Industrial chromatography full-automatic quantitative analysis method and system based on intelligent sensor

Abstract

The invention relates to the technical field of quantitative analysis, and particularly discloses an industrial chromatography full-automatic quantitative analysis method and system based on an intelligent sensor, and the method comprises the following steps: carrying out chromatographic analysis on a to-be-detected sample based on the intelligent sensor to obtain a chromatographic peak curve of each component in the to-be-detected sample; obtaining a relative correction factor of each component in the sample to be detected to the standard substance; acquiring chromatographic peak parameters of each component based on the component peak shape comprehensive evaluation value of the to-be-detected sample, and determining the mass fraction of each component in the to-be-detected sample based on the chromatographic peak parameters of each component in the to-be-detected sample and the relative correction factor; the method is used for carrying out chromatographic analysis on a to-be-detected sample on the basis of industrial chromatography so as to accurately measure the mass fraction of each component in the to-be-detected sample.

Description

Technical Field

[0001] The present invention relates to the technical field of quantitative analysis, and in particular to a fully automatic quantitative analysis method and system for industrial chromatography based on intelligent sensors. Background Art

[0002] At present, quantitative analysis methods based on industrial chromatography are a widely used technology in the fields of chemistry, biomedicine, etc., which can qualitatively and quantitatively analyze samples by analyzing the interactions between various compounds in the samples. This quantitative analysis method has the advantages of being fast, accurate, and sensitive, and has become an important part of modern analytical technology. The basic principle of chromatography is to achieve separation and detection based on the difference in the distribution coefficients of different chemical substances between the stationary phase and the mobile phase. This method separates the mixture into two parts: one part is called the carrier liquid, in which it flows; the other part is called the stationary phase, whose properties and composition determine which chemical substances will stay where, thus achieving separation. Then, by detecting the separated components, the original sample can be analyzed.

[0003] However, in the prior art, when determining the mass fraction of each component in the sample to be tested by combining the chromatographic peak curve of each component of the sample to be tested with the intelligent sensor and combining the internal standard method, external standard method or normalization method, the peak height and peak area of ​​the chromatographic peak are mostly used. However, since the peak shapes of the chromatographic peaks of different components are different, whether the peak height or peak area of ​​the chromatographic peak is used for calculation will directly affect the accuracy of the component determination results.

[0004] Therefore, the present invention proposes an industrial chromatography fully automatic quantitative analysis method and system based on intelligent sensors. Summary of the invention

[0005] The present invention provides a fully automatic quantitative analysis method and system for industrial chromatography based on intelligent sensors, which are used to perform chromatographic analysis on a sample to be tested using industrial chromatography based on an intelligent sensor, and to reasonably determine which chromatographic peak parameters to use when measuring the mass fraction of each component in the sample to be tested by comprehensively evaluating the chromatographic peaks of each component in the sample to be tested, so as to ensure the measurement accuracy of the mass fraction of each component in the sample to be tested.

[0006] The present invention provides a fully automatic quantitative analysis method of industrial chromatography based on an intelligent sensor, comprising:

[0007] S1: Perform chromatographic analysis on the sample to be tested based on the intelligent sensor to obtain the chromatographic peak curve of each component in the sample to be tested;

[0008] S2: Obtain the relative correction factor of each component in the sample to be tested to the standard;

[0009] S3: Based on the comprehensive evaluation value of the component peak shape of the sample to be tested, the chromatographic peak parameters of each component are obtained, and based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, the mass fraction of each component in the sample to be tested is determined.

[0010] Preferably, S3: obtaining the chromatographic peak parameters of each component based on the comprehensive evaluation value of the peak shape of the component of the sample to be tested, and determining the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, including:

[0011] S301: based on the comprehensive evaluation value of the peak shape of the components of the sample to be tested, obtaining the chromatographic peak parameters of each component in the chromatographic peak curve of each component in the sample to be tested;

[0012] S302: Determine the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested.

[0013] Preferably, S301: based on the comprehensive evaluation value of the component peak shape of the sample to be tested, obtaining the chromatographic peak parameters of each component in the chromatographic peak curve of each component in the sample to be tested, including:

[0014] Evaluate the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested;

[0015] The average value of the peak shape evaluation values ​​of the chromatographic peak curves of all components in the sample to be tested is taken as the comprehensive evaluation value of the peak shape of the components of the sample to be tested;

[0016] When the comprehensive evaluation value of the component peak shape of the sample to be tested is less than the threshold value, the reference peak height of each component is determined based on the chromatographic peak curve of each component in the sample to be tested, as the chromatographic peak parameter of each component in the sample to be tested;

[0017] When the comprehensive evaluation value of the component peak shape of the sample to be tested is not less than the threshold value, the reference peak area of ​​each component is determined based on the chromatographic peak curve of each component in the sample to be tested as the chromatographic peak parameter of each component in the sample to be tested.

