CN106053361A - Spectrum reading and processing method and device of multiple sample cell spectral quantitative analysis - Google Patents
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Abstract
Description
【技术领域】【Technical field】
本发明涉及光谱分析领域,特别涉及物品成分及浓度的光谱分析。The invention relates to the field of spectral analysis, in particular to the spectral analysis of the composition and concentration of articles.
【背景技术】【Background technique】
光谱法可以实现几乎所有极性物品的定量分析。随着计算机技术,数据分析与处理技术的发展,近年来,红外光谱法、紫外光谱法已开始应用于气体、液体、甚至固体成分及浓度的在线分析领域,但目前的应用还存在诸多的问题。下面以气体分析为例来予以说明。Spectroscopy can achieve quantitative analysis of almost all polar substances. With the development of computer technology, data analysis and processing technology, in recent years, infrared spectroscopy and ultraviolet spectroscopy have begun to be used in the field of online analysis of gas, liquid, and even solid components and concentrations, but there are still many problems in the current application . Let's take gas analysis as an example to illustrate.
1)光谱分辨率较高时,可能导致光谱畸变。由于在光谱分辨率较高、扫描次数较多时,光谱扫描时间较长。例如,光谱分辨率为1cm-1,扫描次数为8时,得到一张光谱图所需时间约为60秒。若分辨率提高到0.5cm-1,扫描次数增加到32时,获得一张光谱图则需要约500秒的时间。气体在线分析过程中,待分析气体中的组分及其浓度是时刻都在变化的。由于光谱的获取方法是先获取以光强为输出的背景光谱,然后获得以光强为输出的待分析气体吸收光谱,再用吸收光谱除以背景光谱得到的以透光率为输出的光谱,这个光谱的常用对数值的负值,则为以吸光度为输出的光谱图。在实验分析应用中,一般默认光谱的获取过程中被分析气体成分及其浓度是不变的。显然,如果只采用一个测量气室进行气体的光谱在线分析,而且气体一直处于流动状态,则这个前提是不成立的。于是,在光谱扫描过程中,由于气体浓度的变化,每次得到的光谱图并非相同气体组分及相同浓度情况下的光谱图的均值,致使得到的光谱不稳定,甚至是畸变的,从而使得光谱分析结果出现较大的偏差,特别是在待分析混合气中存在吸收光谱严重交叠的情况下,尤其严重。1) When the spectral resolution is high, it may cause spectral distortion. When the spectral resolution is high and the number of scans is large, the spectral scanning time is longer. For example, when the spectral resolution is 1cm -1 and the number of scans is 8, the time required to obtain a spectral image is about 60 seconds. If the resolution is increased to 0.5cm -1 and the number of scans is increased to 32, it will take about 500 seconds to obtain a spectrogram. During the online gas analysis process, the components and their concentrations in the gas to be analyzed are changing all the time. Since the method of obtaining the spectrum is to obtain the background spectrum with the light intensity as the output first, then obtain the absorption spectrum of the gas to be analyzed with the light intensity as the output, and then divide the absorption spectrum by the background spectrum to obtain the output spectrum with the light transmittance, The negative value of the common logarithm of this spectrum is a spectrogram with absorbance as output. In the application of experimental analysis, the composition and concentration of the analyzed gas are generally unchanged during the acquisition of the default spectrum. Obviously, if only one measuring gas chamber is used for on-line spectral analysis of gas, and the gas is always in a flowing state, then this premise is not valid. Therefore, in the process of spectral scanning, due to the change of gas concentration, the spectral graph obtained each time is not the average value of the spectral graph under the same gas composition and the same concentration, which makes the obtained spectrum unstable or even distorted, thus making The results of spectral analysis have large deviations, especially in the case of serious overlap of absorption spectra in the gas mixture to be analyzed.
2)光谱仪长时间运行后,若环境发生变化,需要重新扫描背景光谱,则可能导致数据丢失。由于常规的光谱仪只有一个测量气室,长时间工作后,若发现环境参数发生较大变化,需要重新扫描背景光谱,则需要关闭气室气路,并通入背景气体,然后扫描背景光谱。由于气室的清洗需要较长时间,一般在数分钟,被测气体通入气室,使得被测组分气体浓度达到稳定,也需要数分钟,甚至更长的时间,因此,这种方法容易导致数据丢失,实时性较差;2) After the spectrometer has been running for a long time, if the environment changes and the background spectrum needs to be re-scanned, data may be lost. Since the conventional spectrometer has only one measuring gas chamber, after working for a long time, if it is found that the environmental parameters have changed greatly and the background spectrum needs to be re-scanned, the gas path of the gas chamber needs to be closed, and the background gas is introduced, and then the background spectrum is scanned. Since the cleaning of the gas chamber takes a long time, generally within a few minutes, the gas to be measured is passed into the gas chamber to stabilize the gas concentration of the measured component, and it also takes several minutes or even longer. Therefore, this method is easy Leading to data loss and poor real-time performance;
3)此外,在矿井瓦斯监测等应用场合,需要用多个气室从多个巷道取气,取气前后的时间可能较长,在数小时左右,难以保证取气前后,仪器的环境参数完全一致,包括环境中二氧化碳气体的浓度。由于被测气体浓度本身很小,因此,环境参数的变化可能导致分析结果偏差较大。3) In addition, in applications such as mine gas monitoring, it is necessary to use multiple gas chambers to obtain gas from multiple tunnels. The time before and after gas collection may be long, about several hours, and it is difficult to ensure that the environmental parameters of the instrument are completely accurate before and after gas collection. consistent, including the concentration of carbon dioxide gas in the environment. Since the measured gas concentration itself is very small, changes in environmental parameters may lead to large deviations in the analysis results.
