WO2024255924A1 - 一种直测流动液体高浓度目标物种浓度的方法 - Google Patents

一种直测流动液体高浓度目标物种浓度的方法 Download PDF

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WO2024255924A1
WO2024255924A1 PCT/CN2024/109811 CN2024109811W WO2024255924A1 WO 2024255924 A1 WO2024255924 A1 WO 2024255924A1 CN 2024109811 W CN2024109811 W CN 2024109811W WO 2024255924 A1 WO2024255924 A1 WO 2024255924A1
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concentration
optical path
absorbance
wavelength
target species
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段宁
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Tongji University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/12—Circuits of general importance; Signal processing
    • G01N2201/129—Using chemometrical methods

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  • the invention relates to the technical field of chemical analysis and environmental protection, and in particular to a method for directly measuring the concentration of high-concentration target species in flowing liquid.
  • the object of the present invention is to provide a method and device for directly measuring the concentration of high-concentration target species in flowing liquids, aiming to solve the problem that the prior art cannot quickly and directly measure the original valence, original form, original phase and concentration of target species in a high concentration range.
  • a method for directly measuring the concentration of a high-concentration target species in a flowing liquid comprising the steps of:
  • solution samples of different concentrations are configured, and within the wavelength range of ultraviolet, visible light and near-infrared light, absorbance scanning of the solution samples is performed in sequence using different optical path lengths to prepare absorption spectra of the solution samples at each optical path length;
  • a matching absorbance point is selected on the Abs axis, and a straight line parallel to the ⁇ axis is drawn from the absorbance point so that it intersects with all the spectral curves on the relevant side of the target species at ( ⁇ , Abs).
  • the straight line parallel to the ⁇ axis is the matching absorbance line;
  • the type information of the monitored species is given, and when it flows through the quantitative optical path, the wavelength information of the monitored species is given.
  • the wavelength information is substituted into the wavelength-concentration model to give the valence state, form, phase state and concentration of the target species in the flowing liquid to be measured.
  • the method for directly measuring the concentration of a high-concentration target species in a flowing liquid wherein, in the step of successively scanning the absorbance of the solution sample with different optical pathlengths and preparing an absorption spectrum of the solution sample at each optical pathlength, the selected optical pathlength ensures that the peak absorbance value of the curve obtained by scanning the solution sample is higher than half of the maximum absorbance of the instrument, and the absorbance curve of the non-peak part near half of the maximum absorbance of the instrument is a smooth curve without burrs.
  • the method for directly measuring the concentration of a high-concentration target species in a flowing liquid wherein the conditions for selecting an adapted absorbance point on the Abs axis include: a. the intersection of a straight line starting from the point and all spectral curves on the relevant side of the target species and the curve segments nearby are smooth and free of burrs, and the curve segments have no intersecting trend; b. the Abs value of this point is the largest among all points on the Abs axis that meet condition a; c. the spectrum at the intersection of a straight line starting from the point and all spectral curves on the relevant side of the target species is not interfered by the spectra of other species; d. the wavelengths at the intersections of the straight line starting from the point and the lowest concentration and highest concentration spectral curves on the relevant side of the target species are both within the optimal energy wavelength range of the light source used.
  • the method for directly measuring the concentration of a high-concentration target species in a flowing liquid wherein the screening conditions for setting the quantitative optical path length and screening the quantitative optical path length based on the adapted absorbance line and the absorption spectrum diagram include:
  • ⁇ C j is the jth concentration difference, i.e., the difference between the j+1th concentration and the jth concentration
  • ⁇ ij is the j-th perpendicular wavelength difference of the ith optical path, That is, the perpendicular wavelength from the intersection of the curve of the j+1th concentration under the ith optical path and the adapted absorbance line to the horizontal axis, and the perpendicular wavelength from the intersection of the curve of the jth concentration under the same optical path and the adapted absorbance line to the horizontal axis.
  • the difference between the perpendicular wavelengths; kij is the ratio of the jth perpendicular wavelength difference of the i-th optical path to the jth concentration difference;
  • the method provided by the present invention for directly measuring the concentration of high-concentration target species in flowing liquids does not require large-multiple dilution of high-concentration complex solutions or the addition of multiple chemical agents. Therefore, there is no dilution error and secondary pollution risk.
