基于频分复用激光吸收光谱技术的高湿烟气中痕量甲烷-氨双元燃料逃逸测量

doi:10.16085/j.issn.1000-6613.2024-1726

化工进展 ›› 2025, Vol. 44 ›› Issue (4): 1913-1922.DOI: 10.16085/j.issn.1000-6613.2024-1726

基于频分复用激光吸收光谱技术的高湿烟气中痕量甲烷-氨双元燃料逃逸测量

王昊¹(), 马柳昊¹(), 杜建国², 周晨¹, 王玮¹, 王伟³, 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
^3.香港理工大学建筑环境及能源工程学系，香港 999077

收稿日期:2024-10-28 修回日期:2025-01-13 出版日期:2025-04-25 发布日期:2025-05-07
通讯作者: 马柳昊
作者简介:王昊（2000—），男，硕士研究生，研究方向为高温气体传感技术。E-mail：333993@whut.edu.cn。
基金资助:
国家自然科学基金青年基金(52106221);广东省基础与应用基础研究计划(2023B1515120012);佛山仙湖实验室重大科研项目(XHD2024-21000000-03)

Measurement for trace-level methane-ammonia binary fuel slip in high-humidity flue gases based on frequency-division multiplexing laser absorption spectroscopy

WANG Hao¹(), MA Liuhao¹(), DU Jianguo², ZHOU Chen¹, WANG Wei¹, WANG Wei³, WANG Yu¹^,²

^1.Center for Low-carbon Combustion and Propulsion, Wuhan University of Technology, Wuhan 430070, Hubei, China
^2.National Energy Key Laboratory for New Hydrogen-Ammonia Energy Technologies, Foshan Xianhu Laboratory, Foshan 528200, Guangdong, China
^3.Department of Building Environment and Energy Engineering, The Hong Kong Polytechnic University, Hong Kong 999077, China

Received:2024-10-28 Revised:2025-01-13 Online:2025-04-25 Published:2025-05-07
Contact: MA Liuhao

摘要/Abstract

摘要：

甲烷（CH₄）掺氨（NH₃）燃烧是实现高温热工过程减碳的可靠技术路径之一，在高通量双元燃料进给时，燃烧组织欠佳会导致痕量级燃料逃逸问题，脱硝系统的非正常运行也会加剧氨逃逸，因此急需对双元燃料逃逸进行同步测量。此外，甲烷掺氨燃烧中烟气水汽浓度较高，显著的气体分子展宽效应给传统且广泛使用的激光吸收光谱检测带来挑战。本文发展了适用于高湿背景痕量双元燃料同步测量的频分复用-波长调制光谱技术，通过测量配制的10%~50%（体积分数）高水气氛下痕量（1×10^-6~100×10^-6）双元燃料混合气体，定量分析了水汽对CH₄和NH₃光谱展宽的影响，获得了CH₄和NH₃浓度与目标谐波信号峰值的线性关系，系统地对比了频分复用测量与单路测量结果，验证测量结果的可靠性。通过Allan方差评估甲烷和氨检测下限分别为82×10^-9和88×10^-9，进一步通过对已知浓度的混合气体实时测量验证了该方法具有足够的灵敏度和快速响应的能力。

关键词: 频分多路复用, 测量, 高湿烟气, 增湿, 二元混合物, 燃料逃逸

Abstract:

Co-firing of methane (CH‍₄) and ammonia (NH‍₃) is reliable technological pathway for decarbonization in high-temperature thermal processes. During high-flux binary fuel feeding, poor combustion organization can lead to trace-level fuel leakage, and abnormal operation of the de-nitrification system can exacerbate ammonia slip. Therefore, simultaneous measurement of binary fuel slip is urgently needed. Additionally, the high concentration of water vapor in the flue gas during methane-ammonia combustion introduces significant molecular broadening effects, posing challenges for traditional and widely-used laser absorption-based spectroscopic detection. This study presented a frequency-division multiplexing-wavelength modulation spectroscopy technique for simultaneous trace-level binary fuels under high-humidity environments. By configuring trace-level (1×10^-6—100×10^-6) mixtures in 10%—50% high-humidity atmospheres, the effect of water vapor on the spectral broadening of CH₄ and NH₃ was quantified, and a linear relationship between CH₄ and NH₃ concentrations and the target harmonic signal peaks was established. A systematic comparison between frequency-division multiplexing and single-channel measurements was conducted to verify the reliability of the results. Allan variance analysis showed that detection limits for methane and ammonia were both below 82×10^-9 and 88×10^-9. Real-time measurements of the known concentration gas mixtures further verified the method's sensitivity and rapid response capabilities.

Key words: frequency-division multiplexing, measurement, high-humidity flue gases, humidification, binary mixture, fuel slip

中图分类号:

TK31

王昊, 马柳昊, 杜建国, 周晨, 王玮, 王伟, 王宇. 基于频分复用激光吸收光谱技术的高湿烟气中痕量甲烷-氨双元燃料逃逸测量[J]. 化工进展, 2025, 44(4): 1913-1922.

WANG Hao, MA Liuhao, DU Jianguo, ZHOU Chen, WANG Wei, WANG Wei, WANG Yu. Measurement for trace-level methane-ammonia binary fuel slip in high-humidity flue gases based on frequency-division multiplexing laser absorption spectroscopy[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 1913-1922.

图/表 8

图1 多物质吸收谱线强度与不同水汽浓度下的NH3、CH4等物质吸收仿真

图2 高温高湿痕量NH3/CH4测量实验系统

图3 直接吸收光谱测量高温水汽含量结果

图4 1512nm和1654nm激光器不同调制电压下的2f/1f峰值信号

图5 不同测量方式的原始信号与不同浓度下的WMS-2f/1f曲线

图6 不同测量方式下NH3、CH4 WMS-2f/1f峰值信号

图7 连续测量下的NH3、CH4 Allan方差

图8 痕量NH3/CH4混合气体连续测量结果

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基于频分复用激光吸收光谱技术的高湿烟气中痕量甲烷-氨双元燃料逃逸测量

Measurement for trace-level methane-ammonia binary fuel slip in high-humidity flue gases based on frequency-division multiplexing laser absorption spectroscopy

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