为了克服上述问题,可以考虑增加一个、甚至多个气室,用其中一个气室充满背景气体,作为背景光谱扫描气室,其它作为测量气室,即扫描背景光谱时,将背景气室切入到光路中,光谱仪获得以光强为输出的背景光谱Back0,而在分析待测气体时,则将测量气室切入光路中,此时,光谱仪会扫描得到以光强为输出的测量光谱Measij(表示第i个测量气室第j次测量获得的光谱),然后执行式(1)获得以吸光度为输出的光谱。In order to overcome the above problems, it is possible to consider adding one or even more gas chambers, use one of the gas chambers to be filled with background gas, and use it as the background spectrum to scan the gas chamber, and the other as the measurement gas chamber, that is, when scanning the background spectrum, cut the background gas chamber into In the optical path, the spectrometer obtains the background spectrum Back0 with light intensity as the output, and when analyzing the gas to be measured, the measuring gas chamber is cut into the optical path, at this time, the spectrometer will scan to obtain the measurement spectrum Measij with the light intensity as the output (indicate The i-th measurement gas cell is the spectrum obtained by the j-th measurement), and then execute formula (1) to obtain the spectrum with the absorbance as the output.
Absorbij=-log(Measij/Back0) 式(1)Absorbij=-log(Measij/Back0) formula (1)
式中log(·)为常用对数,Absorbij表示第i个测量气室第j次测量获得的以吸光度为输出的光谱。发明专利ZL201110091432.4、ZL201410097985.4和ZL201410119733.7都是基于这种思想的。这种方法理论上可以解决上述问题,但前提条件是气室的物理参数必须完全一样,即不同气室的尺寸须做到几乎完全一样,框架材料也须加工成完全一样的。但窗片镀膜,如中红外光谱的KBr镀膜,要做到完全一样,那是非常困难的。由于窗片的吸收光谱不完全一样,这将给气体的吸收光谱带来如图1所示的基线漂移,甚至畸变,从而导致气体分析浓度偏差较大。In the formula, log(·) is the common logarithm, and Absorbij represents the spectrum with absorbance as the output obtained from the jth measurement of the i-th measuring cell. Invention patents ZL201110091432.4, ZL201410097985.4 and ZL201410119733.7 are all based on this idea. This method can theoretically solve the above problems, but the prerequisite is that the physical parameters of the air chambers must be exactly the same, that is, the dimensions of different air chambers must be almost exactly the same, and the frame materials must also be processed to be exactly the same. However, it is very difficult for window coatings, such as KBr coatings in the mid-infrared spectrum, to be exactly the same. Since the absorption spectra of the windows are not exactly the same, this will bring baseline drift or even distortion to the absorption spectra of the gas as shown in Figure 1, resulting in large deviations in gas analysis concentrations.
【发明内容】【Content of invention】
本发明的目的在于,提供一种多样品池光谱定量分析的光谱读取与处理方法及装置,以克服参考池与测量池之间的参数差异,特别是窗片吸收光谱不一致对吸收光谱所带来的影响。The purpose of the present invention is to provide a spectrum reading and processing method and device for multi-sample cell spectral quantitative analysis, to overcome the parameter difference between the reference cell and the measurement cell, especially the inconsistency of the absorption spectrum of the window to the absorption spectrum. Impact.
为了实现上述目的,本发明采用如下方式来进行吸收光谱读取与处理:In order to achieve the above object, the present invention uses the following methods to read and process the absorption spectrum:
一种多样品池光谱定量分析的光谱读取与处理方法,包括以下步骤:A spectral reading and processing method for spectral quantitative analysis of multi-sample cells, comprising the following steps:
(1)将样品池分为参考池和测量池,参考池标示为0,测量池依次标示为1、2、···N;(1) The sample pool is divided into a reference pool and a measurement pool, the reference pool is marked as 0, and the measurement pool is marked as 1, 2, ... N;
(2)对参考池和所有的测量池充满参考物,并按照背景光谱的方式扫描光谱,得到分别标示为Back0、Back1、Back2、···Back N的以光强为输出的光谱;其中Back0表示对参考池扫描得到的光谱,Back1表示对1号测量池扫描得到的光谱,其它依次类推;(2) Fill the reference cell and all the measuring cells with the reference substance, and scan the spectrum according to the background spectrum, and obtain the output spectra marked as Back0, Back1, Back2, Back N with light intensity as the output; where Back0 Indicates the spectrum obtained by scanning the reference cell, Back1 represents the spectrum obtained by scanning the No. 1 measuring cell, and so on;
(3)将样品池内的参考物更换为待分析物,再将参考池和测量池依次切入光路中,进行光谱扫描,得到分别标示为meas0、meas1、meas2、···meas N的以光强为输出的光谱;其中meas0表示对参考池扫描得到的光谱,meas1表示对1号测量池扫描得到的光谱,其它依次类推;(3) Replace the reference substance in the sample cell with the analyte, then cut the reference cell and the measurement cell into the optical path in turn, and perform spectral scanning to obtain the light intensities marked as meas0, meas1, meas2, and meas N respectively. is the output spectrum; where meas0 represents the spectrum obtained by scanning the reference cell, meas1 represents the spectrum obtained by scanning the No. 1 measuring cell, and so on;
(4)按照下面的式(2)进行光谱处理,以吸光度为输出的吸收光谱;(4) carry out spectral processing according to following formula (2), take absorbance as the absorption spectrum of output;
Absorbi=-log(measi/Backi)+log(meas0/Back0),其中i=1、2、···N 式(2),Absorbi=-log(measi/Backi)+log(meas0/Back0), where i=1, 2,...N formula (2),
式中Absorbi即为测量池i的以吸光度为输出的吸收光谱。In the formula, Absorbi is the absorption spectrum with the absorbance as the output of the measurement cell i.
