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CN103105366B - CO2 carbon isotope infrared spectrum detection method and device - Google Patents

CO2 carbon isotope infrared spectrum detection method and device Download PDF

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CN103105366B
CN103105366B CN201310023557.2A CN201310023557A CN103105366B CN 103105366 B CN103105366 B CN 103105366B CN 201310023557 A CN201310023557 A CN 201310023557A CN 103105366 B CN103105366 B CN 103105366B
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CN103105366A (en
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徐亮
李相贤
高闽光
王亚萍
石建国
童晶晶
金岭
李胜
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Hefei Zhongke Environmental Monitoring Technology National Engineering Laboratory Co ltd
Hefei Institutes of Physical Science of CAS
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Anhui Institute of Optics and Fine Mechanics of CAS
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Abstract

本发明公开了一种CO2碳同位素红外光谱检测方法及装置,装置采用、反射池、红外光源、离轴抛物面反射镜、干涉仪、与计算机连接的红外探测器、输入含有CO2待测气体的待测气输入气路和输入已知δ13CO2值的标准CO2气体的标准气输入气路,本发明方法根据红外探测器获得的红外光谱来得到被测气体的δ13CO2值。

The invention discloses a CO 2 carbon isotope infrared spectrum detection method and device. The device adopts a reflection pool, an infrared light source, an off-axis parabolic reflector, an interferometer, an infrared detector connected with a computer, and an input gas containing CO 2 to be measured. The input gas path of the gas to be measured and the standard gas input gas path of the standard CO gas with a known δ 13 CO 2 value, the method of the present invention obtains the δ 13 CO 2 value of the gas to be measured according to the infrared spectrum obtained by the infrared detector .

Description

CO2碳同位素红外光谱检测方法及装置CO2 carbon isotope infrared spectrum detection method and device

技术领域 technical field

    本发明涉及环境监测技术与分析及光学技术领域,具体为一种CO2碳同位素红外光谱检测装置。     The invention relates to the field of environmental monitoring technology and analysis and optical technology, in particular to a CO2 carbon isotope infrared spectrum detection device.

背景技术 Background technique

CO2是大气中最重要的温室气体之一,由于不同同位素存在不同的物理、化学、生物变化过程,因此,分析CO2碳同位素比有利于确定碳元素源与汇,为全球碳排放预算提供数据支持。近年来,CO2气体碳同位素比值检测技术在多个研究领域都得到了广泛应用。譬如:在环境科学和生态系统科学领域,自然界中的能量转换过程大多会伴随产生CO2,但不同的碳同位素反映不同的反应过程,揭示了土壤、植物等自然因素和各类人为活动的不同影响;在火山爆发预测研究中,地壳释放气体可与地表上通过路径的岩石或其他液体反应,因此,δ13CO2值的变化可以作为判断火山活动增强,火山喷发预测的有效指标;在医学诊断领域,气体同位素检测还可以作为非入侵性医疗诊断,CO2的同位素比值被认为幽门螺旋杆菌存在的标志物(2005年诺贝尔医学或生理学奖),消化性溃疡和胃癌与这种细菌相关,因此,可以通过对人体呼出CO2气体δ13CO2值变化的检测来早期诊断消化性溃疡和胃癌等疾病。 CO 2 is one of the most important greenhouse gases in the atmosphere. Because different isotopes have different physical, chemical, and biological change processes, the analysis of the carbon isotope ratio of CO 2 is conducive to determining the source and sink of carbon elements and providing a basis for the global carbon emission budget. data support. In recent years, CO 2 gas carbon isotope ratio detection technology has been widely used in many research fields. For example: in the fields of environmental science and ecosystem science, most energy conversion processes in nature are accompanied by the production of CO 2 , but different carbon isotopes reflect different reaction processes, revealing the differences between natural factors such as soil and plants and various human activities. Influence; in the study of volcanic eruption prediction, the gas released from the crust can react with rocks or other liquids passing through the path on the surface, therefore, the change of δ 13 CO 2 value can be used as an effective indicator for judging the enhancement of volcanic activity and volcanic eruption prediction; in medicine In the field of diagnosis, gas isotope detection can also be used as a non-invasive medical diagnosis. The isotope ratio of CO 2 is considered as a marker for the presence of Helicobacter pylori (Nobel Prize in Medicine or Physiology in 2005), peptic ulcer and gastric cancer are related to this bacterium Therefore, diseases such as peptic ulcer and gastric cancer can be diagnosed early by detecting changes in the value of δ 13 CO 2 in exhaled CO 2 gas.

目前,CO2碳同位素比值检测的传统方法是同位素质谱(IRMS)法。同位素质谱法测量同位素的基本原理是依据分子质量不同所造成的弯曲路径不同而区分同位素分子。该方法却无法分辨分子质量相同的异构体,比如:分子量同为45的13C16O212C16O17O将无法利用同位素质谱法进行分辨,另外,同位素质谱法检测需要取样预处理,且仪器系统庞大、操作复杂,只能进行实验室分析,具有一定的局限性,尤其不适合实时的连续测量。 At present, the traditional method for CO2 carbon isotope ratio detection is the isotope mass spectrometry (IRMS) method. The basic principle of measuring isotopes by isotope mass spectrometry is to distinguish isotope molecules according to the different curved paths caused by different molecular masses. However, this method cannot distinguish isomers with the same molecular weight. For example, 13 C 16 O 2 and 12 C 16 O 17 O with the same molecular weight of 45 cannot be resolved by isotope mass spectrometry. Processing, and the instrument system is huge and the operation is complicated, so it can only be used for laboratory analysis, which has certain limitations, especially not suitable for real-time continuous measurement.