  • the original valence, original form, original phase and concentration and other chemical information of the target species in the high-concentration solution in the flowing liquid can be directly measured within 10 seconds. The problem of changes in the target species in the solution to be measured will not occur. After the measurement, the solution can be directly returned to the original system, and the production process can be guided in real time.
  • the method of the present invention overcomes the problem that the Lambert-Beer linear law cannot be satisfied when directly measuring high-concentration complex solutions, and even the absorbance far exceeds the upper limit of the instrument measurement, and it is impossible to quickly provide important information such as the valence, form, phase and concentration of the species in the solution.
  • FIG1 is a flow chart of a method for directly measuring the concentration of a high-concentration target species in a flowing liquid provided by the present invention.
  • FIG. 2 is a graph showing the absorbance curve in the ultraviolet region of a sample with an arsenic ion concentration of 4665.43 mg/L provided by the present invention.
  • FIG3 is an absorption spectrum diagram of the solution sample at each optical path length, obtained by scanning the absorbance of a 10-20 g/L trivalent arsenic (As 3+ ) ion sample at different optical path lengths in the ultraviolet wavelength range.
  • the present invention provides a method for directly measuring the concentration of a high-concentration target species in a flowing liquid.
  • the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.
  • FIG. 1 is a flow chart of a method for directly measuring the concentration of a high-concentration target species in a flowing liquid provided by the present invention. As shown in the figure, the method comprises the following steps:
  • the appropriate optical path length is selected according to the different concentrations of the actual liquid samples of the enterprise.
  • the flowing liquid containing different concentrations of the target is used as a sample, and the absorbance curve of the sample in the ultraviolet visible light and near-infrared light range is measured to ensure that the absorbance curve in the ultraviolet visible light and near-infrared light wavelength range has a sharp characteristic absorption peak at the top, and the absorbance corresponding to the absorption peak is within a reasonable range.
  • the curve waveform should be complete, smooth and free of burrs.
  • the characteristic wavelength corresponding to the sharp peak with the highest absorbance is the qualitative wavelength ⁇ qual
  • its corresponding optical path length is the qualitative optical path length b qual .
  • all concentration samples are scanned for absorbance using different optical path lengths in turn, and absorption spectra ( ⁇ -Abs graphs) of all concentrations under each optical path length are prepared.
  • the selected optical path length should ensure that the peak absorbance value of the curve obtained by scanning each concentration solution is higher than half of the maximum absorbance of the instrument (50% Abs value), and the absorbance curve of the non-peak part near half of the maximum absorbance of the instrument should be smooth and free of burrs.
  • an adaptive absorbance point is selected on the Abs axis, and a straight line parallel to the ⁇ axis is generated from the point, so that it intersects with all the spectral curves on the relevant side of the target species at ( ⁇ , Abs).
  • the selection principle of the adaptive absorbance point is: a. The intersection of the straight line starting from this point and all the spectral curves on the relevant side of the target species and the curve segments nearby are smooth and burr-free, and the curve segments have no intersecting trend; b.
  • the Abs value of this point is the largest among all the points on the Abs axis that meet a; c.
  • the spectrum at the intersection of the straight line starting from this point and all the spectral curves on the relevant side of the target species is not interfered by the spectra of other species; d.
  • the wavelengths at the intersection of the straight line starting from this point with the lowest concentration and highest concentration spectral curves on the relevant side of the target species are all within the optimal energy wavelength range of the light source used.
  • this straight line parallel to the ⁇ axis is called the adaptive absorbance line.
  • ⁇ C j is the jth concentration difference, that is, the difference between the j+1th concentration and the jth concentration
  • ⁇ ij is the jth perpendicular wavelength difference of the i-th optical path, that is, the perpendicular wavelength from the intersection of the curve of the j+1th concentration and the adaptive absorbance line to the horizontal axis under the i-th optical path, and the perpendicular wavelength difference from the intersection of the curve of the jth concentration and the adaptive absorbance line to the horizontal axis under the same optical path
  • k ij is the ratio of the jth perpendicular wavelength difference of the i-th optical path to the jth concentration difference.