进一步地,所述的步骤(2)中的背景光谱是以波数为横轴,以光强为纵轴的光谱。Further, the background spectrum in the step (2) is a spectrum with wavenumber as the horizontal axis and light intensity as the vertical axis.
进一步地,所述的步骤(3)的光路中,每次只有一个样品池。Further, in the optical path of step (3), there is only one sample cell at a time.
进一步地,所述的步骤(3)中,每次进行物品分析时,必须重新扫描测量池,获取meas1、meas2、···meas N;但meas0的更新方式可根据实际情况进行设定。Further, in the step (3), each time the item is analyzed, the measurement cell must be re-scanned to obtain meas1, meas2, ... meas N; however, the update method of meas0 can be set according to the actual situation.
进一步地,所述的meas0的更新方式可从以下几种方式中任选一种:Further, the update method of meas0 can be selected from the following several methods:
方式一:每次分析时都获取;Method 1: Get it every time you analyze;
方式二:按固定时间间隔来获取;Method 2: Acquire at fixed time intervals;
方式三:根据光谱的自确认情况来决定是否获取;Method 3: Determine whether to acquire according to the self-confirmation of the spectrum;
方式四:将方式二和方式三同时使用,即满足两个条件之一,就更新meas0;Method 4: Use method 2 and method 3 at the same time, that is, update meas0 if one of the two conditions is met;
而在重新扫描参考池,获取新的meas0之前,meas0保持不变。Before rescanning the reference pool to get a new meas0, meas0 remains unchanged.
进一步地,所述的光谱的自确认情况是:根据光谱是否发生漂移和畸变来决定是否要更新meas0,若基线漂移严重,或发生基线畸变,则重新获取meas0;否则,meas0保持不变。Further, the self-confirmation of the spectrum is to decide whether to update meas0 according to whether the spectrum is drifted or distorted, and if the baseline drifts seriously or the baseline is distorted, reacquire meas0; otherwise, meas0 remains unchanged.
一种多样品池光谱定量分析的光谱读取与处理的装置,包括一个背景气体气室、多个测量气体气室、支撑背景气体气室和测量气体气室的底座,以及驱动测量气体气室移动和转动的垂直移动驱动机构和旋转运动机构,所述底座上进一步安装有感应测量气体气室位置的上限位传感器和下限位传感器;进气管道通过管道转接装置与多个测量气体气室的气体进气口连接,每个测量气体气室的气体出气口通过管道转接装置与出气管道连接,所述的管道转接装置包括有M+1个接口,其中,一个接口与进气管道或出气管道连接,剩下的M个接口分别与测量气体气室的气体进气口或气体出气口连接。A device for spectral reading and processing of multi-sample cell spectral quantitative analysis, comprising a background gas chamber, multiple measuring gas chambers, a base supporting the background gas chamber and measuring gas chamber, and driving the measuring gas chamber The vertical movement drive mechanism and the rotary motion mechanism for moving and rotating, the upper limit sensor and the lower limit sensor for sensing the position of the measuring gas chamber are further installed on the base; the intake pipe is connected with multiple measuring gas chambers through the pipeline adapter The gas inlet port of each measuring gas chamber is connected to the gas outlet of each measuring gas chamber through a pipeline adapter device. The pipeline adapter device includes M+1 interfaces, wherein one interface is connected to the inlet pipeline Or the gas outlet pipe is connected, and the remaining M ports are respectively connected with the gas inlet or gas outlet of the measuring gas chamber.
进一步地,所述的旋转运动机构包括电机以及被电机驱动且相互啮合的小齿轮和大齿轮,其中,多个测量气体气室从所述的大齿轮中穿过。Further, the rotary motion mechanism includes a motor, and a pinion gear and a large gear driven by the motor and intermeshed, wherein a plurality of measuring gas chambers pass through the large gear.
进一步地,所述的垂直移动驱动机构包括电机、螺杆和移动螺母,所述电机通过电机安装座固定在底座上,所述螺杆与电机的输出轴固定连接,所述移动螺母与螺杆配合安装。Further, the vertical movement driving mechanism includes a motor, a screw and a moving nut, the motor is fixed on the base through the motor mount, the screw is fixedly connected to the output shaft of the motor, and the moving nut is mounted in cooperation with the screw.
进一步地,所述多样品池光谱定量分析的光谱读取与处理的装置进一步包括有连接安装板,所述移动螺母安装在连接安装板上;所述测量气体气室和背景气体气室固定安装在气室安装座上,气室安装座通过螺钉与连接安装板固定连接。Further, the device for spectral reading and processing of multi-sample cell spectral quantitative analysis further includes a connecting mounting plate, and the moving nut is mounted on the connecting mounting plate; the measuring gas chamber and the background gas chamber are fixedly installed On the air chamber installation seat, the air chamber installation seat is fixedly connected with the connection installation plate through screws.