红外光谱法是利用气体分子红外吸收光谱特性进行气体定性定量测量的光谱分析技术,具有测量精度高,可以实现实时、在线、无人值守等优势,可以实现CO2碳同位素比值实验现场在线分析测量,利用红外光谱法分析CO2碳同位素比值可以有效弥补传统检测技术的缺陷。 Infrared spectroscopy is a spectral analysis technology that uses the infrared absorption spectrum characteristics of gas molecules to perform qualitative and quantitative gas measurement. It has high measurement accuracy and can realize the advantages of real-time, online, and unattended, and can realize on-site analysis and measurement of CO2 carbon isotope ratio experiments. , using infrared spectroscopy to analyze the carbon isotope ratio of CO2 can effectively make up for the defects of traditional detection techniques.

发明内容 Contents of the invention

本发明的目的是提供一种CO2碳同位素红外光谱检测装置,以解决传统检测CO2碳同位素比值技术无法实现实时、在线检测的缺陷。 The object of the present invention is to provide a CO 2 carbon isotope infrared spectrum detection device to solve the defect that the traditional CO 2 carbon isotope ratio detection technology cannot realize real-time and online detection.

为了达到上述目的,本发明所采用的技术方案为: In order to achieve the above object, the technical scheme adopted in the present invention is:

CO2碳同位素红外光谱检测装置,其特征在于:包括反射池,反射池入光口处设置有红外光源、离轴抛物面反射镜、干涉仪,反射池出光口处设置有与计算机连接的红外探测器,反射池进气口通过三通阀接入有输入含有CO2气体待测气的待测气输入气路和输入已知δ13CO2值的标准CO2气体的标准气输入气路,红外光源辐射具有连续红外光波的红外光,红外光依次经过离轴抛物面反射镜准直、干涉仪调制后由反射池的入光口进入反射池,并在反射池内经过多次往复反射后由反射池出光口出射至红外探测器。 The CO 2 carbon isotope infrared spectrum detection device is characterized in that it includes a reflective pool, an infrared light source, an off-axis parabolic reflector, and an interferometer are arranged at the light entrance of the reflective pool, and an infrared detector connected to a computer is arranged at the light exit of the reflective pool The air inlet of the reflective cell is connected to the test gas input circuit for inputting the test gas containing CO 2 gas and the standard gas input circuit for inputting the standard CO 2 gas with known δ 13 CO 2 value through the three-way valve. The infrared light source radiates infrared light with continuous infrared light waves. The infrared light is sequentially collimated by an off-axis parabolic reflector and modulated by an interferometer, and then enters the reflective pool from the light entrance of the reflective pool. The light outlet of the pool emits to the infrared detector.

所述的CO2碳同位素红外光谱检测装置,其特征在于:所述待测气输入气路包括依次通过管路连通的待测气采样口、粉尘过滤器、装有液氮的杜瓦罐、Nafion管、装有HE-3型干燥剂的干燥管、气体流量计,待测气从待测气采样口进入待测气输入气路,再依次经过过滤器滤掉粉尘、杜瓦罐进行一级干燥、 Nafion管进行二级干燥、装有HE-3型干燥剂的干燥管进行三级干燥、气体流量计计量后通过三通阀送入反射池中。 The CO2 carbon isotope infrared spectrum detection device is characterized in that: the input gas path of the gas to be tested includes a gas sampling port to be tested, a dust filter, a Dewar tank equipped with liquid nitrogen, Nafion tube, drying tube with HE-3 type desiccant, gas flow meter, the gas to be tested enters the gas input path from the gas sampling port to be tested, and then passes through the filter to filter out dust, and the Dewar tank for a Stage drying, Nafion tube for secondary drying, drying tube equipped with HE-3 desiccant for tertiary drying, gas flowmeter metered and sent to the reflection pool through the three-way valve.

所述标准气输入气路包括依次通过管路连通的标准气进气口、气体流量计,标准气从标准气进气口进入标准气输入气路,再经过气体流量计计量后通过三通阀送入反射池中。 The standard gas input gas path includes a standard gas inlet and a gas flowmeter connected through the pipeline in turn. The standard gas enters the standard gas input gas path from the standard gas inlet, and then passes through the three-way valve after being measured by the gas flowmeter. into the reflecting pool.

所述的CO2碳同位素红外光谱检测装置,其特征在于:所述三通阀具有a、b、c三个方向的阀口,三通阀a方向阀口与反射池进气口连接,三通阀b方向阀口接入标准气输入气路,三通阀c方向阀口接入待测气输入气路,,三通阀a方向阀口常通;当反射池进气为标准气时,三通阀a-b方向阀口气路通气,a-c方向阀口气路闭合;当反射池进气为待测气时,三通阀a-b方向阀口气口闭合,a-c方向阀口气路通气。 The CO2 carbon isotope infrared spectrum detection device is characterized in that: the three-way valve has valve ports in three directions a, b and c, and the valve port in direction a of the three-way valve is connected with the air inlet of the reflection pool, and the three-way valve The valve port in the direction b of the one-way valve is connected to the input gas path of the standard gas, the valve port in the direction c of the three-way valve is connected to the input gas path of the gas to be tested, and the valve port in the direction a of the three-way valve is normally open; , the three-way valve ab direction valve port is ventilated, and the ac direction valve port is closed.