[0018] Preferably, evaluating the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested includes:

[0019] Determine the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested;

[0020] The intersection point of the vertical line of the drift baseline of the corresponding chromatographic peak curve drawn through the peak apex of the chromatographic peak curve of each component in the sample to be tested and the drift baseline of the corresponding chromatographic peak curve is regarded as the midpoint of the peak bottom of the corresponding chromatographic peak curve;

[0021] The distance from the peak top to the midpoint of the peak bottom of the chromatographic peak curve of each component in the sample to be tested is regarded as the de-drifted peak height of each component in the sample to be tested;

[0022] The midpoint of the line segment from the peak top to the peak bottom midpoint of the chromatographic peak curve of each component in the sample to be tested is regarded as the midpoint of the drift-free peak of the corresponding chromatographic peak curve;

[0023] The distance between the two intersection points of the corresponding chromatographic peak curve and the parallel line corresponding to the drift baseline passing through the midpoint of the de-drifted peak of the chromatographic peak curve of each component in the sample to be tested is regarded as the de-drifted half-peak width of the chromatographic peak curve of each component in the sample to be tested;

[0024] The distance between the two intersection points of the chromatographic peak curve of each component in the sample to be tested and the drift baseline is regarded as the drift-free peak width of the chromatographic peak curve of each component in the sample to be tested;

[0025] Based on the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested, the de-drifted peak height of each component, the de-drifted half-peak width of the chromatographic peak curve of each component, and the de-drifted peak width of the chromatographic peak curve of each component, the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested is obtained.

[0026] Preferably, based on the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested, the drift-free peak height of each component, the drift-free half-peak width of the chromatographic peak curve of each component, and the drift-free peak width of the chromatographic peak curve of each component, the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested is obtained, including:

[0027]

[0028] Where P is the peak shape evaluation value of the chromatographic peak curve of the i-th component in the sample to be tested, μ 1 is the preset drift component weight, |tanα i | is the angle α between the drift baseline and the time coordinate of the chromatographic peak curve of the i-th component in the sample to be tested i The tangent value of tanα i The absolute value of μ 2 is the preset peak height component weight, h 0 is the de-drifted peak height of the i-th component in the sample to be tested, μ 3 is the preset peak width weight, w 1 / 2 max is the half-peak width of the chromatographic peak curve of the i-th component in the sample to be tested, w max is the de-drifted peak width of the chromatographic peak curve of the i-th component in the sample to be tested, for The logarithmic function value with the natural constant e as the base, the value of e is 2.718.

[0029] Preferably, determining the reference peak height of each component based on the chromatographic peak curve of each component in the sample to be tested includes:

[0030] The intersection of a vertical line drawn through the peak apex of the chromatographic peak curve of each component in the sample to be tested and the drift baseline of the corresponding chromatographic peak curve is regarded as the lowest peak height point of the corresponding chromatographic peak curve;

[0031] The distance from the peak apex of the chromatographic peak curve of each component in the sample to be tested to the lowest peak height point of the corresponding chromatographic peak curve is taken as the reference peak height of each component.

[0032] Preferably, determining the reference peak area of ​​each component based on the chromatographic peak curve of each component in the sample to be tested includes:

[0033] The intersection of a vertical line drawn through the peak apex of the chromatographic peak curve of each component in the sample to be tested and the drift baseline of the corresponding chromatographic peak curve is regarded as the lowest peak height point of the corresponding chromatographic peak curve;

[0034] The length of the line segment from the peak apex of the chromatographic peak curve of each component in the sample to be tested to the lowest point of the peak height of the corresponding chromatographic peak curve is taken as the reference peak height of the corresponding chromatographic peak curve;

[0035] Determine the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested;

[0036] The product of the reference peak height and the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested is taken as the reference peak area of ​​each component.

[0037] Preferably, determining the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested includes:

[0038] The midpoint of the line segment from the peak apex of the chromatographic peak curve of each component in the sample to be tested to the lowest peak height point of the corresponding chromatographic peak curve is regarded as the peak height midpoint of the corresponding chromatographic peak curve;

[0039] The parallel line passing through the peak midpoint of the chromatographic peak curve of each component in the sample to be tested and corresponding to the drift baseline and the two intersection points of the corresponding chromatographic peak curve are regarded as the two half-peak height position points of the corresponding chromatographic peak curve;

[0040] The intersection point between the vertical line of the time coordinate passing through each half-peak height position point of the chromatographic peak curve of each component in the sample to be tested and the time coordinate is regarded as the time coordinate projection point of each half-peak height position point of the chromatographic peak curve of each component in the sample to be tested;

[0041] The distance between the time coordinate projection points of the two half-peak height position points of the chromatographic peak curve of each component in the sample to be tested is taken as the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested.