相对于现有技术,本发明至少具有以下有益效果:Compared with the prior art, the present invention has at least the following beneficial effects:
本发明提供的一种多样品池光谱定量分析的光谱读取与处理的方法,解决了多样品池的参数,特别是窗片的透光或光吸收特性无法完全保证一致,采用常规参考光谱比对容易引起光谱基线漂移,甚至畸变,从而导致分析结果偏大的问题;本发明避免了基线的漂移与畸变带来的偏差,大大提高了分析结果的准确性(测量光谱除以背景光谱得到以透射率为输出的光谱,该光谱的常用对数值的负值,即为以吸光度为输出的光谱,多样品池光谱分析中,用测量气室获得光谱除以背景气室扫描的光谱,得到以透射率为输出的光谱,由于两个气室窗片参数的不同,使得两者的差异被当成了吸收光谱,从而使得基线发生漂移,甚至畸变。本发明提出的方法,是通过两个气室各自扫描背景光谱和测量光谱,然后求吸收光谱的差值,而不是用常规的两个气室直接相除来获得光谱,因此窗片的差异就不再包含在基线中);同时,本发明可以解决重新扫描背景光谱时,数据易丢失,实时性较差的问题。The method for reading and processing the spectrum of a multi-sample cell spectrum quantitative analysis provided by the present invention solves the problem that the parameters of the multi-sample cell, especially the light transmission or light absorption characteristics of the window cannot be completely consistent, and the conventional reference spectrum ratio is used. For the problem that it is easy to cause the spectral baseline to drift or even distort, thereby causing the analysis results to be too large; the present invention avoids the deviation caused by the drift and distortion of the baseline, and greatly improves the accuracy of the analysis results (dividing the measured spectrum by the background spectrum to obtain the following The transmittance is the output spectrum, and the negative value of the common logarithm of the spectrum is the output spectrum with absorbance. In multi-sample cell spectrum analysis, the spectrum obtained by measuring the gas cell is divided by the spectrum scanned by the background gas cell to obtain the following: The transmittance is the output spectrum, due to the difference of the window parameters of the two air chambers, the difference between the two is regarded as the absorption spectrum, thereby causing the baseline to drift or even distort. The method proposed by the present invention is to use two air chambers Respectively scan the background spectrum and the measurement spectrum, and then ask for the difference of the absorption spectrum, instead of using conventional two gas chambers to directly divide to obtain the spectrum, so the difference of the window is no longer included in the baseline); meanwhile, the present invention It can solve the problems of easy data loss and poor real-time performance when re-scanning the background spectrum.
进一步地,若想节省时间,可以根据实际情况,设定更新meas0的方式,操作方便。Furthermore, if you want to save time, you can set the way to update meas0 according to the actual situation, which is easy to operate.
【附图说明】【Description of drawings】
图1是以背景气室扫描得到的背景为参考光谱,以测量气室扫描得到的光谱为吸收光谱,按照式(1)计算得到的光谱;Fig. 1 takes the background obtained by scanning the background gas chamber as the reference spectrum, the spectrum obtained by measuring the gas chamber as the absorption spectrum, and the spectrum calculated according to formula (1);
图2是三气室切换示意图;其中(a)是竖直排列的三气室的连接示意图,图(b)是三角形排列的三气室的连接示意图;图中1为两个测量气室,2为电磁阀,3是三通,4是进气管道,5是出气管道,6为背景气体气室;Fig. 2 is a schematic diagram of switching three air chambers; wherein (a) is a schematic diagram of the connection of three air chambers arranged vertically, and figure (b) is a schematic diagram of the connection of three air chambers arranged in a triangle; among the figures 1 is two measuring air chambers, 2 is a solenoid valve, 3 is a tee, 4 is an air inlet pipe, 5 is an air outlet pipe, and 6 is a background gas chamber;
图3(a)是垂直与水平移动方式气室切换装置结构剖面图;图中1为第一测量气室,6为背景气体气室,7为电机,11为第二测量气室,12为底座,13为导杆,14为螺杆,15为可移动螺母,16为轴承座,17为下限位传感器,18为上限位传感器,19为连接安装板,20为测量气室进气口,21为气室安装座,22为测量气室出气口,23为紧定螺钉;Fig. 3(a) is a cross-sectional view of the structure of the gas chamber switching device in the vertical and horizontal movement mode; in the figure, 1 is the first measuring gas chamber, 6 is the background gas chamber, 7 is the motor, 11 is the second measuring gas chamber, and 12 is Base, 13 is a guide rod, 14 is a screw rod, 15 is a movable nut, 16 is a bearing seat, 17 is a lower limit sensor, 18 is an upper limit sensor, 19 is a connection mounting plate, 20 is the air inlet of the measuring air chamber, 21 For the air chamber installation seat, 22 is the air outlet of the measuring air chamber, and 23 is the set screw;
图3(b)是回转方式气室切换装置结构示意图,图中1为第一测量气室,2为电磁阀,3是三通,4是进气管道,5是出气管道,6为背景气体气室,7为电机,8为小齿轮,9为与三个气室紧固在一起的与外部气室支架相连的轴,10为大齿轮,11为第二测量气室;Figure 3(b) is a schematic diagram of the structure of the rotary air chamber switching device. In the figure, 1 is the first measuring air chamber, 2 is the solenoid valve, 3 is the tee, 4 is the inlet pipe, 5 is the outlet pipe, and 6 is the background gas. Air chamber, 7 is the motor, 8 is the pinion gear, 9 is the shaft connected with the external air chamber support fastened together with the three air chambers, 10 is the large gear, and 11 is the second measuring air chamber;
图4是背景气室和测量气室两次扫描得到的以光强为输出的光谱图;Fig. 4 is the spectrogram with light intensity as the output obtained by two scans of the background gas chamber and the measurement gas chamber;
图5是分别按照式(2)和式(1)得到的以吸光度为输出的光谱。Fig. 5 is the spectrum with absorbance as the output obtained according to formula (2) and formula (1) respectively.