  • the device when the flowing liquid to be measured flows through the qualitative optical path, the device gives the type information of the monitored species, and when it flows through the quantitative optical path, it gives accurate wavelength information. Substituting the wavelength information into the wavelength concentration model, the valence, morphology, phase state and concentration and other chemical information of the target species in the flowing state high-concentration liquid can be accurately given within 10 seconds.
  • the method for directly measuring the concentration of high-concentration target species in the flowing liquid provided by this embodiment does not require large-multiple dilution of the high-concentration complex solution, and does not require the addition of multiple chemical agents. Therefore, there is no risk of dilution error and secondary pollution.
  • the original valence, original morphology, original phase state and concentration and other chemical information of the target species in the high-concentration solution in the flowing liquid can be directly measured within 10 seconds, and the problem of the target species in the solution to be measured will not occur. After the measurement, the solution can be directly returned to the original system, and the production process can be guided in real time.
  • the method of this embodiment overcomes the problem that the Lambert-Beer linear law cannot be satisfied when directly measuring high-concentration complex solutions, and even the absorbance far exceeds the upper limit of the instrument measurement, and the valence, morphology, phase state and concentration of the species in the solution cannot be quickly given.

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Abstract

本发明公开了一种直测流动液体高浓度目标物种浓度的方法，其中，所述方法包括步骤：通过测定目标物种的定性光程和定量光程，构建波长-浓度模型和算法，可在紫外可见光和近红外光的波长区域内实时测定液体目标物种的光度信号和浓度。运行时液体流过设备，定性光程确定目标物种的种类，定量光程维持合理的高吸光度并测定液体的波长，由此计算目标物种浓度；不投加化学药剂、不稀释溶液，10秒内测定流动液体中高浓度目标物种原价态原形态原相态浓度。

Description

一种直测流动液体高浓度目标物种浓度的方法 技术领域
本发明涉及化学分析及环境保护技术领域，特别涉及一种直测流动液体高浓度目标物种浓度的方法。
背景技术
流程工业过程往往发生复杂的化学反应，上下游单元联动明显，资源转化、产污状况取决于反应的进度和效率，对液相体系物种的价态、形态、相态及浓度的实时监测调控水平决定了工业过程的资源转化效率和产污总量及毒性，工业复杂液体中物种的价态、形态、相态及浓度的实时监测对于流程工业过程控制极为重要。然而受限于工业液体多相多组分共存、浓度高跨度大且变化快速的复杂性，现有监测方法普遍基于朗伯比尔线性定律，检测前往往需要对溶液进行复杂的预处理，如投加多种化学药剂，大倍数稀释等，容易产生二次污染，样品制备误差大，且分析时间过长，大多数情形下用现有国内外设备分析企业高浓度溶液需3-4小时，甚至使目标物种发生改变，不能快速直接测定高浓度范围目标物种的原价态原形态原相态和浓度，无法用于实时指导工业过程调控。现有技术迫切需要一种对高浓度工业液体中物种的价态、形态、相态和浓度等微观化学信息进行快速直测的方法。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种直测流动液体高浓度目标物种浓度的方法及设备，旨在解决现有技术不能快速直接测定高浓度范围目标物种的原价态原形态原相态和浓度的问题。
本发明的技术方案如下：
一种直测流动液体高浓度目标物种浓度的方法，其中，包括步骤：
以含不同浓度目标物的流动液体作为样本，测量所述样本在紫外可见光和近红外光范围内的吸光度曲线，获取所述吸光度曲线中吸光度最高的尖锐峰对应的特征波长作为定性波长λqual，其对应的光程作为定性光程bqual；
根据流动液体实际浓度范围配置不同浓度的溶液样品，在紫外可见光和近红外光波长范围内，依次用不同光程对所述溶液样品进行吸光度扫描，制作各光程下所述溶液样品的吸收光谱图；
在所述溶液样品的吸收光谱图中，在Abs轴上选择一个适配的吸光度点，从所述吸光度点出发作一条平行于λ轴的直线，使其与目标物种的相关侧的所有光谱曲线相交于(λ，Abs)，此时平行于λ轴的直线为适配吸光度线；
设定定量光程的筛选条件，并基于所述适配吸光度线以及吸收光谱图筛选得到定量光程；
观察定性光程下实际流动液体中目标物种的不同浓度所对应的特征波长与光谱曲线形状的变化规律，将其与在实际液体目标物种的不同浓度的静态样品中测得的定性波长λqual及光谱曲线形状的变化规律进行比对分析，确定在实际流动液体情形下目标物种不同浓度时定性波长λqual f的位置和曲线形状；
获得定量光程在实际流动液体情形下从最低浓度到最高浓度Cj范围内不同浓度对应的波长λj，在定量光程下依据(Cj，λj)，制作以C为横坐标值、λ为纵坐标值的浓度-波长曲线；
按统计学指标将所述浓度-波长曲线进一步划分为分段线性曲线，通过分段线性拟合得到C＝f(λ)的分段线性函数，即得到符合要求的波长-浓度法模型；
将待测流动液体流过定性光程bqual时给出监测物种的种类信息，在其流过定量光程时给出监测物种的波长信息，将所述波长信息代入所述波长-浓度模型，给出待测流动液体中目标物种的价态、形态、相态和浓度。
所述直测流动液体高浓度目标物种浓度的方法，其中，所述依次用不同光程对所述溶液样品进行吸光度扫描，制作各光程下所述溶液样品的吸收光谱图的步骤中，所选择的光程保证对溶液样品扫描所得曲线的峰顶吸光度值高于仪器最大吸光度的一半，且仪器最大吸光度一半附近非峰顶部分的吸光度曲线为光滑无毛刺曲线。
所述直测流动液体高浓度目标物种浓度的方法，其中，在Abs轴上选择一个适配的吸光度点的条件包括：a、从该点出发的直线与目标物种的相关侧所有光谱曲线交点处及其附近曲线段光滑无毛刺，各曲线段无相交趋势；b、Abs轴上满足条件a的所有各点中该点Abs值最大；c、从该点出发的直线与目标物种的相关侧的所有光谱曲线交点处的光谱不受其它物种光谱干扰；d、从该点出发的直线与目标物种相关侧的最低浓度和最高浓度光谱曲线交点处波长均在所用光源的最佳能量波长范围。