所述的CO2碳同位素红外光谱检测装置,其特征在于:所述反射池出气口通过流量控制阀与Nafion管连通,反射池排出的干燥气体通过流量控制阀送入Nafion管,作为Nafion管的反吹气体。 The CO carbon isotope infrared spectrum detection device is characterized in that: the gas outlet of the reflective pool is communicated with the Nafion tube through a flow control valve, and the dry gas discharged from the reflective pool is sent into the Nafion tube through the flow control valve, as the Nafion tube. Blowback gas.

所述的CO2碳同位素红外光谱检测装置,其特征在于:所述红外光源、红外探测器、干涉仪构成傅里叶变换红外光谱仪,其中红外光源采用硅碳棒加热元件,红外探测器采用锑化铟探测器,干涉仪为迈克尔逊干涉仪;傅里叶红外光谱仪与反射池共同置于密封箱内,所述密封箱接入有吹扫口,密封箱在采集光谱过程中以0.5l/min流速实时吹扫高纯氮气。 The CO2 carbon isotope infrared spectrum detection device is characterized in that: the infrared light source, infrared detector, and interferometer constitute a Fourier transform infrared spectrometer, wherein the infrared light source adopts a silicon carbide rod heating element, and the infrared detector adopts antimony The indium detector, the interferometer is a Michelson interferometer; the Fourier transform infrared spectrometer and the reflective cell are placed in a sealed box together, and the sealed box is connected with a purge port, and the sealed box is used in the process of collecting spectra with 0.5l/ The min flow rate is used to purge high-purity nitrogen in real time.

所述的CO2碳同位素红外光谱检测装置,其特征在于:还包括压力监测系统、温度监测系统、温度控制系统,其中: The CO carbon isotope infrared spectrum detection device is characterized in that it also includes a pressure monitoring system, a temperature monitoring system, and a temperature control system, wherein:

压力监测系统包括高精度的压力传感探头和设置在计算机中的压力显示记录软件,压力传感探头置于反射池内,压力传感探头的数据线接到计算机上以实时记录反射池内压力数据,以及监测反射池内压力随时间变化情况,压力精度达±1mb; The pressure monitoring system includes a high-precision pressure sensing probe and pressure display and recording software set in the computer. The pressure sensing probe is placed in the reflection pool, and the data line of the pressure sensing probe is connected to the computer to record the pressure data in the reflection pool in real time. And monitor the change of pressure in the reflection pool with time, the pressure accuracy can reach ±1mb;

温度监测系统包括高精度的温度传感探头和设置在计算机中的温度显示记录软件,温度传感探头置于反射池内,温度传感探头的数据线接到电脑上以实时记录反射池内温度数据,以及监测反射池内温度随时间变化情况,温度精度达±0.01℃; The temperature monitoring system includes a high-precision temperature sensing probe and temperature display and recording software set in the computer. The temperature sensing probe is placed in the reflection pool, and the data line of the temperature sensing probe is connected to the computer to record the temperature data in the reflection pool in real time. And monitor the temperature change with time in the reflecting pool, the temperature accuracy is up to ±0.01℃;

温度控制系统包括加热板、温度反馈控制电路、pt100温度探头和温度显示表头,加热板包围在反射池内壁,pt100温度探头包在加热板内侧以实时监测反射池表面温度,将加热板预加热温度设置为28℃,温度反馈控制电路根据pt100监测的温度控制加热板通断,pt100温度探头与加热板均接入温度控制盒,温度显示表头安装在控制盒内,温度显示表头实时显示设置加热温度和pt100监测的实际温度。 The temperature control system includes a heating plate, a temperature feedback control circuit, a pt100 temperature probe and a temperature display head. The heating plate is surrounded by the inner wall of the reflecting pool, and the pt100 temperature probe is wrapped inside the heating plate to monitor the surface temperature of the reflecting pool in real time and preheat the heating plate. The temperature is set to 28°C, the temperature feedback control circuit controls the heating plate on and off according to the temperature monitored by pt100, the pt100 temperature probe and the heating plate are connected to the temperature control box, the temperature display head is installed in the control box, and the temperature display head is displayed in real time Set heating temperature and actual temperature monitored by pt100.