【具体实施方式】【detailed description】
下面结合附图及实施方式对本发明作进一步详细描述。The present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments.
一种多样品池光谱定量分析的光谱读取与处理方法,包括以下步骤:A spectral reading and processing method for spectral quantitative analysis of multi-sample cells, comprising the following steps:
(1)将样品池分为参考池和测量池,进行标号,参考池标示为0,其它测量池依次标示为1、2、···N;(1) Divide the sample cell into a reference cell and a measurement cell, and carry out labeling. The reference cell is marked as 0, and the other measurement cells are marked as 1, 2, ... N in turn;
(2)对所有的样品池充满参考物,并按照背景光谱的方式扫描光谱,所述的背景光谱是以波数为横轴,以光强为纵轴的光谱;得到分别标示为Back0、Back1、Back2、···BackN的以光强为输出的光谱;其中Back0表示对参考池扫描得到的光谱,Back1表示对1号测量池扫描得到的光谱,其它依次类推;(2) All sample pools are full of reference matter, and scan the spectrum according to the background spectrum, the background spectrum is the spectrum with the wave number as the horizontal axis and the light intensity as the vertical axis; The output spectra of Back2 and BackN with light intensity as the output; among them, Back0 represents the spectrum obtained by scanning the reference cell, Back1 represents the spectrum obtained by scanning the No. 1 measuring cell, and so on;
(3)在对气体、液体或固体物品进行分析的过程中,将参考池,以及充满待分析物的所有测量池依次切入光路中,可以采用手动的方式切换,也可以采用自动装置自动切换,保证光路中每次只有一个样品池;再一次对所有的样品池进行光谱扫描,并得到分别标示为meas0、meas1、meas2、···measN的以光强为输出的光谱;其中meas0表示对参考池扫描得到的光谱,meas1表示对1号测量池扫描得到的光谱,其它依次类推;(3) In the process of analyzing gas, liquid or solid objects, the reference cell and all the measurement cells filled with the analytes are sequentially cut into the optical path, which can be switched manually or automatically by an automatic device. Ensure that there is only one sample cell in the optical path at a time; scan the spectra of all sample cells again, and obtain the output spectra with light intensity as meas0, meas1, meas2, and measN respectively; where meas0 represents the reference The spectrum obtained by cell scanning, meas1 means the spectrum obtained by scanning the No. 1 measuring cell, and so on for others;
(4)按照下面的式(2)进行光谱处理,以吸光度为输出的吸收光谱;(4) carry out spectral processing according to following formula (2), take absorbance as the absorption spectrum of output;
Absorbi=-log(measi/Backi)+log(meas0/Back0),其中i=1、2、···N 式(2),Absorbi=-log(measi/Backi)+log(meas0/Back0), where i=1, 2,...N formula (2),
式中Absorbi即为测量池i的以吸光度为输出的吸收光谱。In the formula, Absorbi is the absorption spectrum with the absorbance as the output of the measurement cell i.
进一步地,所述的步骤(3)中,每次进行物品分析时,必须重新扫描测量池,获取meas1、meas2、···;但meas0的更新方式可根据实际情况进行设定,从以下几种方式中任选一种:Further, in the step (3), each time the article is analyzed, the measurement pool must be re-scanned to obtain meas1, meas2, ...; but the update method of meas0 can be set according to the actual situation, from the following Choose one of the ways:
方式一:每次分析时都获取;Method 1: Get it every time you analyze;
方式二:按固定时间间隔0.5~8小时来获取;Method 2: Obtain at a fixed time interval of 0.5 to 8 hours;
方式三:根据光谱是否发生漂移和畸变来决定是否要更新meas0,若基线漂移严重,或发生基线畸变,则重新获取meas0;否则,meas0保持不变。Method 3: Determine whether to update meas0 according to whether the spectrum drifts or distorts. If the baseline drifts seriously or the baseline is distorted, then reacquire meas0; otherwise, meas0 remains unchanged.
方式四:将方式二和方式三同时使用,即满足两个条件之一,就更新meas0;Method 4: Use method 2 and method 3 at the same time, that is, update meas0 if one of the two conditions is met;
而在重新扫描参考池,获取新的meas0之前,meas0保持不变。Before rescanning the reference pool to get a new meas0, meas0 remains unchanged.
下面用三个气室切换的气体傅里叶变换红外光谱分析为例,来具体说明本发明的实施方式。The embodiment of the present invention will be described in detail below by taking gas Fourier transform infrared spectroscopic analysis with switching of three gas chambers as an example.
气体成分与浓度在线光谱分析的两个测量气室和一个背景气室连接如图2所示,可以是竖直排列,如附图2(a);也可以是三角形排列,如附图2(b)。两个测量气室的两个进气口各装有一个电磁阀2,电磁阀2通过三通3与进气管道4相连,两个测量气室的两个出气口则直接通过三通3与气路的出气口相连,背景气室6中充满背景气体。对于一般的极性分子气体在线分析应用,该背景气体为氮气。本实施例以竖直排列的气室连接方式为例来说明本发明的实施方式。Two measuring gas chambers and a background gas chamber of gas composition and concentration online spectroscopic analysis are connected as shown in Figure 2, which can be arranged vertically, as shown in Figure 2 (a); also can be arranged in a triangle, as shown in Figure 2 ( b). The two air inlets of the two measuring air chambers are respectively equipped with a solenoid valve 2, and the solenoid valve 2 is connected with the inlet pipe 4 through the tee 3, and the two air outlets of the two measuring air chambers are directly connected with the air inlet pipe 4 through the tee 3. The gas outlets of the gas path are connected, and the background gas chamber 6 is filled with background gas. For general online analysis of polar molecular gases, the background gas is nitrogen. In this embodiment, the embodiment of the present invention is described by taking the connection mode of the gas chambers arranged vertically as an example.
