吸收光谱法在实际应用中的关键问题的研究
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摘要
由于光谱技术具有探测灵敏度高的特点以及其他很多的优点,近年来光谱检测技术应用越来越广泛。
吸收光谱检测技术的依据是朗伯-比尔(Lambert-Beer)定律,但是该定律是在理想的情况下所得,如被测物质浓度适中且为纯吸收物质、入射光源为单色光等。在实际应用中,会有较多的情况不符合定律的限制条件。本文研究了朗伯-比尔定律的适用范围以及被测物质的浓度太高、光源的非单色性、温度的变化、被测物质中的散射现象不可忽略和吸收重叠等问题对吸收光谱的影响。
首先,针对散射影响问题作了详细的研究,结合光传输模型以及光散射理论得出了当散射现象不可忽略时的扩展的朗伯-比尔定律。
其次,温度的变化对吸收光谱检测也有较大影响。本文主要针对两种不同的实验对象去研究,一是温度对气体的吸收截面的影响,选用实验对象为空气中常见的污染气体SO2和NO2,在实验的基础上得到了吸收截面与温度之间的关系式;二是温度对液体的吸光度的影响,选用的实验对象为葡萄糖水溶液,得出了在近红外波段的吸光度的标定曲线。
第三,在光谱检测过程中,当在很窄的波长范围内多种成分吸收谱重叠且吸收峰位置接近时,提出用可调谐激光光谱技术与建立模型相结合的方法来进行检测,并对此方法作了系统研究和数学推导。
根据上述的研究结果,在对吸收光谱检测的原理以及影响因素作了详细研究的基础上,针对目前的实际要求,设计出了两套应用系统:差分吸收光谱(DOAS)大气环境质量监测系统和烟气污染物排放在线连续监测应用系统(CEMS)。在本部分中还针对实际应用中光学系统的防污染问题作了深入的探讨,并解决了相应的工程问题。
本论文主要创新工作有:
1、运用光传输模型和光散射理论得到了扩展的朗伯-比尔定律;2、针对温度对吸收光谱的影响得出了吸收截面与温度的关系式和标定曲线;3、当被测样品中的多种物质的吸收重叠严重时,提出用多个可调谐激光二极管的光谱检测技术与数据建模方法相结合的检测技术;4、设计了两套应用测量系统,并解决了光路防尘等相应的工程问题。
Recently, with the advantages of high sensitivity and other merits, the technology of spectroscopy to measure is applied more and more widely.
The absorption spectroscopy is based on Lambert-Beer Law. However, the Lambert-Beer Law is only applicable in ideal conditions, such as the suitable concentration of component under detection, the homogeneous light to incident and so on. And during the actual measurement, there often are many factors not to obey the restrictive conditions. In this thesis, through doing some research on the tenable conditions of Lambert-Beer law, the influences on the absorption spectrum caused by some factors like the concentration of measured material, the non-monochromatic light, the temperature, the scattering and the ingredient absorption overlap and so on are analyzed in detail.
First, the affect caused by the scattering on the measurement is studied in detail. Combined with the light transport model and light scattering theory, the correctional Lambert-Beer Law is deduced when there is scattering medium in the detected substance.
Secondly, the temperature change can also bring much impact on the absorption spectrum examination. In this article, aiming at the temperature affect, two different experiments are studied. One is the temperature influence on the gas absorption cross-section, in which the common pollution gases in the air SO2 and NO2 are selected as the experimental objects, and the absorption cross-section calibration formula has been given at the experimental foundation. The other is the temperature influence on the liquid absorbance, in which the glucose water is selected as the experimental object. Also, the absorbance calibration curve has been obtained in the near-infrared wave band.
Thirdly in the process of spectrum examination, when there includes many kinds of material ingredient absorption in the object and the absorption overlap among different components is serious, the method of tunable diode laser absorption spectroscopy combined with data modeling is proposed to carry on the examination. Also systematic research about this method and the mathematical derivation are given.
According to above findings and the certain analysis basis to the absorption spectrum principle as well as the influence factors, in view of present practical application, two sets of hardware systems are designed. The one is the differential optics absorption spectroscopy (DOAS) atmospheric environment quality monitor system and another one is continuous emission monitoring system (CEMS). In this part thorough discussion about the optical system is also made to guard against the contamination and one kind of simple mechanical structure is designed to prevent the dust dropping on the optical system in the examination.
Main innovation works in this thesis mainly include:
1. The correctional Lambert-Beer law is obtained using the optical transport model and the light scattering theory;
2. The calibration formula and the calibration curve in view of the temperature influence to the absorption spectrum have been obtained;
3. When examination material includes many ingredients and the absorption overlaps seriously one another, the method of tunable diode laser absorption spectroscopy combined with data modeling is proposed to carry on the examination
4. On the basis of designing two sets of application systems, one simple mechanical structure which will replace the traditional way of blowing dry pure air onto the lens is designed to prevent the dust dropping on the optical system in the examination.