所述装置的CO2碳同位素红外光谱检测方法,其特征在于:首先将反射池抽成固定的低压,然后通过标准气输入气路向反射池中充入高纯氮气至1013mb,重复以上过程3次,待反射池内高纯氮气保持在1013mb恒定压力、28℃恒定温度后,利用红外光源向反射池辐射红外光,并利用红外探测器采集高纯氮气光谱作为背景光谱,用作定量分析的背景; The CO carbon isotope infrared spectrum detection method of the described device is characterized in that: first pump the reflective pool into a fixed low pressure, then fill the reflective pool with high-purity nitrogen to 1013 mb through the standard gas input gas path, and repeat the above process 3 times After the high-purity nitrogen gas in the reflection pool is kept at a constant pressure of 1013 mb and a constant temperature of 28 ° C, the infrared light source is used to radiate infrared light to the reflection pool, and the infrared detector is used to collect the spectrum of high-purity nitrogen gas as the background spectrum, which is used as the background of quantitative analysis;

当采集完背景光谱,将反射池内抽成固定的低压,然后通过标准气输入气路充入已知δ13CO2值的标准CO2标准气至1013mb,重复以上过程3次,待反射池内标准CO2气体保持在1013mb恒定压力、28℃恒定温度后,利用红外光源向反射池辐射红外光,并利用红外探测器采集标准CO2气体光谱,由背景光谱和标准CO2气体光谱反演得到标准CO2气体的δ13CO2反演值,由反演的δ13CO2反演值与标准CO2气体实际的δ13CO2值进行比较得到校准系数,作为下面待测气体校准的依据; When the background spectrum is collected, the reflection cell is pumped to a fixed low pressure, and then the standard CO 2 standard gas with a known δ 13 CO 2 value is filled to 1013mb through the standard gas input gas path, and the above process is repeated 3 times until the standard gas in the reflection cell After the CO 2 gas is kept at a constant pressure of 1013mb and a constant temperature of 28°C, the infrared light source is used to radiate infrared light to the reflection pool, and the standard CO 2 gas spectrum is collected by an infrared detector. The standard CO 2 gas spectrum is retrieved from the background spectrum and the standard CO 2 gas spectrum. The δ 13 CO 2 inversion value of CO 2 gas, the calibration coefficient is obtained by comparing the inversion δ 13 CO 2 inversion value with the actual δ 13 CO 2 value of the standard CO 2 gas, as the basis for the calibration of the gas to be measured below;

最后通过待测气输入气路向反射池中充入待测气CO2至1013mb恒定压力、28℃恒定温度后,利用红外光源向反射池辐射红外光,并利用红外探测器采集待测气红外光谱,由背景光谱和待测气红外光谱反演得到待测气体的δ13CO2反演值,再结合校准系数对待测气体的δ13CO2反演值进行修正得到待测气的δ13CO2测量值。 Finally, the gas to be tested is filled into the reflective cell through the input gas path of the gas to be tested, after the constant pressure of CO 2 to 1013mb and the constant temperature of 28°C, the infrared light source is used to radiate infrared light to the reflective pool, and the infrared detector is used to collect the infrared spectrum of the gas to be tested , the δ 13 CO 2 inversion value of the gas to be measured is obtained from the inversion of the background spectrum and the infrared spectrum of the gas to be measured, and the δ 13 CO 2 inversion value of the gas to be measured is corrected by combining the calibration coefficient to obtain the δ 13 CO 2 of the gas to be measured 2 measured values.

所述的CO2碳同位素红外光谱检测方法,其特征在于:经过干涉仪调制的红外光形成干涉信号,红外光经过反射池,由干涉信号进行傅里叶变换得到的光谱图表征了反射池内气体的吸收特征。 The CO2 carbon isotope infrared spectrum detection method is characterized in that: the infrared light modulated by the interferometer forms an interference signal, the infrared light passes through the reflective cell, and the spectrum obtained by Fourier transform of the interference signal characterizes the gas in the reflective cell absorption characteristics.

所述的CO2碳同位素红外光谱检测方法,其特征在于:在CO2碳同位素比值定量反演中将12CO213CO2作为两种独立的组分来对待。 The CO 2 carbon isotope infrared spectrum detection method is characterized in that 12 CO 2 and 13 CO 2 are treated as two independent components in the quantitative inversion of the CO 2 carbon isotope ratio.

本发明可以实现实时、在线、无人值守测量CO2碳同位素比值,拓宽了红外光谱法的应用领域范围。 The invention can realize the real-time, on-line and unattended measurement of the carbon isotope ratio of CO 2 , which broadens the scope of the application field of the infrared spectrometry.

附图说明 Description of drawings

图1为本发明结构原理图。 Fig. 1 is a structural schematic diagram of the present invention.

具体实施方式 Detailed ways

CO2碳同位素红外光谱检测装置,包括反射池,反射池入光口处设置有红外光源、离轴抛物面反射镜、干涉仪,反射池出光口处设置有与计算机连接的红外探测器,反射池进气口通过三通阀接入有输入含有CO2气体待测气的待测气输入气路和输入已知δ13CO2值的标准CO2气体的标准气输入气路,红外光源辐射具有连续红外光波的红外光,红外光依次经过离轴抛物面反射镜准直、干涉仪调制后由反射池的入光口进入反射池,并在反射池内经过多次往复反射后由反射池出光口出射至红外探测器。 The CO 2 carbon isotope infrared spectrum detection device includes a reflection pool, an infrared light source, an off-axis parabolic reflector, and an interferometer are arranged at the light entrance of the reflection pool, an infrared detector connected to a computer is arranged at the light exit of the reflection pool, and the reflection pool The air inlet is connected to the test gas input gas path containing CO 2 gas to be tested through the three-way valve and the standard gas input gas path to input the standard CO 2 gas with known δ 13 CO 2 value. The infrared light source radiation has The infrared light of the continuous infrared light wave, the infrared light is collimated by the off-axis parabolic reflector and modulated by the interferometer, enters the reflective pool from the light entrance of the reflective pool, and exits from the light exit of the reflective pool after multiple reciprocating reflections in the reflective pool to the infrared detector.