[0042] Preferably, S302: determining the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, including:

[0043]

[0044] In the formula, θ i is the mass fraction of the i-th component in the sample to be tested, R i is the chromatographic peak parameter of the i-th component in the sample to be tested, δ i is the relative correction factor of the i-th component in the sample to be tested to the standard, and n is the total number of components in the sample to be tested.

[0045] The present invention provides an industrial chromatography fully automatic quantitative analysis system based on an intelligent sensor, which is used to perform any of the above industrial chromatography fully automatic quantitative analysis methods based on an intelligent sensor, comprising:

[0046] The chromatographic analysis module is used to perform chromatographic analysis on the sample to be tested based on the intelligent sensor to obtain the chromatographic peak curve of each component in the sample to be tested;

[0047] A correction factor acquisition module is used to obtain the relative correction factor of each component in the sample to be tested to the standard;

[0048] The quantitative analysis module is used to obtain the chromatographic peak parameters of each component based on the comprehensive evaluation value of the component peak shape of the sample to be tested, and determine the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested.

[0049] The beneficial effects of the present invention compared with the prior art are as follows: based on the intelligent sensor, the industrial chromatography is used to perform chromatographic analysis on the sample to be tested, and by comprehensively evaluating the chromatographic peaks of each component in the sample to be tested, it is reasonably determined which chromatographic peak parameters to use when measuring the mass fraction of each component in the sample to be tested, so as to ensure the measurement accuracy of the mass fraction of each component in the sample to be tested.

[0050] Other features and advantages of the present invention will be described in the following description, and partly become apparent from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention can be realized and obtained by the structures specifically pointed out in this application document.

[0051] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings:

[0053] Figure 1 This is a flow chart of a fully automatic quantitative analysis method of industrial chromatography based on an intelligent sensor in an embodiment of the present invention;

[0054] Figure 2 is a flowchart of the specific execution process of step S3 in an embodiment of the present invention;

[0055] Figure 3 Schematic diagram of the internal functional modules of the fully automatic quantitative analysis system for industrial chromatography based on intelligent sensors in an embodiment of the present invention. DETAILED DESCRIPTION

[0056] The preferred embodiments of the present invention are described below in conjunction with the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0057] Embodiment 1:

[0058] The present invention provides a fully automatic quantitative analysis method for industrial chromatography based on intelligent sensors. Figure 1 ,include:

[0059] S1: Perform chromatographic analysis on the sample to be tested based on the intelligent sensor to obtain the chromatographic peak curve of each component in the sample to be tested;

[0060] S2: Obtain the relative correction factor of each component in the sample to be tested to the standard;

[0061] S3: Based on the comprehensive evaluation value of the component peak shape of the sample to be tested, the chromatographic peak parameters of each component are obtained, and based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, the mass fraction of each component in the sample to be tested is determined.

[0062] In this embodiment, "chromatographic analysis of the sample to be tested is performed based on the intelligent sensor to obtain the chromatographic peak curve of each component in the sample to be tested" means that the chromatographic analysis operation of the sample to be tested is performed using a sensor with intelligent functions, so as to obtain the chromatographic peak curves corresponding to different components in the sample. For example, the intelligent sensor can automatically control the injection volume, adjust the analysis conditions (such as flow rate, temperature, etc.), and monitor and record data in real time. For example, when detecting the components in a certain drug, the intelligent sensor can accurately control the amount of sample entering the chromatograph, and then through a series of detection and processing, give clear chromatographic peak curves of components such as aspirin and acetaminophen to reflect their content in the sample.

[0063] In this embodiment, the sample for quantitative analysis by industrial chromatography can be solid, liquid or gaseous. Among them, the analysis of liquid samples is the most common. When performing quantitative analysis by industrial chromatography, the sample is generally loaded into a capillary column, and the interior of the column is filled with a solid carrier material, called a stationary phase. What flows in the column is a carrier fluid, usually an organic solvent or an aqueous solution. When the carrier fluid flows through the stationary phase, the fixed target compound will be separated. Then, by detecting the components entering the detector, quantitative analysis can be performed.

[0064] In this embodiment, the chromatographic peak curve is a curve generated by the continuous signal of the response when the component flows through the detector.

