, et al. Quantum cascade lasers: 20 years of challenges[J]. Optics express, 2015, 23(4): 5167-5182.
[24]Peng W Y, Sur R, Strand C L, et al. High-sensitivity in situ QCLAS-based ammonia concentration sensor for high-temperature applications[J]. Applied Physics B, 2016, 122(7): 188.
[25]Ji Y, Duan K, Lu Z, et al. Mid-infrared absorption spectroscopic sensor for simultaneous and in-situ measurements of ammonia, water and temperature[J]. Sensors and Actuators B: Chemical, 2022, 371: 132574.
[26]Sur R, Spearrin R M, Peng W Y, et al. Line intensities and temperature-dependent line broadening coefficients of Q-branch transitions in the v2 band of ammonia near 10.4 μm[J]. Journal of Quantitative Spectroscopy and Radiative Transfer, 2016, 175: 90-99.
[27]Duan K, Ji Y, Wen D, et al. Mid-infrared fiber-coupled laser absorption sensor for simultaneous NH3 and NO monitoring in flue gases[J]. Sensors and Actuators B: Chemical, 2023, 374: 132805.
[28]Zhuang Xiaoyao, Zhou Bin, Wang Yihong, etc Gas concentration measurement method based on fixed point wavelength modulation spectroscopy technology [J] Acta Optica Sinica, 2021, 41 (23): 254-260.
庄欠瑶, 周宾, 王一红, 等.基于固定点波长调制光谱技术的气体浓度测量方法[J].光学学报, 2021, 41(23):254-260.
[29]Gordon I E, Rothman L S, Hargreaves R J, et al. The HITRAN2020 molecular spectroscopic database[J]. Journal of quantitative spectroscopy and radiative transfer, 2022, 277: 107949.
[30]Hanson RK, Spearrin RM, Goldenstein CS. Spectroscopy and optical diagnostics for gases. Springer International Publishing Switzerland; 2016. 131-148.

基于 10.4 μm 量子级联激光器及波长调制光谱技术的高温痕量氨检测

High‑temperature trace ammonia detection based on a 10.4 μm quantum cascade laser and wavelength modulation spectroscopy

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	陈威, 徐亮, 徐睆垚, 花谷彪, 徐寒扬, 徐家求, 潘帅 . 基于怀特池的多光程高精度痕量气体检测系统研究[J]. 量子电子学报, 2026, 43(4): 612-622.
[2]	陈兴龙, 陈可友, 万国华, 张春晓, 陈珂 . 基于光声光谱的变压器油中溶解气体高灵敏检测技术[J]. 量子电子学报, 2025, 42(5): 620-628.
[3]	陈亮, 胡仁志, 谢品华, 童金钊, 林川, 杨欢 . 一种 NO₃自由基双分子反应速率常数的测量方法[J]. 量子电子学报, 2025, 42(5): 629-640.
[4]	陈威, 徐亮, 徐寒扬, 徐睆垚, 花谷彪, . 基于 FTIR 开放式多次反射式怀特池系统[J]. 量子电子学报, 2025, 42(5): 641-651.
[5]	许汪洋, 杨同坤, 李良晔, 李豪, 孙琪真, . 基于量子点掺杂聚合物光纤的温度传感研究 (特邀)[J]. 量子电子学报, 2025, 42(4): 526-536.
[6]	魏亚雄, 扶婷婷, 刘毅, 许新胜, . 基于时间分辨光波谱技术的维生素 C 与 9,10-蒽醌光诱导反应机制研究[J]. 量子电子学报, 2025, 42(3): 295-303.
[7]	张敏, 秦晨 . 外电场下 5-溴-2-氟硝基苯分子的解离及激发特性[J]. 量子电子学报, 2025, 42(3): 304-312.
[8]	高翔堃, 董璇, 刘超, 詹杰, 黄青 . 近红外光谱联合机器学习测定樱桃番茄中的番茄红素[J]. 量子电子学报, 2025, 42(3): 313-323.
[9]	房村, 禹胜林, 滕雪松 . 长光程A字型甲烷传感器气室的研究[J]. 量子电子学报, 2025, 42(3): 324-333.
[10]	王旭东, 姜黎明, 梅教旭, 王瑞峰, 古明思, 陈家金, 谈图, 王贵师, 刘锟, 高晓明, . 煤炭地下气化产物甲烷高温高压光谱测量技术研究[J]. 量子电子学报, 2025, 42(1): 27-0.
[11]	刘庆辉 , 黄文健 , 高光珍 , 张铭珂 , 王宣 , 杨玉冰 , 蔡廷栋 . 高温高压下基于 TDLAS 的乙炔浓度和温度同时探测[J]. 量子电子学报, 2025, 42(1): 37-0.
[12]	宋泽阳 , 梁立振 , 柳山虎 , 田镇虎 , 韦江龙 , 许永建 , 谢亚红 , 胡纯栋 , . 基于激光吸收光谱的 Cs 原子浓度检测系统设计研究[J]. 量子电子学报, 2024, 41(6): 852-860.
[13]	赵跃 , 马凤翔 , 王安静 , 李大成 , 崔方晓 , 吴军 , 李扬裕 , 董王朝 . 密闭空间六氟化硫红外光谱仿真技术研究[J]. 量子电子学报, 2024, 41(6): 861-871.
[14]	符小清, 王静鸽, 代博, 梁方圆, 刘佳鑫. 基于柱面聚焦透镜的激光诱导击穿光谱特性研究[J]. 量子电子学报, 2024, 41(4): 578-586.
[15]	张兴龙, 张启航, 刘玉柱, . 锌的激光诱导击穿光谱与等离子体温度研究[J]. 量子电子学报, 2024, 41(4): 587-594.