垂直移动方式与水平移动的切换装置截面图如图3(a)所示,包括第一测量气室1、第二测量气室11和背景气室6、直线轴承、垂直移动机构、限位传感器等;导杆13和轴承座16构成直线轴承,导杆13固定安装在地板上,轴承座16固定安装在连接安装板19上;电机7、电机安装座、螺杆14、可移动螺母15构成垂直移动机构,电机7安装在电机安装座上,可进行连续的正反转,电机安装座通过紧定螺钉23固定安装在底板上,螺杆14与电机7的输出轴固联,可移动螺母15固定安装在连接安装板19上;第一测量气室1、第二测量气室11和背景气室6固定安装在气室安装座21上,气室安装座21与连接安装板19通过紧定螺钉23进行固定连接,连接安装板19上还安装有3个轴承座16、一个螺母。上限位传感器18、下限位传感器17固定安装在底座12上,传感器的间距根据所需的垂直移动位移进行调整。当需要将第一测量气室1切换到光路中时,控制电机7正转驱动螺杆14转动,进而驱动与螺杆14配合的螺母向上移动,从而驱动连接安装板19、第一测量气室1顺着直线轴承中心向上移动,直至上限位传感器18检测到到位信号为止,即将第一测量气室1移至光路中,此时,计算机发出信号,关闭第一测量气室1的电磁阀,打开第二测量气室11的电磁阀;扫描完光谱后,控制电机反转驱动连接安装板19、两个测量气室顺着直线轴承中心向下移动,直至下限位传感器17检测到到位信号为止,即把第二测量气室11切换到光路中,此时,计算机发出信号,关闭第二测量气室11的电磁阀,打开第一测量气室1的电磁阀。这样,周而复始,使得光谱仪进行光谱扫描时,气室中的气体成分及其浓度是稳定的。The cross-sectional view of the switching device for vertical movement and horizontal movement is shown in Figure 3(a), including the first measurement gas chamber 1, the second measurement gas chamber 11 and the background gas chamber 6, linear bearings, vertical movement mechanism, limit sensor etc.; guide rod 13 and bearing seat 16 form a linear bearing, guide rod 13 is fixedly installed on the floor, and bearing seat 16 is fixedly installed on the connection mounting plate 19; motor 7, motor mounting seat, screw rod 14, movable nut 15 form a vertical The moving mechanism, the motor 7 is installed on the motor mounting base, which can carry out continuous forward and reverse rotation, the motor mounting base is fixedly installed on the bottom plate through the set screw 23, the screw rod 14 is fixedly connected with the output shaft of the motor 7, and the movable nut 15 is fixed Installed on the connection mounting plate 19; the first measuring gas chamber 1, the second measuring gas chamber 11 and the background gas chamber 6 are fixedly installed on the gas chamber mounting base 21, and the gas chamber mounting base 21 and the connecting mounting plate 19 are connected by set screws 23 is fixedly connected, and 3 bearing blocks 16 and a nut are also installed on the connection mounting plate 19. The upper limit sensor 18 and the lower limit sensor 17 are fixedly installed on the base 12, and the distance between the sensors is adjusted according to the required vertical displacement. When it is necessary to switch the first measurement gas chamber 1 into the optical path, the control motor 7 rotates forwardly to drive the screw 14 to rotate, and then drives the nut matched with the screw 14 to move upwards, thereby driving the connecting mounting plate 19, the first measurement gas chamber 1 to move forward The center of the linear bearing moves upward until the upper limit sensor 18 detects the in-position signal, that is, the first measuring air chamber 1 is moved to the optical path. At this time, the computer sends a signal to close the solenoid valve of the first measuring air chamber 1 and open the second measuring air chamber. 2. The solenoid valve of the measurement air chamber 11; after scanning the spectrum, the control motor is reversely driven to connect the mounting plate 19, and the two measurement air chambers move downward along the center of the linear bearing until the lower limit sensor 17 detects the signal in place, that is Switch the second measuring gas chamber 11 to the optical path, at this time, the computer sends a signal to close the solenoid valve of the second measuring gas chamber 11 and open the solenoid valve of the first measuring gas chamber 1 . In this way, it goes round and round, so that when the spectrometer scans the spectrum, the gas composition and its concentration in the gas chamber are stable.