待测气输入气路包括依次通过管路连通的待测气采样口、粉尘过滤器、装有液氮的杜瓦罐、Nafion管、装有HE-3型干燥剂的干燥管、气体流量计,待测气从待测气采样口进入待测气输入气路,再依次经过过滤器滤掉粉尘、杜瓦罐进行一级干燥、 Nafion管进行二级干燥、装有HE-3型干燥剂的干燥管进行三级干燥、气体流量计计量后通过三通阀送入反射池中。 The input gas path of the gas to be tested includes the sampling port of the gas to be tested, a dust filter, a Dewar tank filled with liquid nitrogen, a Nafion tube, a drying tube filled with a HE-3 desiccant, and a gas flowmeter, which are connected sequentially through the pipeline. , the gas to be tested enters the input gas path of the gas to be tested from the sampling port of the gas to be tested, and then passes through the filter to filter out dust, the Dewar tank is used for primary drying, the Nafion tube is used for secondary drying, and HE-3 desiccant is installed The drying pipe is subjected to three-stage drying, and the gas flow meter measures it and sends it into the reflection pool through the three-way valve.

标准气输入气路包括依次通过管路连通的标准气进气口、气体流量计,标准气从标准气进气口进入标准气输入气路,再经过气体流量计计量后通过三通阀送入反射池中。 The standard gas input gas path includes the standard gas inlet and the gas flowmeter connected through the pipeline in turn. The standard gas enters the standard gas input gas path from the standard gas inlet, and then is sent through the three-way valve after being measured by the gas flowmeter. in the reflecting pool.

三通阀具有a、b、c三个方向的阀口,三通阀a方向阀口与反射池进气口连接,三通阀b方向阀口接入标准气输入气路,三通阀c方向阀口接入待测气输入气路,,三通阀a方向阀口常通;当反射池进气为标准气时,三通阀a-b方向阀口气路通气,a-c方向阀口气路闭合;当反射池进气为待测气时,三通阀a-b方向阀口气口闭合,a-c方向阀口气路通气。 The three-way valve has valve ports in three directions a, b, and c. The valve port in the direction a of the three-way valve is connected to the air inlet of the reflection pool. The direction valve port is connected to the input gas path of the gas to be tested, and the three-way valve a direction valve port is normally open; when the inlet air of the reflection pool is standard gas, the gas path of the three-way valve a-b direction valve port is ventilated, and the a-c direction valve port gas path is closed; When the inlet air of the reflecting pool is the gas to be tested, the gas port of the three-way valve a-b direction valve port is closed, and the gas path of the a-c direction valve port is ventilated.

反射池出气口通过流量控制阀与Nafion管连通,反射池排出的干燥气体通过流量控制阀送入Nafion管,作为Nafion管的反吹气体。 The gas outlet of the reflection pool is connected with the Nafion tube through the flow control valve, and the dry gas discharged from the reflection pool is sent into the Nafion tube through the flow control valve as the blowback gas of the Nafion tube.

红外光源、红外探测器、干涉仪构成傅里叶变换红外光谱仪,其中红外光源采用硅碳棒加热元件,红外探测器采用锑化铟探测器,干涉仪为迈克尔逊干涉仪;傅里叶红外光谱仪与反射池共同置于密封箱内,所述密封箱接入有吹扫口,密封箱在采集光谱过程中以0.5l/min流速实时吹扫高纯氮气。 Infrared light source, infrared detector, and interferometer constitute a Fourier transform infrared spectrometer, in which the infrared light source uses a silicon carbide rod heating element, the infrared detector uses an indium antimonide detector, and the interferometer is a Michelson interferometer; the Fourier transform infrared spectrometer It is placed in a sealed box together with the reflection pool, and the sealed box is connected with a purge port, and the sealed box is purged with high-purity nitrogen gas at a flow rate of 0.5 l/min in real time during the spectrum collection process.

还包括压力监测系统、温度监测系统、温度控制系统,其中: Also includes pressure monitoring system, temperature monitoring system, temperature control system, of which:

压力监测系统包括高精度的压力传感探头和设置在计算机中的压力显示记录软件,压力传感探头置于反射池内,压力传感探头的数据线接到计算机上以实时记录反射池内压力数据,以及监测反射池内压力随时间变化情况,压力精度达±1mb; The pressure monitoring system includes a high-precision pressure sensing probe and pressure display and recording software set in the computer. The pressure sensing probe is placed in the reflection pool, and the data line of the pressure sensing probe is connected to the computer to record the pressure data in the reflection pool in real time. And monitor the change of pressure in the reflection pool with time, the pressure accuracy can reach ±1mb;

温度监测系统包括高精度的温度传感探头和设置在计算机中的温度显示记录软件,温度传感探头置于反射池内,温度传感探头的数据线接到电脑上以实时记录反射池内温度数据,以及监测反射池内温度随时间变化情况,温度精度达±0.01℃; The temperature monitoring system includes a high-precision temperature sensing probe and temperature display and recording software set in the computer. The temperature sensing probe is placed in the reflection pool, and the data line of the temperature sensing probe is connected to the computer to record the temperature data in the reflection pool in real time. And monitor the temperature change with time in the reflecting pool, the temperature accuracy is up to ±0.01℃;