[0065] In this embodiment, the samples to be tested can be the following:

[0066] Petrochemical products: such as crude oil, gasoline, kerosene, diesel, etc. The hydrocarbon compounds in these samples can be quantitatively analyzed by chromatography to determine their respective contents and proportions;

[0067] Pharmaceuticals: such as antibiotics, hormones, and biological agents. These drug compounds have high chemical stability and specific pharmacological activity, so high performance liquid chromatography (HPLC) is required for quantitative and qualitative analysis;

[0068] Food and beverages: such as coffee, tea, juice, dairy products, etc. The volatile components in these samples can be analyzed by gas chromatography (GC);

[0069] Cosmetics and personal care products: such as facial cleansers, toners, lipsticks, perfumes, etc. The fragrance compounds in these products can be quantitatively and qualitatively analyzed by gas chromatography and mass spectrometry (GC-MS);

[0070] Environmental samples: such as soil, water and air samples. Hazardous substances in these samples can be quantitatively and qualitatively analyzed by gas chromatography and mass spectrometry (GC-MS);

[0071] Pesticides and fertilizers: such as herbicides, insecticides, fertilizers, etc. The pesticide residues in these samples can be quantitatively and qualitatively analyzed by gas chromatography.

[0072] In this embodiment, the components in the sample to be tested are the compounds contained in the sample to be tested.

[0073] In this embodiment, the relative (mass or molar) correction factor of each component in the sample to be tested to the standard substance (benzene) is:

[0074] In gas chromatography, quantitative calculations are based on the fact that the content (mass or amount of substance) of each component is proportional to the peak area (or peak height) of each component;

[0075] When using gas chromatography to analyze the content of different components in a mixture, the peak areas of different components cannot be directly compared because the response values ​​produced by different components on the same detector are different (that is, the corresponding peak areas of different components with the same content are not equal). In order to perform quantitative calculations, it is necessary to introduce a quantitative correction factor, using the peak area of ​​a certain component as a standard, and calibrate the peak areas of other components according to this standard. After calibration, the peak areas of different components can be compared, and the percentage content of each component can be calculated;

[0076] Quantitative correction factors can be divided into absolute correction factors and relative correction factors;

[0077] The absolute correction factor is equal to the ratio of the mass fraction of the component to the chromatographic peak parameter of the component;

[0078] The absolute calibration factor of a compound compared to the absolute calibration factor of another standard (benzene) is called the relative calibration factor of the compound;

[0079] When determining the relative correction factor, first prepare a series of mixed solutions of the analyte and the standard with known mass fractions. The concentration of the analyte components should be equivalent to the concentration of the analyte in the sample. Under certain operating conditions, perform gas chromatography analysis, and then plot the ratio of mass fraction to peak area to obtain a straight line passing through the origin. The slope of the straight line, tanQ, is the relative correction factor of the analyte.

[0080] In this embodiment, the comprehensive evaluation value of the component peak shape of the sample to be tested is a numerical value that is evaluated based on the degree to which the components of the sample to be tested are not offset, the comprehensive width of the chromatographic peak, and the height of the chromatographic peak, and represents the degree of excellence of the chromatographic peak shape of all components in the sample to be tested. Among them, the higher and narrower the chromatographic peaks of all components of the sample to be tested, the smaller the comprehensive evaluation value of the component peak shape of the sample to be tested, and vice versa.

[0081] In this embodiment, the mass fraction of each component is the percentage of the mass of a certain component in a substance to the total mass of the substance in the sample.

[0082] The beneficial effects of the above technology are: based on the intelligent sensor, industrial chromatography is used to perform chromatographic analysis on the sample to be tested, and by comprehensively evaluating the chromatographic peaks of each component in the sample to be tested, it is reasonably determined which chromatographic peak parameters to use when measuring the mass fraction of each component in the sample to be tested, so as to ensure the accuracy of the measurement of the mass fraction of each component in the sample to be tested.

[0083] Embodiment 2:

[0084] On the basis of Example 1, S3: based on the comprehensive evaluation value of the peak shape of the components of the sample to be tested, the chromatographic peak parameters of each component are obtained, and based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, the mass fraction of each component in the sample to be tested is determined, referring to Figure 2 ,include:

[0085] S301: based on the comprehensive evaluation value of the peak shape of the components of the sample to be tested, obtaining the chromatographic peak parameters of each component in the chromatographic peak curve of each component in the sample to be tested;

[0086] S302: Determine the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested.

[0087] The beneficial effect of the above technology is: by evaluating the performance of the chromatographic peak shapes of all components in the sample to be tested, the evaluation value is obtained, and the chromatographic peak parameters used to determine the mass fraction of each component in the sample to be tested are reasonably determined, thereby ensuring the accuracy of the determined mass fraction of each component in the sample to be tested.