所述直测流动液体高浓度目标物种浓度的方法，其中，所述设定定量光程的筛选条件，并基于所述适配吸光度线以及吸收光谱图筛选得到定量光程，包括：
令bi表示第i个光程，i＝1、2、…m，Cj表示第j个浓度，j＝1、2、……n，λij表示用第i个光程测得的第j个浓度的光谱曲线与适配吸光度线交点的波长，即在第i个光程的Abs-λ图中从第j个浓度的光谱曲线与适配吸光度线交点作λ轴垂线所得垂足的波长；
令ΔCj＝Cj+1-Cj，j＝1、2、…n-1；令Δλij＝λi，j+1-λij，对任何i，j＝1、2、…n-1，i＝1、2、…m，其中，ΔCj为第j个浓度差，即第j+1个浓度与第j个浓度之差；Δλij为第i个光程的第j个垂足波长差， 即第i个光程下第j+1个浓度的曲线与适配吸光度线交点至横轴的垂足波长，以及同一光程下第j个浓度的曲线与适配吸光度线交点至横轴的垂足波长之差；kij为第i个光程的第j个垂足波长差与第j个浓度差的比值；
同时满足如下两个条件的光程为定量光程：kij≥δ，i＝1、2…m,j＝1,2,…n-1，δ是一个用户自定义的大于0的正数；
有益效果：本发明提供的直测流动液体高浓度目标物种浓度的方法不需要对高浓度复杂溶液进行大倍数稀释、无需投加多种化学药剂，因此，无稀释误差和二次污染风险，10秒内可直接测定流动液体中高浓度溶液中目标物种的原价态、原形态、原相态及浓度等化学信息，不会出现待测溶液中目标物种发生改变的问题，测定后溶液可直接返回原系统，可以实时指导生产过程。本发明方法克服了直接测定高浓度复杂溶液时朗伯比尔线性定律无法得到满足，甚至吸光度远超出仪器测定上限、无法快速给出溶液中物种的价态、形态、相态及浓度等重要信息的难题。
附图说明
图1为本发明提供的一种直测流动液体高浓度目标物种浓度的方法流程图。
图2为本发明提供的以4665.43mg/L的砷离子浓度为样本，测量其紫外区域的吸光度曲线图。
图3为在紫外波长范围内，依次用不同光程对10-20g/L三价砷(As3+)离子样品进行吸光度扫描，制作各光程下所述溶液样品的吸收光谱图。
图4为按统计学指标将所述浓度-波长曲线进一步划分为分段线性曲线，通过分段线性拟合得到C＝f(λ)的分段线性函数，即得到符合要求的波长-浓度法模型示意图。
具体实施方式
本发明提供一种直测流动液体高浓度目标物种浓度的方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
请参阅图1，图1为本发明提供的一种直测流动液体高浓度目标物种浓度的方法流程图，如图所示，其包括步骤：
S10、以含不同浓度目标物的流动液体作为样本，测量所述样本在紫外可见光和近红外光范围内的吸光度曲线，获取所述吸光度曲线中吸光度最高的尖锐峰对应的特征波长作为定性波长λqual，其对应的光程作为定性光程bqual；
在本实施例中，在不投加任何化学药剂的前提下，根据企业实际液体样品的不同浓度选择匹配的适宜光程。以含不同浓度目标物的流动液体作为样本，测量所述样本在紫外可见光和近红外光范围内的吸光度曲线，保证在紫外可见光和近红外光波长范围内的吸光度曲线有顶部尖锐的特征吸收峰，且吸收峰对应的吸光度位于合理范围内，曲线波形应完整、光滑无毛刺，吸光度最高的尖锐峰对应的特征波长为定性波长λqual，其对应的光程为定性光程bqual。
作为举例，如图2所示，以4665.43mg/L的砷离子浓度为样本，测量其紫外区域的吸光度曲线，获取其吸光度曲线中吸光度最高的尖锐峰对应的特征波长(λmax＝193nm)作为定性波长λqual，其对应的光程(b＝1mm)作为定性光程bqual。
S20、根据流动液体实际浓度范围配置不同浓度的溶液样品，在紫外可见光和近红外光波长范围内，依次用不同光程对所述溶液样品进行吸光度扫描，制作各光程下所述溶液样品的吸收光谱图；
在本实施例中，在紫外可见光和近红外光波长范围内，不进行稀释不投加任何化学药剂的情形下，依次用不同光程对所有浓度样品进行吸光度扫描，制作各光程下所有浓度的吸收光谱图(λ-Abs图)。选择的光程应保证对各浓度溶液扫描所得曲线的峰顶吸光度值高于仪器最大吸光度的一半(50％Abs值)，且仪器最大吸光度一半附近非峰顶部分的吸光度曲线应光滑无毛刺。
S30、在所述溶液样品的吸收光谱图中，在Abs轴上选择一个适配的吸光度点，从所述吸光度点出发作一条平行于λ轴的直线，使其与目标物种的相关侧的所有光谱曲线相交于(λ，Abs)，此时平行于λ轴的直线为适配吸光度线；