连续回转方式的切换装置示意图如图3(b)所示,三个气室的中间有两个轴,该轴与三个气室紧固在一起,与外部之间相连。此外,三个气室的中部从一个大齿轮10中穿过,步进电机7在工控机等的控制下转动,小齿轮8与步进电机7同轴相连,因而与步进电机7同步转动,大齿轮10在该小齿轮8的驱动下,产生转动。由于步进电机7的进给量是以脉冲的形式给出的,步进电机7本身就可以识别自身转子的角位置。因此,三个气室中任何一个均可以通过工控机发送相应数量的脉冲切换到光路中,从一个气室切换到另一个气室所需脉冲数量,可通过试验确定。由于三个气室相互之间成120度,因此也可通过步进电机7的角位置确定。若以图中电机箭头方向为正方向,第一测量气室1在光路中,则通过反转120度,即可将第二测量气室11切换到光路中,再继续反转120度,则可将背景气室6切换至光路中。若要重新把第一测量气室1切换至光路中,则正转240度即可。The schematic diagram of the switching device in the continuous rotation mode is shown in Figure 3(b). There are two shafts in the middle of the three air chambers, which are fastened to the three air chambers and connected to the outside. In addition, the middle parts of the three air chambers pass through a large gear 10, and the stepping motor 7 rotates under the control of an industrial computer, etc., and the pinion 8 is coaxially connected with the stepping motor 7, so that it rotates synchronously with the stepping motor 7 , the large gear 10 rotates under the drive of the pinion 8 . Since the feed amount of the stepping motor 7 is given in the form of pulses, the stepping motor 7 itself can recognize the angular position of its own rotor. Therefore, any one of the three gas chambers can be switched to the optical path by sending a corresponding number of pulses through the industrial computer, and the number of pulses required to switch from one gas chamber to another can be determined through experiments. Since the three air chambers are at 120° to each other, this can also be determined by the angular position of the stepper motor 7 . If the direction of the motor arrow in the figure is taken as the positive direction, and the first measuring gas chamber 1 is in the optical path, then the second measuring gas chamber 11 can be switched to the optical path by reversing 120 degrees, and then continue to reverse 120 degrees, then The background gas cell 6 can be switched into the light path. To switch the first measuring gas chamber 1 to the optical path again, just turn forward 240 degrees.
在进行气体的光谱分析之前,三个气室中都充满氮气,然后根据上述切换功能,依次将三个气室切换到光谱仪光路中,并扫描得到以光强为输出的光谱作为背景光谱,三个背景光谱分别标示为Back0、Back1和Back2。其中Back0为背景气室6的光谱,Back1和Back2分别为第一测量气室1和第二测量气室11的背景光谱。Before the spectral analysis of the gas, the three gas chambers are filled with nitrogen, and then according to the above switching function, the three gas chambers are switched to the optical path of the spectrometer in turn, and the spectrum with the light intensity as the output is scanned as the background spectrum. The background spectra are labeled Back0, Back1 and Back2, respectively. Where Back0 is the spectrum of the background gas chamber 6 , and Back1 and Back2 are the background spectra of the first measuring gas chamber 1 and the second measuring gas chamber 11 respectively.
在进行气体光谱分析过程中,测量气室中充满待测气体,第一测量气室1切入光路时,它与气路切断,第二测量气室11切入气路,进行气体更新。光谱仪对第一测量气室1进行光谱扫描,得到以光强为输出的光谱Meas1,然后再将第二测量气室11切入光路,将第一测量气室1切入气路。光谱仪对第二测量气室11进行光谱扫描,得到以光强为输出的光谱Meas2。若短时间内(2小时内)完成了Back0、Back1和Back2、以及Meas1和Meas2的获取,则按式(3)进行处理:During the process of gas spectrum analysis, the measuring gas chamber is filled with the gas to be measured. When the first measuring gas chamber 1 is cut into the optical path, it is cut off from the gas path, and the second measuring gas chamber 11 is cut into the gas path for gas renewal. The spectrometer scans the spectrum of the first measuring gas chamber 1 to obtain the spectrum Meas1 with light intensity as the output, and then cuts the second measuring gas chamber 11 into the optical path, and cuts the first measuring gas chamber 1 into the gas path. The spectrometer scans the spectrum of the second measuring gas chamber 11 to obtain a spectrum Meas2 whose output is light intensity. If the acquisition of Back0, Back1 and Back2, as well as Meas1 and Meas2 is completed within a short period of time (within 2 hours), it will be processed according to formula (3):
Absorbi=-log(measi/Backi),其中i=1、2 式(3)Absorbi=-log(measi/Backi), where i=1, 2 Formula (3)
得到Absorb1和Absorb2。若时间较长(3小时以上),则在获得Meas1和Meas2之后,重新将气室3切入光路,重新获取Meas0,按式(2)进行处理,获得Absorb1和Absorb2。若时间在2~3小时内,用户可自行选择式(2)或式(3)进行处理。Absorb1 and Absorb2 are obtained. If the time is longer (more than 3 hours), after obtaining Meas1 and Meas2, cut the gas chamber 3 into the light path again, obtain Meas0 again, and process according to formula (2) to obtain Absorb1 and Absorb2. If the time is within 2 to 3 hours, the user can choose formula (2) or formula (3) for processing.
背景气室6和第一测量气室1获得Back0、Back1,以及Meas0和Meas1如图4所示。从图可以看出,Back0和Meas0基本重合,Back1和Meas1基本重合,这说明光谱仪预热充分,实验程序没有问题;Back0和Back1的强度差异较大,Back1的光强约为Back0的2/3,这说明两个气室的窗片吸收差异较大,测量气室的窗片,对红外光谱吸收整体较强。The background gas chamber 6 and the first measurement gas chamber 1 obtain Back0, Back1, and Meas0 and Meas1 as shown in FIG. 4 . It can be seen from the figure that Back0 and Meas0 basically coincide, and Back1 and Meas1 basically coincide, which shows that the spectrometer is fully warmed up and there is no problem with the experimental procedure; the intensity difference between Back0 and Back1 is large, and the light intensity of Back1 is about 2/3 of Back0 , which shows that there is a large difference in the absorption of the windows of the two gas chambers, and the window of the measurement gas chamber has a strong absorption of the infrared spectrum as a whole.