[0088] Embodiment 3:

[0089] On the basis of Example 2, S301: based on the comprehensive evaluation value of the component peak shape of the sample to be tested, the chromatographic peak parameters of each component in the chromatographic peak curve of each component in the sample to be tested are obtained, including:

[0090] Evaluate the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested;

[0091] The average value of the peak shape evaluation values ​​of the chromatographic peak curves of all components in the sample to be tested is taken as the comprehensive evaluation value of the peak shape of the components of the sample to be tested;

[0092] When the comprehensive evaluation value of the component peak shape of the sample to be tested is less than the threshold value, the reference peak height of each component is determined based on the chromatographic peak curve of each component in the sample to be tested, as the chromatographic peak parameter of each component in the sample to be tested;

[0093] When the comprehensive evaluation value of the component peak shape of the sample to be tested is not less than the threshold value, the reference peak area of ​​each component is determined based on the chromatographic peak curve of each component in the sample to be tested as the chromatographic peak parameter of each component in the sample to be tested.

[0094] In this embodiment, the peak shape evaluation value of the chromatographic peak curve is a numerical value that is evaluated based on the degree to which a single component has not shifted, the comprehensive width of the chromatographic peak, and the height of the chromatographic peak, and represents the degree of excellence of the chromatographic peak shape of a single component. The higher and narrower the chromatographic peak of a single component, the smaller the comprehensive evaluation value of its component peak shape, and vice versa.

[0095] In this embodiment, the threshold value is a preset division value of the component peak shape comprehensive evaluation value based on which the chromatographic peak parameters of each component in the sample to be tested are determined. Since the higher and narrower the chromatographic peak is, the lower the accuracy of calculating the mass fraction of the component using the peak area, the chromatographic peak parameters used to determine the mass fraction of each component in the sample to be tested can be reasonably determined by threshold division. The threshold value can be determined through multiple experiments using big data technology.

[0096] The beneficial effects of the above technology are as follows: by evaluating the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested, and taking the average value of the peak shape evaluation values ​​of the chromatographic peak curves of all components as the comprehensive evaluation value of the component peak shape of the sample to be tested, the evaluation of the performance excellence of the chromatographic peak shapes of all components in the sample to be tested is achieved; and then by comparing the comprehensive evaluation value of the component peak shape of the sample to be tested with the threshold value, the chromatographic peak parameters used to determine the mass fraction of each component in the sample to be tested are reasonably determined, thereby ensuring the accuracy of the determined mass fraction of each component in the sample to be tested.

[0097] Embodiment 4:

[0098] On the basis of Example 3, the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested is evaluated, including:

[0099] Determine the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested;

[0100] The intersection point B of the vertical line AB of the drift baseline of the corresponding chromatographic peak curve drawn through the peak apex A of the chromatographic peak curve of each component in the sample to be tested and the drift baseline of the corresponding chromatographic peak curve is regarded as the peak bottom midpoint B of the corresponding chromatographic peak curve;

[0101] The distance from the peak apex A to the peak bottom midpoint B of the chromatographic peak curve of each component in the sample to be tested is regarded as the de-drifted peak height of each component in the sample to be tested;

[0102] The midpoint C of the line segment from the peak apex A to the peak bottom midpoint B of the chromatographic peak curve of each component in the sample to be tested is regarded as the midpoint C of the de-drifted peak of the corresponding chromatographic peak curve;

[0103] The distance between the parallel line DE corresponding to the drift baseline passing through the midpoint C of the de-drifted peak of the chromatographic peak curve of each component in the sample to be tested and the two intersection points (point D and point E) of the corresponding chromatographic peak curve is regarded as the de-drifted half-peak width of the chromatographic peak curve of each component in the sample to be tested;

[0104] The distance between the two intersection points F and G of the chromatographic peak curve of each component in the sample to be tested and the drift baseline is regarded as the drift-free peak width of the chromatographic peak curve of each component in the sample to be tested;

[0105] Based on the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested, the de-drifted peak height of each component, the de-drifted half-peak width of the chromatographic peak curve of each component, and the de-drifted peak width of the chromatographic peak curve of each component, the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested is obtained.

[0106] In this embodiment, the drift baseline of the chromatographic peak curve is: since the chromatographic peak is a normal distribution curve when the experimental conditions are stable, but the chromatographic analysis may produce a baseline drift due to unstable experimental conditions during the actual operation. Therefore, the straight line connecting the starting point and the end point of the chromatographic peak obtained during the actual operation is the drift baseline of the chromatographic peak curve.

