基于紫外差分-自适应干扰对消的NO浓度高精度检测技术

邓勤

doi:10.5768/JAO202243.0604003

基于紫外差分-自适应干扰对消的NO浓度高精度检测技术

doi: 10.5768/JAO202243.0604003

邓勤

中煤科工集团重庆研究院有限公司，重庆 400039

基金项目: 中煤科工集团重庆研究院有限公司重点项目（2019ZDXM03）；中国煤炭科工集团重点项目(2021-2-TD-ZD009)

详细信息

作者简介:
邓勤（1987—），女，硕士研究生，助理研究员，主要从事粉尘及大气污染物监测治理技术研究。E-mail：shard1025@126.com

中图分类号: TN247;X511
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出版历程
- 收稿日期: 2022-06-13
- 修回日期: 2022-08-03
- 网络出版日期: 2022-08-05
- 刊出日期: 2022-11-14

High-precision detection technology of NO concentration based on UV differential-adaptive interference cancellation

DENG Qin

Chongqing Research Institute Co.,Ltd., China Coal Technology and Engineering Group, Chongqing 400039, China

摘要

摘要: 为实现机动车尾气高精度监测，提出一种高精度宽量程NO测量方法。针对尾气中SO₂及NO在紫外波段存在吸收峰重合从而无法直接进行单组分气体反演问题，首先用紫外差分光学吸收光谱（ultra-violet differential optical absorption spectroscopy, UV-DOAS）法计算得到混合气体在NO敏感波段（200 nm～230 nm）的差分光学密度（differential optical density, DOD），并引入自适应干扰对消技术以实现混合气体DOD的快速分离，最终利用最小二乘法对分离出的NO进行浓度反演。该方法可实现100×10⁻⁶～3 000×10⁻⁶范围内NO浓度（气体的体积分数）快速反演，经测试，在100×10⁻⁶～200×10⁻⁶浓度范围内反演相对误差绝对值小于10%，在300×10⁻⁶～3000×10⁻⁶浓度范围内，反演相对误差绝对值小于5%。该方法具有测量量程大、速度快的特点，可满足汽车尾气中3 000×10⁻⁶范围内NO浓度测量要求。
- 紫外差分光学吸收光谱 /
- 差分光学密度 /
- 自适应干扰对消 /
- 最小二乘法 /
- 混合气体浓度反演 /
- 递归最小二乘法
Abstract: In order to realize high-precision monitoring of vehicle emission, a high-precision and wide-range NO measurement method was proposed. Aiming at the problem that the absorption peaks of SO2 and NO in emission overlapping in the UV band, and it was impossible to directly perform single-component gas inversion, the differential optical density (DOD) of mixed gas in the NO sensitive band (200 nm～230 nm) was first calculated by the ultraviolet differential optical absorption spectroscopy (UV-DOAS) method. Then, the adaptive interference cancellation technology was introduced to achieve rapid separation of mixed gas DOD. Finally, the least square method was used to perform the concentration inversion of separated NO. This method could achieve rapid inversion of NO concentration (volume fraction of gas) in the range of 100×10⁻⁶ to 3 000×10⁻⁶. After testing, the absolute value of the relative error of inversion is less than 10% in the concentration range of 100×10⁻⁶ to 200×10⁻⁶, and less than 5% in the concentration range of 300×10⁻⁶ to 3 000×10⁻⁶. This method has the characteristics of large measurement range and fast speed, and can meet the measurement requirements of NO concentration in the range of 3 000×10⁻⁶ in vehicle emission.

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图 1 自适应干扰对消

Fig. 1 Schematic of adaptive interference cancellation

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图 2 实验系统框图

Fig. 2 Block diagram of experimental system

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图 3 实验系统实物图

① 氘灯；②光纤；③气室；④ 光谱仪；⑤计算机；⑥配气系统；⑦ 气瓶；⑧微阀； ⑨气体管路。

Fig. 3 Physical drawing of experimental system

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图 4 NO、SO₂及混合气体的差分光学厚度图

Fig. 4 Diagram of DOD of NO, SO₂ and mixed gas

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图 5 3条参考曲线

Fig. 5 Three reference curves

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表 1 参考曲线中不同浓度气体DOD占比

Table 1 DOD ratio of gas at different concentrations in reference curves

DOD	SO₂浓度值/10⁻⁶
DOD	10	20	30	40	50	60	70	80
参考曲线1	0.6	0.1	0.1	0.1	0.1	0	0	0
参考曲线2	0	0.1	0.1	0.6	0.1	0.1	0	0
参考曲线3	0	0	0	0.1	0.1	0.1	0.6	0.1

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表 2 第1组实验NO差分光学厚度计算值与标准值相关系数

Table 2 Correlation coefficient between calculated value and standard value of NO differential optical thickness in the first group of experiments

标准值（NO/SO₂）/10⁻⁶	200/10	200/20	200/30	200/40	200/50	200/60	200/70	200/80
相关系数（参考曲线1）	0.998	0.999	0.997	0.994	0.990	0.984	0.979	0.974
相关系数（参考曲线2）	0.997	0.997	0.998	0.998	0.996	0.994	0.991	0.986
相关系数（参考曲线3）	0.993	0.991	0.991	0.993	0.996	0.998	0.997	0.996

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表 3 第2组实验NO计算结果

Table 3 Calculation results of NO in the second group of experiments

标准值（NO/SO₂）/10⁻⁶	100/15	200/40	300/30	300/40	400/10	400/60	500/20	500/40
与标准曲线相关系数	0.992	0.993	0.993	0.995	0.995	0.998	0.995	0.996
反演NO浓度c/10⁻⁶	93.35	183.44	294.82	293.55	391.74	387.66	493.75	490.89
相对误差ε/%	−6.65	−8.28	−1.73	−2.15	−2.07	−3.09	−1.25	−1.82

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表 4 第2组实验NO计算结果

Table 4 Calculation results of NO in the second group of experiments

标准值（NO/SO₂）/10⁻⁶	600/25	600/35	700/40	700/70	800/45	800/80	1 000/50	1 500/35
与标准曲线相关系数	0.995	0.996	0.997	0.999	0.998	0.998	0.998	0.997
反演NO浓度c/10⁻⁶	601.95	597.72	687.06	691.85	781.60	786.69	986.66	1 468.05
相对误差ε/%	0.33	−0.38	−1.85	−1.16	−2.30	−1.66	−1.33	−2.13

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表 5 第2组实验NO计算结果

Table 5 Calculation results of NO in the second group of experiments

标准值（NO/SO₂）/10⁻⁶	1 700/45	1 900/35	2 100/70	2 300/80	2 500/50	2 700/25	2 900/40	3 000/55
相关系数	0.998	0.997	0.999	0.998	0.998	0.997	0.997	0.999
反演NO浓度c/10⁻⁶	1 647.89	1 856.46	2 041.95	2 218.30	2 449.08	2 595.23	2 776.82	2 891.79
相对误差ε/%	3.07	2.29	2.76	3.55	2.04	3.88	4.25	3.61

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