在本实施例中，在上述步骤S20中获得的各Abs-λ图中，在Abs轴上选择一个适配吸光度点、从该点出发作一条平行于λ轴的直线，使其与目标物种的相关侧的所有光谱曲线相交于(λ，Abs)。适配吸光度点的选取原则为：a.从该点出发的直线与目标物种的相关侧所有光谱曲线交点处及其附近曲线段光滑无毛刺，各曲线段无相交趋势；b.Abs轴上满足a的所有各点中该点Abs值最大；c.从该点出发的直线与目标物种的相关侧的所有光谱曲线交点处的光谱不受其它物种光谱干扰；d.从该点出发的直线与目标物种相关侧的最低浓度和最高浓度光谱曲线交点处波长均在所用光源的最佳能量波长范围。本实施例中，这条平行于λ轴的直线称之为适配吸光度线。
作为举例，如图3所示，在紫外波长范围内，依次用不同光程对10-20g/L三价砷(As3+)离子样品进行吸光度扫描，制作各光程下所述溶液样品的吸收光谱图；在b＝3mm条件下的吸收光谱图中，在Abs轴上选择一个适配的吸光度点(Abs＝3)，从所述吸光度点出发作一条平行于λ轴的直线，使其与目标物种的相关侧的所有光谱曲线相交于(λ，Abs)，此时平行于λ轴的直线为适配吸光度线。
S40、设定定量光程的筛选条件，并基于所述适配吸光度线以及吸收光谱图筛选得到定量光程；
在本实施例中，令bi表示第i个光程，i＝1、2、…m，Cj表示第j个浓度，j＝1、2、……n，λij表示用第i个光程测得的第j个浓度的光谱曲线与适配吸光度线交点的波长，即在第i个光程的λ-Abs图中、从第j个浓度的光谱曲线与适配吸光度线交点作λ轴垂线所得垂足的波长；又令ΔCj＝Cj+1-Cj，j＝1、2、…n-1；令Δλij＝λi，j+1-λij，对任何i，j＝1、2、…n-1，i＝1、2、…m，其中：ΔCj为第j个浓度差，即第j+1个浓度与第j个浓度之差；Δλij为第i个光程的第j个垂足波长差，即第i个光程下第j+1个浓度的曲线与适配吸光度线交点至横轴的垂足波长，以及同一光程下第j个浓度的曲线与适配吸光度线交点至横轴的垂足波长之差；kij为第i个光程的第j个垂足波长差与第j个浓度差的比值。同时满足如下两个条件的光程为定量光程：a.kij≥δ，i＝1,2,…m，j＝1,2,…n-1，δ是一个用户自定义的大于0的正数，如0.6、0.65等；b.如果根据所选适配吸光度线无法获得满足所有条件的定量光程，在Abs轴上另选一个吸光度略低于适配吸光点的点位，将其作为新的适配吸光度点重新确定定量光程。
S50、观察定性光程下实际流动液体中目标物种的不同浓度所对应的特征波长与光谱曲线形状的变化规律，将其与在实际液体目标物种的不同浓度的静态样品中测得的定性波长λqual及光谱曲线形状的变化规律进行比对分析，确定在实际流动液体情形下目标物种不同浓度时定性波长λqual f的位置和曲线形状；
S60、获得定量光程在实际流动液体情形下从最低浓度到最高浓度Cj范围内不同浓度对应的波长λj，在定量光程下依据(Cj，λj)，制作以C为横坐标值、λ为纵坐标值的浓度-波长曲线；
S70、按统计学指标将所述浓度-波长曲线进一步划分为分段线性曲线，通过分段线性拟合得到C＝f(λ)的分段线性函数，即得到如图4所示符合要求的波长-浓度法模型；
S80、将待测流动液体流过定性光程bqual时给出监测物种的种类信息，在其流过定量光程时给出监测物种的波长信息，将所述波长信息代入所述波长-浓度模型，给出待测流动液体中目标物种的价态、形态、相态和浓度。
在本实施例实际运行过程中，在待测流动液体流过定性光程时设备给出监测物种的种类信息，在其流过定量光程时给出准确的波长信息，将波长信息代入波长浓度模型，可在10秒内准确给出流动状态高浓度液体中目标物种的价态、形态、相态和浓度等化学信息。本实施例提供的直测流动液体高浓度目标物种浓度的方法不需要对高浓度复杂溶液进行大倍数稀释、无需投加多种化学药剂，因此，无稀释误差和二次污染风险，10秒内可直接测定流动液体中高浓度溶液中目标物种的原价态、原形态、原相态及浓度等化学信息，不会出现待测溶液中目标物种发生改变的问题，测定后溶液可直接返回原系统，可以实时指导生产过程。本实施例方法克服了直接测定高浓度复杂溶液时朗伯比尔线性定律无法得到满足，甚至吸光度远超出仪器测定上限、无法快速给出溶液中物种的价态、形态、相态及浓度等重要信息的难题。