[0107] In this embodiment, the time coordinate is the abscissa of the coordinate system representing the chromatographic peak curve.

[0108] In this embodiment, the peak apex of the chromatographic peak curve is the highest point in the chromatographic peak curve.

[0109] The beneficial effects of the above technology are: by defining and determining the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested, the de-drifted peak height of each component, the de-drifted half-peak width of the chromatographic peak curve of each component, and the de-drifted peak width of the chromatographic peak curve of each component, a specific parameter basis is provided for the peak shape evaluation of the chromatographic peak curve of each component in the sample to be tested.

[0110] Embodiment 5:

[0111] On the basis of Example 4, based on the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested, the drift-free peak height of each component, the drift-free half-peak width of the chromatographic peak curve of each component, and the drift-free peak width of the chromatographic peak curve of each component, the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested is obtained, including:

[0112]

[0113] Where P is the peak shape evaluation value of the chromatographic peak curve of the i-th component in the sample to be tested, μ 1 is the preset drift component weight, |tanα i | is the angle α between the drift baseline and the time coordinate of the chromatographic peak curve of the i-th component in the sample to be tested i The tangent value of tanα i The absolute value of μ 2 is the preset peak height component weight, h 0 is the de-drifted peak height of the i-th component in the sample to be tested, μ 3 is the preset peak width weight, w 1 / 2max is the half-peak width of the chromatographic peak curve of the i-th component in the sample to be tested, w max is the de-drifted peak width of the chromatographic peak curve of the i-th component in the sample to be tested, for The logarithmic function value with the natural constant e as the base, the value of e is 2.718.

[0114] In this embodiment, the preset drift component weight is a preset representation |tanα i |The numerical ratio in the peak shape evaluation value of the chromatographic peak curve of the component.

[0115] In this embodiment, the preset peak height component weight is a preset representation h 0 The numerical ratio in the peak shape evaluation value of the chromatographic peak curve of the component.

[0116] In this embodiment, the preset peak width weight is a preset representation The numerical ratio in the peak shape evaluation value of the chromatographic peak curve of the component.

[0117] In this embodiment, μ 1 , μ 2 , μ 3 The sum is 1.

[0118] The beneficial effects of the above technology are: by taking a weighted sum of the angle between the drift baseline and the time coordinate of the chromatographic peak curve of a single component in the sample to be tested, the de-drifted peak height, the de-drifted half-peak width of the chromatographic peak curve, and the standardized values ​​of the de-drifted peak width ratio, and by comprehensively considering the degree to which the single component has not shifted, the comprehensive width of the chromatographic peak, and the height of the chromatographic peak, a reasonable evaluation of the peak shape of the chromatographic peak curve of a single component is achieved.

[0119] Embodiment 6:

[0120] On the basis of Example 4, the reference peak height of each component is determined based on the chromatographic peak curve of each component in the sample to be tested, including:

[0121] The intersection point I of the vertical line AH of the time coordinate drawn through the peak apex A of the chromatographic peak curve of each component in the sample to be tested and the drift baseline of the corresponding chromatographic peak curve is regarded as the lowest peak height point of the corresponding chromatographic peak curve;

[0122] The distance from the peak point A of the chromatographic peak curve of each component in the sample to be tested to the lowest peak height point I of the corresponding chromatographic peak curve is taken as the reference peak height of each component.

[0123] The beneficial effect of the above technology is: under the premise that the chromatographic peak waveform is narrow and high, the meaning of the peak height used to determine the mass fraction of each component in the sample to be tested is reasonably defined.

[0124] Embodiment 7:

[0125] On the basis of Example 3, the reference peak area of ​​each component is determined based on the chromatographic peak curve of each component in the sample to be tested, including:

[0126] The intersection point I of the vertical line AH of the time coordinate drawn through the peak apex A of the chromatographic peak curve of each component in the sample to be tested and the drift baseline of the corresponding chromatographic peak curve is regarded as the lowest peak height point I of the corresponding chromatographic peak curve;

[0127] The length of the line segment from the peak apex A of the chromatographic peak curve of each component in the sample to be tested to the lowest peak height point I of the corresponding chromatographic peak curve is taken as the reference peak height of the corresponding chromatographic peak curve;

[0128] Determine the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested;

[0129] The product of the reference peak height and the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested is taken as the reference peak area of ​​each component.

[0130] In this embodiment, since the shape of the chromatographic peak is close to an isosceles triangle, according to the calculation method for calculating the area of ​​an isosceles triangle, the product of the reference peak height and the reference half-peak width of the chromatographic peak curve is approximately taken as the reference peak area of ​​each component.