温度控制系统包括加热板、温度反馈控制电路、pt100温度探头和温度显示表头,加热板包围在反射池内壁,pt100温度探头包在加热板内侧以实时监测反射池表面温度,将加热板预加热温度设置为28℃,温度反馈控制电路根据pt100监测的温度控制加热板通断,pt100温度探头与加热板均接入温度控制盒,温度显示表头安装在控制盒内,温度显示表头实时显示设置加热温度和pt100监测的实际温度。 The temperature control system includes a heating plate, a temperature feedback control circuit, a pt100 temperature probe and a temperature display head. The heating plate is surrounded by the inner wall of the reflecting pool, and the pt100 temperature probe is wrapped inside the heating plate to monitor the surface temperature of the reflecting pool in real time and preheat the heating plate. The temperature is set to 28°C, the temperature feedback control circuit controls the heating plate on and off according to the temperature monitored by pt100, the pt100 temperature probe and the heating plate are connected to the temperature control box, the temperature display head is installed in the control box, and the temperature display head is displayed in real time Set heating temperature and actual temperature monitored by pt100.

一种CO2碳同位素红外光谱检测方法,首先将反射池抽成固定的低压,然后通过标准气输入气路向反射池中充入高纯氮气至1013mb,重复以上过程3次,待反射池内高纯氮气保持在1013mb恒定压力、28℃恒定温度后,利用红外光源向反射池辐射红外光,并利用红外探测器采集高纯氮气光谱作为背景光谱,用作定量分析的背景; A CO 2 carbon isotope infrared spectrum detection method, first pumping the reflective pool to a fixed low pressure, then filling the reflective pool with high-purity nitrogen to 1013 mb through the standard gas input gas path, repeating the above process 3 times, and waiting for high-purity nitrogen in the reflective pool After the nitrogen gas is kept at a constant pressure of 1013mb and a constant temperature of 28°C, the infrared light source is used to radiate infrared light to the reflection pool, and the infrared detector is used to collect the spectrum of high-purity nitrogen gas as the background spectrum, which is used as the background of quantitative analysis;

当采集完背景光谱,将反射池内抽成固定的低压,然后通过标准气输入气路充入已知δ13CO2值的标准CO2标准气至1013mb,重复以上过程3次,待反射池内标准CO2气体保持在1013mb恒定压力、28℃恒定温度后,利用红外光源向反射池辐射红外光,并利用红外探测器采集标准CO2气体光谱,由背景光谱和标准CO2气体光谱反演得到标准CO2气体的δ13CO2反演值,由反演的δ13CO2反演值与标准CO2气体实际的δ13CO2值进行比较得到校准系数,作为下面待测气体校准的依据; When the background spectrum is collected, the reflection cell is pumped to a fixed low pressure, and then the standard CO 2 standard gas with a known δ 13 CO 2 value is filled to 1013mb through the standard gas input gas path, and the above process is repeated 3 times until the standard gas in the reflection cell After the CO 2 gas is kept at a constant pressure of 1013mb and a constant temperature of 28°C, the infrared light source is used to radiate infrared light to the reflection pool, and the standard CO 2 gas spectrum is collected by an infrared detector. The standard CO 2 gas spectrum is retrieved from the background spectrum and the standard CO 2 gas spectrum. The δ 13 CO 2 inversion value of CO 2 gas, the calibration coefficient is obtained by comparing the inversion δ 13 CO 2 inversion value with the actual δ 13 CO 2 value of the standard CO 2 gas, as the basis for the calibration of the gas to be measured below;

最后通过待测气输入气路向反射池中充入待测气CO2至1013mb恒定压力、28℃恒定温度后,利用红外光源向反射池辐射红外光,并利用红外探测器采集待测气红外光谱,由背景光谱和待测气红外光谱反演得到待测气体的δ13CO2反演值,再结合校准系数对待测气体的δ13CO2反演值进行修正得到待测气的δ13CO2测量值。 Finally, the gas to be tested is filled into the reflective cell through the input gas path of the gas to be tested, after the constant pressure of CO 2 to 1013mb and the constant temperature of 28°C, the infrared light source is used to radiate infrared light to the reflective pool, and the infrared detector is used to collect the infrared spectrum of the gas to be tested , the δ 13 CO 2 inversion value of the gas to be measured is obtained from the inversion of the background spectrum and the infrared spectrum of the gas to be measured, and the δ 13 CO 2 inversion value of the gas to be measured is corrected by combining the calibration coefficient to obtain the δ 13 CO 2 of the gas to be measured 2 measured values.

经过干涉仪调制的红外光形成干涉信号,红外光经过反射池,由干涉信号进行傅里叶变换得到的光谱图表征了反射池内气体的吸收特征。 The infrared light modulated by the interferometer forms an interference signal, and the infrared light passes through the reflection cell, and the spectrum obtained by Fourier transform of the interference signal characterizes the absorption characteristics of the gas in the reflection cell.

