中国激光, 2024, 51 (8): 0811004, 网络出版: 2024-03-29  

基于标定直接吸收光谱方法的近红外乙烯检测【增强内容出版】

Near-infrared C2H4 Detection Based on Calibrated Direct Absorption Spectroscopy
作者单位
1 中国科学技术大学环境科学与光电技术学院,安徽 合肥 230026
2 中国科学院合肥物质科学研究院安徽光学精密机械研究所光子器件与材料安徽省重点实验室,安徽 合肥 230031
3 中国科学院合肥物质科学研究院安徽光学精密机械研究所中国科学院环境光学与技术重点实验室,安徽 合肥 230031
4 国防科技大学先进激光技术安徽省实验室,安徽 合肥 230037
5 国家管网集团科学技术研究总院分公司,河北 廊坊 065000
摘要
实现乙烯气体(C2H4)实时在线精确检测对石油化工、煤矿等行业安全具有重要意义,但是C2H4在近红外波段的谱线强度信息不明确,具有谱带吸收特征,且与CH4有明显的混叠干扰,因此对其浓度进行精确检测是目前激光吸收光谱测量面临的共性技术难题。将波长调制光谱中的标定方法与直接吸收光谱相结合,提出了一种适用于C2H4气体检测的标定直接吸收光谱法(CDAS)。该方法不需要激光吸收光谱反演过程中的确切谱线强度信息,并克服了波长调制光谱在测量过程中出现的非线性效应。为了避免特定工况(如煤矿)中CH4的干扰,实验装置采用了高精度压强控制系统,并且在100 mbar(1 bar=105 Pa)稳定压强下实现了CH4和C2H4混叠光谱的分离。实验过程中对1626 nm附近的CH4和C2H4仿真和实测吸收光谱进行了分析,确定了C2H4的标定光谱范围,进而验证了该方法在体积分数低于100×10-6的范围内,对C2H4气体的检测误差不超过-1.47×10-6,并且测量体积分数与标准体积分数之间的线性拟合优度达到了0.999。对体积分数为10×10-6的C2H4直接吸收光谱进行分析,以1倍信噪比对应的浓度作为检测下限进行等效计算,得到检测下限为1.38×10-6。在Allan方差分析中,积分时间为77 s时检测精度达到了0.04×10-6。以上实验结果充分说明了标定直接吸收光谱法能够在近红外波段实现C2H4的精确检测,并为此类气体的检测提供了一种新思路。
Abstract
Objective

The real-time detection of ethylene (C2H4) is significant for the safety of coal mines, the petrochemical industry, and other industries. Currently, the mainstream methods for C2H4 gas concentration detection include gas chromatography and electrochemical sensors. Gas chromatography can separate multicomponent gases and avoid mutual interference. However, this method requires long-term preheating and frequent calibration, making it difficult to complete real-time measurements in industrial scenarios. Although electrochemical sensors have the advantages of small size and low cost, their selectivity is poor, and it is difficult to avoid cross-interference. In contrast, tunable diode laser absorption spectroscopy (TDLAS) has the advantages of real-time measurements, high sensitivity, and strong selectivity. They are widely used in industrial gas detection and environmental monitoring. Unfortunately, there are still some difficulties in real-time high-precision detection of C2H4. First, information regarding the absorption line of C2H4 in the near-infrared band cannot be obtained. Second, the absorption spectrum of C2H4 is described as complex band absorption. Third, the absorption spectra of C2H4 and CH4 in the near-infrared band interfere with each other. Therefore, real-time high-precision detection of C2H4 is a common problem that urgently needs to be addressed.

Methods

First, the gas concentration can be calculated using traditional direct absorption spectroscopy if the accurate parameters of the absorption line are known. However, for C2H4, it does not contain an absorption line intensity within the near-infrared band in the HITRAN database. This results in an inability to use a calibration-free method to directly calculate the C2H4 concentration. Notably, the concentration calculation method in wavelength modulation spectroscopy does not require accurate spectral line intensity. Therefore, the calibration concept of wavelength modulation spectroscopy is applied to the direct absorption spectroscopy, forming a method named calibrated direct absorption spectroscopy. In addition, faced with the problems of the band absorption of C2H4 and the interference of CH4, a high-precision pressure control system is utilized to complete the spectral line separation under low pressure. In contrast to previous studies, it is necessary to select an appropriately calibrated spectrum in this study. Specifically, standard CH4 and C2H4 gases are measured at a pressure of 100 mbar (1 bar=105 Pa) and the corresponding direct absorption spectra are obtained. By comparing with the simulated spectrum of CH4 in the HITRAN database, the appropriate calibrated spectrum of C2H4 is determined.

Results and Discussions

Stable pressure plays a vital role in the experiments. After the pressure value stabilizes to 100 mbar, the pressure results of the continuous measurement within 1 h are collected, and the distribution of the pressure results is well fitted by a Gaussian function; the full width at half maximum is 0.008 mbar, which proves the stability of the experimental system for pressure control. The subsequent experiments are conducted at 100 mbar. Within the volume fraction of less than 100×10-6, the direct absorption spectrum signals of five sets of C2H4 are acquired and the concentration results are also calculated. The correlated coefficient of linear fitting between the result and the standard concentration is greater than 0.999, and the maximum measurement error is -1.47×10-6. In addition, a direct absorption spectrum signal of 10×10-6 C2H4 is selected for limit of detection (LoD) analysis. The peak value of the signal is 5.80×10-4, and that of the background signal is 0.80×10-4, which can be calculated to obtain a signal-to-noise ratio (SNR) of 7.25. The concentration corresponding to one SNR is defined as the LoD, and its value is 1.38×10-6. Finally, C2H4 with a volume fraction of 20×10-6 is continuously measured for 40 min, and Allan variance analysis is performed on the volume fraction results. At an integral time of 1 s, the precision of measurement for C2H4 is 0.61×10-6. As the integral time increases, the detection precision can reach 0.04×10-6.

Conclusions

To address the challenges faced in near-infrared ethylene detection, a calibrated method in wavelength modulation spectroscopy is applied to direct absorption spectroscopy, forming a new method known as calibrated direct absorption spectroscopy. An experimental device for C2H4 detection with a high-precision pressure-control system is established, and the direct absorption spectrum of C2H4 is measured at approximately 1626 nm. Based on experimental verification, the calibrated direct absorption spectroscopy method can complete the real-time detection of C2H4, overcoming the limitations of traditional direct absorption spectroscopy. We also hope to address real-time detection problems of other similar gases, which can significantly expand the application of direct absorption spectroscopy.

王前进, 孙鹏帅, 张志荣, 蔡永军, 黄文彪, 庞涛, 夏滑, 吴边. 基于标定直接吸收光谱方法的近红外乙烯检测[J]. 中国激光, 2024, 51(8): 0811004. Qianjin Wang, Pengshuai Sun, Zhirong Zhang, Yongjun Cai, Wenbiao Huang, Tao Pang, Hua Xia, Bian Wu. Near-infrared C2H4 Detection Based on Calibrated Direct Absorption Spectroscopy[J]. Chinese Journal of Lasers, 2024, 51(8): 0811004.

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