[0131] The beneficial effect of the above technology is: under the premise that the chromatographic peak waveform is not too narrow and not too high, the meaning of the peak area used to determine the mass fraction of each component in the sample to be tested is reasonably defined.

[0132] Embodiment 8:

[0133] Based on Example 7, the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested is determined, including:

[0134] The midpoint J of the line segment from the peak apex A of the chromatographic peak curve of each component in the sample to be tested to the lowest peak height point I of the corresponding chromatographic peak curve is regarded as the peak height midpoint J of the corresponding chromatographic peak curve;

[0135] The parallel line KL passing through the peak midpoint J of the chromatographic peak curve of each component in the sample to be tested and corresponding to the drift baseline and the two intersection points (point K and point L) of the corresponding chromatographic peak curve are regarded as the two half-peak height position points (point K and point L) of the corresponding chromatographic peak curve;

[0136] The intersection points M and N between the vertical lines KM and LN of the time coordinate passing through each half-peak height position point of the chromatographic peak curve of each component in the sample to be tested and the time coordinate are regarded as the time coordinate projection points M and N of each half-peak height position point of the chromatographic peak curve of each component in the sample to be tested;

[0137] The distance between the time coordinate projection points of the two half-peak height position points of the chromatographic peak curve of each component in the sample to be tested is taken as the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested.

[0138] The beneficial effect of the above technology is: under the premise that the chromatographic peak waveform is not too narrow and not too high, the reference half-peak width required in the process of determining the peak area for determining the mass fraction of each component in the sample to be tested is reasonably defined.

[0139] Embodiment 9:

[0140] On the basis of Example 2, S302: determining the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, including:

[0141]

[0142] In the formula, θ i is the mass fraction of the i-th component in the sample to be tested, R i is the chromatographic peak parameter of the i-th component in the sample to be tested, δ i is the relative correction factor of the i-th component in the sample to be tested to the standard, and n is the total number of components in the sample to be tested.

[0143] The beneficial effect of the above technology is: using the normalization method, and based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, the mass fraction of each component in the sample to be tested can be accurately determined.

[0144] Embodiment 10:

[0145] The present invention provides an industrial chromatography fully automatic quantitative analysis system based on an intelligent sensor, which is used to perform the industrial chromatography fully automatic quantitative analysis method based on an intelligent sensor described in any one of embodiments 1 to 9, with reference to Figure 3 ,include:

[0146] The chromatographic analysis module is used to perform chromatographic analysis on the sample to be tested based on the intelligent sensor to obtain the chromatographic peak curve of each component in the sample to be tested;

[0147] A correction factor acquisition module is used to obtain the relative correction factor of each component in the sample to be tested to the standard;

[0148] The quantitative analysis module is used to obtain the chromatographic peak parameters of each component based on the comprehensive evaluation value of the component peak shape of the sample to be tested, and determine the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested.

[0149] The beneficial effects of the above technology are: based on the intelligent sensor, industrial chromatography is used to perform chromatographic analysis on the sample to be tested, and by comprehensively evaluating the chromatographic peaks of each component in the sample to be tested, it is reasonably determined which chromatographic peak parameters to use when measuring the mass fraction of each component in the sample to be tested, so as to ensure the accuracy of the measurement of the mass fraction of each component in the sample to be tested.

[0150] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A fully automatic quantitative analysis method for industrial chromatography based on intelligent sensors, characterized in that: include: S1: Perform chromatographic analysis on the sample to be tested based on the intelligent sensor to obtain the chromatographic peak curve of each component in the sample to be tested; S2: Obtain the relative correction factor of each component in the sample to be tested to the standard; S3: Based on the comprehensive evaluation value of the component peak shape of the sample to be tested, the chromatographic peak parameters of each component are obtained, and based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, the mass fraction of each component in the sample to be tested is determined.

2. The fully automatic quantitative analysis method of industrial chromatography based on intelligent sensor according to claim 1 is characterized in that: S3: Based on the comprehensive evaluation value of the component peak shape of the sample to be tested, the chromatographic peak parameters of each component are obtained, and based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, the mass fraction of each component in the sample to be tested is determined, including: S301: based on the comprehensive evaluation value of the peak shape of the components of the sample to be tested, obtaining the chromatographic peak parameters of each component in the chromatographic peak curve of each component in the sample to be tested; S302: Determine the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested.