在CO2碳同位素比值定量反演中将12CO213CO2作为两种独立的组分来对待。 12 CO 2 and 13 CO 2 are treated as two independent components in the quantitative inversion of CO 2 carbon isotope ratio.

如图1所示。傅里叶变换红外光谱仪18、探测器15、光源17和多次反射池11均置于密封箱13内,在光谱采集过程中密封箱实时以0.5l/min流速的高纯氮气吹扫,保证密封箱内光谱仪光路上不含有多余的水汽和CO2气体。当三通阀8的a-b方向关闭,a-c方向通气时,现场待测气在抽气泵的工作下,先经过过滤器2的过滤,滤除掉空气中的粉尘,然后气管经过杜瓦罐3内液氮的冷凝可以除掉待测气中的一部分水汽,经过一级干燥的待测气依次再经过Nafion管4和装有HE-3高效变色干燥剂的干燥管5的二、三级干燥,再经过气体流量计7和三通阀8进入多次反射样品池11。当三通阀8的a-c方向关闭,a-b方向通气时,标准气体经过气体流量计7和三通阀8进入反射池。CO2碳同位素红外光谱检测装置每日校准一次,校准时,首先将反射池抽成固定的低压(<1mb),然后充入高纯氮气至1013mb,重复以上过程3次,待反射池内高纯氮气保持在1013mb、28℃恒定温度、压力后,采集高纯氮气光谱作为背景光谱用作以后定量分析的背景;当采集完背景光谱,将反射池内抽成低压(<1mb),然后充入校准气体至1013mb,重复以上过程3次,待反射池内标准气体保持在1013mb、28℃恒定温度、压力后,采集标准气体光谱,反演标准气体碳同位素比值作为下面气体校准的依据。采集光谱过程中,每条光谱采用64scans扫描,在CO2碳同位素比值定量反演中将12CO213CO2作为两种独立的组分来对待。 As shown in Figure 1. The Fourier transform infrared spectrometer 18, detector 15, light source 17 and multiple reflection cell 11 are all placed in the sealed box 13, and the sealed box is purged with high-purity nitrogen at a flow rate of 0.5 l/min in real time during the spectrum collection process to ensure The optical path of the spectrometer in the sealed box does not contain excess water vapor and CO 2 gas. When the ab direction of the three-way valve 8 is closed and the ac direction is ventilated, the gas to be tested on site is filtered by the filter 2 under the work of the air pump to filter out the dust in the air, and then the gas pipe passes through the Dewar tank 3 Condensation of liquid nitrogen can remove part of the water vapor in the gas to be tested, and the gas to be tested after the primary drying is then passed through the Nafion tube 4 and the drying tube 5 equipped with HE-3 high-efficiency color-changing desiccant for the second and third stages of drying, and then Pass through the gas flow meter 7 and the three-way valve 8 into the multiple reflection sample cell 11 . When the ac direction of the three-way valve 8 is closed and the ab direction is ventilated, the standard gas enters the reflection pool through the gas flow meter 7 and the three-way valve 8 . The CO 2 carbon isotope infrared spectrum detection device is calibrated once a day. When calibrating, first pump the reflection pool to a fixed low pressure (<1mb), then fill it with high-purity nitrogen to 1013mb, repeat the above process 3 times, and wait until the reflection pool is high-purity. After the nitrogen gas is kept at 1013mb, 28°C constant temperature and pressure, the high-purity nitrogen spectrum is collected as the background spectrum for subsequent quantitative analysis; when the background spectrum is collected, the reflection cell is pumped to a low pressure (<1mb), and then filled into the calibration When the gas reaches 1013mb, repeat the above process 3 times. After the standard gas in the reflection cell is kept at 1013mb and 28°C at a constant temperature and pressure, collect the standard gas spectrum and invert the carbon isotope ratio of the standard gas as the basis for the following gas calibration. In the process of collecting spectra, each spectrum was scanned by 64scans, and 12 CO 2 and 13 CO 2 were treated as two independent components in the quantitative inversion of CO 2 carbon isotope ratio.

Claims (2)