分别按照式(2)和(1)得到的以吸光度为输出的光谱分别如图5所示的Absorbance1和Absorbance2。从图5中可以看出:Absorbance1的基线值基本为0,而Absorbance2的基线则有明显的倾斜,随着波数从4000cm-1减小到400cm-1,吸光度从0.13增大到约0.3,而且基线并非一条直线,在1000cm-1至1200cm-1范围内,有三个明显朝下的峰,这说明按照式(1)得到的光谱基线漂移较大,而且有畸变,而按照式(2)获得的光谱基线非常规则,相比于式(1)获得的光谱,可以避免基线的漂移与畸变带来的偏差。According to the formulas (2) and (1), the spectra with the absorbance as the output are respectively shown as Absorbance1 and Absorbance2 in FIG. 5 . It can be seen from Figure 5 that the baseline value of Absorbance1 is basically 0, while the baseline of Absorbance2 has an obvious slope. As the wavenumber decreases from 4000cm -1 to 400cm -1 , the absorbance increases from 0.13 to about 0.3, and The baseline is not a straight line. In the range of 1000cm -1 to 1200cm -1 , there are three obvious downward peaks, which shows that the spectral baseline obtained according to formula (1) has a large drift and distortion, while according to formula (2) The baseline of the spectrum is very regular, compared with the spectrum obtained by formula (1), it can avoid the deviation caused by the drift and distortion of the baseline.
获取Meas0的时间间隔,可根据实际情况来定,可以设定固定时间间隔,也可以通过光谱的自确认来决定是否需要进行重新获取Meas0。如果发现基线发生畸变,则将背景气室切换至光路中重新获取Meas0,否则,Meas0保持不变。基线是否发生畸变,其判定方法参见发明专利“傅里叶变换红外光谱畸变识别与处理方法(ZL201010268039.3)”。The time interval for obtaining Meas0 can be determined according to the actual situation. You can set a fixed time interval, or you can decide whether to re-acquire Meas0 through the self-confirmation of the spectrum. If the baseline is found to be distorted, switch the background gas cell to the optical path to reacquire Meas0, otherwise, Meas0 remains unchanged. Whether the baseline is distorted, the judging method can be found in the invention patent "Fourier Transform Infrared Spectral Distortion Identification and Processing Method (ZL201010268039.3)".
相对于现有技术,本发明至少具有以下有益效果:Compared with the prior art, the present invention has at least the following beneficial effects:
本发明提供的一种多样品池光谱定量分析的光谱读取与处理的方法,解决了多样品池的参数,特别是窗片的光吸收特性无法完全保证一致,采用常规参考光谱比对容易引起光谱基线漂移,甚至畸变,从而导致分析结果偏大的问题;避免了基线的漂移与畸变带来的偏差,大大提高了分析结果的准确性(测量光谱除以背景光谱得到以透射率为输出的光谱,该光谱的常用对数值的负值,即为以吸光度为输出的光谱,多样品池光谱分析中,用测量气室获得光谱除以背景气室扫描的光谱,得到以透射率为输出的光谱,由于两个气室窗片参数的不同,使得两者的差异被当成了吸收光谱,从而使得基线发生漂移,甚至畸变。本发明提出的方法是通过,两个气室各自扫描背景光谱和测量光谱,然后求吸收光谱的差值,而不是用常规的两个气室直接相除来获得光谱,因此窗片的差异就不再包含在基线中);同时,可以解决重新扫描背景光谱时,数据易丢失,实时性较差的问题。The method for reading and processing the spectrum of a multi-sample cell spectrum quantitative analysis provided by the present invention solves the problem that the parameters of the multi-sample cell, especially the light absorption characteristics of the windows cannot be completely consistent, and the comparison of the conventional reference spectrum is easily caused. The spectral baseline drifts or even distorts, which leads to the problem that the analysis results are too large; avoids the deviation caused by the baseline drift and distortion, and greatly improves the accuracy of the analysis results (the measured spectrum is divided by the background spectrum to obtain the output at the transmittance Spectrum, the negative value of the common logarithm value of the spectrum is the spectrum with absorbance as the output. In the multi-sample cell spectrum analysis, the spectrum obtained by measuring the gas cell is divided by the spectrum scanned by the background gas cell to obtain the output with the transmittance Spectrum, due to the difference of two gas chamber window parameters, the difference between the two is regarded as the absorption spectrum, thereby making the baseline drift or even distortion. The method proposed by the present invention is by scanning the background spectrum and the background spectrum of the two gas chambers respectively Measure the spectrum, and then calculate the difference of the absorption spectrum, instead of directly dividing the two gas cells to obtain the spectrum, so the difference of the window is no longer included in the baseline); at the same time, it can solve the problem of rescanning the background spectrum , the data is easily lost, and the real-time performance is poor.
进一步地,若想节省时间,可以根据实际情况,设定更新meas0的方式,操作方便。Furthermore, if you want to save time, you can set the way to update meas0 according to the actual situation, which is easy to operate.
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施方式仅限于此,对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单的推演或替换,都应当视为属于本发明由所提交的权利要求书确定专利保护范围。The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments. It cannot be determined that the specific embodiments of the present invention are limited thereto. Under the present invention, some simple deduction or replacement can also be made, all of which should be regarded as belonging to the scope of patent protection determined by the submitted claims of the present invention.
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