吸收光谱检测技术的依据是朗伯-比尔(Lambert-Beer)定律,但是该定律是在理想的情况下所得,如被测物质浓度适中且为纯吸收物质、入射光源为单色光等。在实际应用中,会有较多的情况不符合定律的限制条件。本文研究了朗伯-比尔定律的适用范围以及被测物质的浓度太高、光源的非单色性、温度的变化、被测物质中的散射现象不可忽略和吸收重叠等问题对吸收光谱的影响。
首先,针对散射影响问题作了详细的研究,结合光传输模型以及光散射理论得出了当散射现象不可忽略时的扩展的朗伯-比尔定律。
其次,温度的变化对吸收光谱检测也有较大影响。本文主要针对两种不同的实验对象去研究,一是温度对气体的吸收截面的影响,选用实验对象为空气中常见的污染气体SO2和NO2,在实验的基础上得到了吸收截面与温度之间的关系式;二是温度对液体的吸光度的影响,选用的实验对象为葡萄糖水溶液,得出了在近红外波段的吸光度的标定曲线。
第三,在光谱检测过程中,当在很窄的波长范围内多种成分吸收谱重叠且吸收峰位置接近时,提出用可调谐激光光谱技术与建立模型相结合的方法来进行检测,并对此方法作了系统研究和数学推导。
根据上述的研究结果,在对吸收光谱检测的原理以及影响因素作了详细研究的基础上,针对目前的实际要求,设计出了两套应用系统:差分吸收光谱(DOAS)大气环境质量监测系统和烟气污染物排放在线连续监测应用系统(CEMS)。在本部分中还针对实际应用中光学系统的防污染问题作了深入的探讨,并解决了相应的工程问题。
本论文主要创新工作有:
1、运用光传输模型和光散射理论得到了扩展的朗伯-比尔定律;2、针对温度对吸收光谱的影响得出了吸收截面与温度的关系式和标定曲线;3、当被测样品中的多种物质的吸收重叠严重时,提出用多个可调谐激光二极管的光谱检测技术与数据建模方法相结合的检测技术;4、设计了两套应用测量系统,并解决了光路防尘等相应的工程问题。
Recently, with the advantages of high sensitivity and other merits, the technology of spectroscopy to measure is applied more and more widely.
The absorption spectroscopy is based on Lambert-Beer Law. However, the Lambert-Beer Law is only applicable in ideal conditions, such as the suitable concentration of component under detection, the homogeneous light to incident and so on. And during the actual measurement, there often are many factors not to obey the restrictive conditions. In this thesis, through doing some research on the tenable conditions of Lambert-Beer law, the influences on the absorption spectrum caused by some factors like the concentration of measured material, the non-monochromatic light, the temperature, the scattering and the ingredient absorption overlap and so on are analyzed in detail.
First, the affect caused by the scattering on the measurement is studied in detail. Combined with the light transport model and light scattering theory, the correctional Lambert-Beer Law is deduced when there is scattering medium in the detected substance.
Secondly, the temperature change can also bring much impact on the absorption spectrum examination. In this article, aiming at the temperature affect, two different experiments are studied. One is the temperature influence on the gas absorption cross-section, in which the common pollution gases in the air SO2 and NO2 are selected as the experimental objects, and the absorption cross-section calibration formula has been given at the experimental foundation. The other is the temperature influence on the liquid absorbance, in which the glucose water is selected as the experimental object. Also, the absorbance calibration curve has been obtained in the near-infrared wave band.
Thirdly in the process of spectrum examination, when there includes many kinds of material ingredient absorption in the object and the absorption overlap among different components is serious, the method of tunable diode laser absorption spectroscopy combined with data modeling is proposed to carry on the examination. Also systematic research about this method and the mathematical derivation are given.
According to above findings and the certain analysis basis to the absorption spectrum principle as well as the influence factors, in view of present practical application, two sets of hardware systems are designed. The one is the differential optics absorption spectroscopy (DOAS) atmospheric environment quality monitor system and another one is continuous emission monitoring system (CEMS). In this part thorough discussion about the optical system is also made to guard against the contamination and one kind of simple mechanical structure is designed to prevent the dust dropping on the optical system in the examination.
Main innovation works in this thesis mainly include:
1. The correctional Lambert-Beer law is obtained using the optical transport model and the light scattering theory;
2. The calibration formula and the calibration curve in view of the temperature influence to the absorption spectrum have been obtained;
3. When examination material includes many ingredients and the absorption overlaps seriously one another, the method of tunable diode laser absorption spectroscopy combined with data modeling is proposed to carry on the examination
4. On the basis of designing two sets of application systems, one simple mechanical structure which will replace the traditional way of blowing dry pure air onto the lens is designed to prevent the dust dropping on the optical system in the examination.
引文
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