以上结合具体实施例描述了本发明的技术原理，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。其描述较为具体和详细，只是为了解释本申请，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的 前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (4)

  1. 一种直测流动液体高浓度目标物种浓度的方法，其特征在于，包括步骤：
    以含不同浓度目标物的流动液体作为样本，测量所述样本在紫外可见光和近红外光范围内的吸光度曲线，获取所述吸光度曲线中吸光度最高的尖锐峰对应的特征波长作为定性波长λqual，其对应的光程作为定性光程bqual；
    根据流动液体实际浓度范围配置不同浓度的溶液样品，在紫外可见光和近红外光波长范围内，依次用不同光程对所述溶液样品进行吸光度扫描，制作各光程下所述溶液样品的吸收光谱图；
    在所述溶液样品的吸收光谱图中，在Abs轴上选择一个适配的吸光度点，从所述吸光度点出发作一条平行于λ轴的直线，使其与目标物种的相关侧的所有光谱曲线相交于(λ，Abs)，此时平行于λ轴的直线为适配吸光度线；
    设定定量光程的筛选条件，并基于所述适配吸光度线以及吸收光谱图筛选得到定量光程；
    观察定性光程下实际流动液体中目标物种的不同浓度所对应的特征波长与光谱曲线形状的变化规律，将其与在实际液体目标物种的不同浓度的静态样品中测得的定性波长λqual及光谱曲线形状的变化规律进行比对分析，确定在实际流动液体情形下目标物种不同浓度时定性波长λqual f的位置和曲线形状；
    获得定量光程在实际流动液体情形下从最低浓度到最高浓度Cj范围内不同浓度对应的波长λj，在定量光程下依据(Cj，λj)，制作以C为横坐标值、λ为纵坐标值的浓度-波长曲线；
    按统计学指标将所述浓度-波长曲线进一步划分为分段线性曲线，通过分段线性拟合得到C＝f(λ)的分段线性函数，即得到符合要求的波长-浓度法模型；
    将待测流动液体流过定性光程bqual时给出监测物种的种类信息，在其流过定量光程时给出监测物种的波长信息，将所述波长信息代入所述波长-浓度模型，给出待测流动液体中目标物种的价态、形态、相态和浓度。
  2. 根据权利要求1所述直测流动液体高浓度目标物种浓度的方法，其特征在于，所述依次用不同光程对所述溶液样品进行吸光度扫描，制作各光程下所述溶液样品的吸收光谱图的步骤中，所选择的光程保证对溶液样品扫描所得曲线的峰顶吸光度值高于仪器最大吸光度的一半，且仪器最大吸光度一半附近非峰顶部分的吸光度曲线为光滑无毛刺曲线。
  3. 根据权利要求1所述直测流动液体高浓度目标物种浓度的方法，其特征在于，在Abs轴上选择一个适配的吸光度点的条件包括：a、从该点出发的直线与目标物种的相关侧所有光谱曲线交点处及其附近曲线段光滑无毛刺，各曲线段无相交趋势；b、Abs轴上满足条件a的所有各点中该点Abs值最大；c、从该点出发的直线与目标物种的相关侧的所有光谱曲线交点处的光谱不受其它物种光谱干扰；d、从该点出发的直线与目标物种相关侧的最低浓度和最高浓度光谱曲线交点处波长均在所用光源的最佳能量波长范围。
  4. 根据权利要求1所述直测流动液体高浓度目标物种浓度的方法，其特征在于，所述设定定量光程的筛选条件，并基于所述适配吸光度线以及吸收光谱图筛选得到定量光程，包括：
    令bi表示第i个光程，i＝1、2、…m，Cj表示第j个浓度，j＝1、2、……n，λij表示用第i个光程测得的第j个浓度的光谱曲线与适配吸光度线交点的波长，即在第i个光程的Abs-λ图中从第j个浓度的光谱曲线与适配吸光度线交点作λ轴垂线所得垂足的波长；
    令ΔCj＝Cj+1-Cj，j＝1、2、…n-1；令Δλij＝λi，j+1-λij，对任何i，j＝1、2、…n-1，i＝1、2、…m，其中，ΔCj为第j个浓度差，即第j+1个浓度与第j个浓度之差；Δλij为第i个光程的第j个垂足波长差，即第i个光程下第j+1个浓度的曲线与适配吸光度线交点至横轴的垂足波长，以及同一光程下第j个浓度的曲线与适配吸光度线交点至横轴的垂足波长之差；kij为第i个光程的第j个垂足波长差与第j个浓度差的比值；
    同时满足如下两个条件的光程为定量光程：kij≥δ，i＝1、2…m,j＝1,2,…n-1，δ是一个用户自定义的大于0的正数；
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