1.CO 2carbon isotope infrared spectrum pick-up unit, it is characterized in that: comprise reflection tank, reflection tank light inlet place is provided with infrared light supply, off-axis parabolic mirror, interferometer, reflection tank light-emitting window place is provided with the infrared eye be connected with computing machine, and reflection tank air intake opening has access to input containing CO by T-valve 2the gas input gas circuit to be measured of gas gas to be measured and the known δ of input 13cO 2the standard C O of value 2the Standard Gases input gas circuit of gas, infrared light supply radiation has the infrared light of continuous infrared waves, infrared light successively through off-axis parabolic mirror collimation, interferometer modulation after enter reflection tank by the light inlet of reflection tank, and in reflection tank through repeatedly after interflection by the outgoing of reflection tank light-emitting window to infrared eye;
Described gas to be measured input gas circuit comprise successively by the gas thief hatch to be measured of pipeline connection, dust filter unit, the Dewar tank that liquid nitrogen is housed, Nafion pipe, drying tube, the gas meter of HE-3 type drying agent are housed, gas to be measured enters gas to be measured input gas circuit from gas thief hatch to be measured, then filter dust through filtrator successively, Dewar tank carries out one-level drying, Nafion pipe carries out secondary drying, be equipped with after the drying tube of HE-3 type drying agent carries out three-stage drying, gas meter metering and sent in reflection tank by T-valve; Described Standard Gases input gas circuit comprises successively by Standard Gases air intake opening, the gas meter of pipeline connection, and Standard Gases from Standard Gases air intake opening Engage of standard gas input gas circuit, then is sent in reflection tank by T-valve after gas meter metering;
Described T-valve has the valve port in a, b, c tri-directions, and T-valve a direction valve port is connected with reflection tank air intake opening, T-valve b direction valve port access Standard Gases input gas circuit, and T-valve c direction valve port accesses gas to be measured input gas circuit, T-valve a direction valve port normal open; When reflection tank air inlet is Standard Gases, ventilate in T-valve a-b direction valve implication road, and a-c direction valve implication road closes; When reflection tank air inlet is gas to be measured, T-valve a-b direction valve implication mouth closes, and ventilates in a-c direction valve implication road;
Described reflection tank gas outlet is communicated with Nafion pipe by flowrate control valve, and the dry gas that reflection tank is discharged sends into Nafion pipe, as the purge gas of Nafion pipe by flowrate control valve;
Described infrared light supply, infrared eye, interferometer form Fourier transform infrared spectrometer, and its mid-infrared light source adopts Globar heating element, and infrared eye adopts indium antimonide detector, and interferometer is Michelson interferometer; Fourier infrared spectrograph and reflection tank are placed in seal box jointly, and described seal box has access to blow valve port, and seal box purges high pure nitrogen in real time with 0.5l/min flow velocity in collection spectroscopy procedure;
Also comprise pressure monitor system, temperature monitoring system, temperature control system, wherein:
Pressure monitor system comprises high-precision pressure sensing probe and arranges pressure display logging software in a computer, pressure sensing probe is placed in reflection tank, the data line of pressure sensing probe is received on computing machine with pressure data in real time record reflection tank, and pressure situation of change in time in monitoring reflection tank, pressure precision reaches ± 1mb;
The Temperature displaying logging software that temperature monitoring system comprises high-precision temperature sensing probe and arranges in a computer, temperature sensing probe is placed in reflection tank, the data line of temperature sensing probe is received on computer with temperature data in real time record reflection tank, and temperature situation of change in time in monitoring reflection tank, temperature accuracy reaches ± and 0.01 DEG C;
Temperature control system comprises heating plate, temperature feedback control circuit, pt100 temp probe and Temperature displaying gauge outfit, heating plate is enclosed in reflection tank inwall, pt100 temp probe wraps in inside heating plate with Real-Time Monitoring reflection tank surface temperature, heating plate pre-heating temperature is set to 28 DEG C, the temperature that temperature feedback control circuit is monitored according to pt100 controls heating plate break-make, pt100 temp probe and the equal cut-in temperature control enclosure of heating plate, Temperature displaying gauge outfit is arranged in control enclosure, Temperature displaying gauge outfit shows the actual temperature arranging heating-up temperature and pt100 monitoring in real time.
2. the CO based on device described in claim 1 2carbon isotope infrared spectrum detection method, it is characterized in that: first reflection tank is pumped into fixing low pressure, then in reflection tank, high pure nitrogen is filled with to 1013mb by Standard Gases input gas circuit, repeat above process 3 times, after in pond to be reflected, high pure nitrogen remains on 1013mb constant pressure, 28 DEG C of steady temperatures, utilize infrared light supply to reflection tank irradiating infrared light, and utilize infrared eye to gather high pure nitrogen spectrum spectrum as a setting, as the background of quantitative test;
When having gathered background spectrum, fixing low pressure will be pumped in reflection tank, then be filled with known δ by Standard Gases input gas circuit 13cO 2the standard C O of value 2standard Gases, to 1013mb, repeats above process 3 times, pond internal standard CO to be reflected 2gas utilizes infrared light supply to reflection tank irradiating infrared light after remaining on 1013mb constant pressure, 28 DEG C of steady temperatures, and utilizes infrared eye to gather standard C O 2gaseous spectrum, by background spectrum and standard C O 2gaseous spectrum inverting obtains standard C O 2the δ of gas 13cO 2inverting value, by the δ of inverting 13cO 2inverting value and standard C O 2the δ of gas reality 13cO 2value compares and obtains calibration factor, as the foundation of gas calibration to be measured below;
In reflection tank, gas CO to be measured is filled with finally by gas input gas circuit to be measured 2to 1013mb constant pressure, 28 DEG C of steady temperatures, utilize infrared light supply to reflection tank irradiating infrared light, and utilize infrared eye to gather gas infrared spectrum to be measured, obtained the δ of gas to be measured by background spectrum and gas infrared spectrum to be measured inverting 13cO 2inverting value, then in conjunction with the δ of calibration factor to gas to be measured 13cO 2inverting value carries out revising the δ obtaining gas to be measured 13cO 2measured value;
Infrared light through interferometer modulation forms interference signal, and infrared light, through reflection tank, carries out by interference signal the Absorption Characteristics that spectrogram that Fourier transform obtains characterizes reflection pool gas;
At CO 2will in carbon isotope ratio quantitative inversion 12cO 2with 13cO 2as two kinds independently component treat.
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