3. The fully automatic quantitative analysis method of industrial chromatography based on intelligent sensor according to claim 2 is characterized in that: S301: Based on the comprehensive evaluation value of the component peak shape of the sample to be tested, the chromatographic peak parameters of each component in the chromatographic peak curve of each component in the sample to be tested are obtained, including: Evaluate the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested; The average value of the peak shape evaluation values ​​of the chromatographic peak curves of all components in the sample to be tested is taken as the comprehensive evaluation value of the peak shape of the components of the sample to be tested; When the comprehensive evaluation value of the component peak shape of the sample to be tested is less than the threshold value, the reference peak height of each component is determined based on the chromatographic peak curve of each component in the sample to be tested as the chromatographic peak parameter of each component in the sample to be tested; When the comprehensive evaluation value of the component peak shape of the sample to be tested is not less than the threshold value, the reference peak area of ​​each component is determined based on the chromatographic peak curve of each component in the sample to be tested as the chromatographic peak parameter of each component in the sample to be tested.

4. The fully automatic quantitative analysis method of industrial chromatography based on intelligent sensor according to claim 3 is characterized in that: Evaluate the peak shape of the chromatographic peak curve of each component in the sample to be tested, including: Determine the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested; The intersection point of the vertical line of the drift baseline of the corresponding chromatographic peak curve drawn through the peak apex of the chromatographic peak curve of each component in the sample to be tested and the drift baseline of the corresponding chromatographic peak curve is regarded as the midpoint of the peak bottom of the corresponding chromatographic peak curve; The distance from the peak top to the midpoint of the peak bottom of the chromatographic peak curve of each component in the sample to be tested is regarded as the de-drifted peak height of each component in the sample to be tested; The midpoint of the line segment from the peak top to the peak bottom midpoint of the chromatographic peak curve of each component in the sample to be tested is regarded as the midpoint of the drift-free peak of the corresponding chromatographic peak curve; The distance between the two intersection points of the corresponding chromatographic peak curve and the parallel line corresponding to the drift baseline passing through the midpoint of the de-drifted peak of the chromatographic peak curve of each component in the sample to be tested is regarded as the de-drifted half-peak width of the chromatographic peak curve of each component in the sample to be tested; The distance between the two intersection points of the chromatographic peak curve of each component in the sample to be tested and the drift baseline is regarded as the de-drifted peak width of the chromatographic peak curve of each component in the sample to be tested; Based on the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested, the de-drifted peak height of each component, the de-drifted half-peak width of the chromatographic peak curve of each component, and the de-drifted peak width of the chromatographic peak curve of each component, the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested is obtained.

5. The fully automatic quantitative analysis method of industrial chromatography based on intelligent sensor according to claim 4 is characterized in that: Based on the angle between the drift baseline and the time coordinate of the chromatographic peak curve of each component in the sample to be tested, the de-drifted peak height of each component, the de-drifted half-peak width of the chromatographic peak curve of each component, and the de-drifted peak width of the chromatographic peak curve of each component, the peak shape evaluation value of the chromatographic peak curve of each component in the sample to be tested is obtained, including: Where P is the peak shape evaluation value of the chromatographic peak curve of the i-th component in the sample to be tested, μ1 is the preset drift component weight, |tanα i | is the angle α between the drift baseline and the time coordinate of the chromatographic peak curve of the i-th component in the sample to be tested i The tangent value of tanα i The absolute value of μ2 is the preset peak height component weight, h0 is the de-drift peak height of the i-th component in the sample to be tested, μ3 is the preset peak width weight, and w 1 / 2 max is the half-peak width of the chromatographic peak curve of the i-th component in the sample to be tested, w max is the de-drifted peak width of the chromatographic peak curve of the i-th component in the sample to be tested, for The logarithmic function value with the natural constant e as the base, the value of e is 2.

718.

6. The fully automatic quantitative analysis method of industrial chromatography based on intelligent sensor according to claim 4 is characterized in that: Based on the chromatographic peak curve of each component in the sample to be tested, the reference peak height of each component is determined, including: The intersection of a vertical line drawn through the peak apex of the chromatographic peak curve of each component in the sample to be tested and the drift baseline of the corresponding chromatographic peak curve is regarded as the lowest peak height point of the corresponding chromatographic peak curve; The distance from the peak apex of the chromatographic peak curve of each component in the sample to be tested to the lowest peak height point of the corresponding chromatographic peak curve is taken as the reference peak height of each component.

7. The fully automatic quantitative analysis method of industrial chromatography based on intelligent sensor according to claim 3 is characterized in that: Based on the chromatographic peak curve of each component in the sample to be tested, the reference peak area of ​​each component is determined, including: The intersection of a vertical line drawn through the peak apex of the chromatographic peak curve of each component in the sample to be tested and the drift baseline of the corresponding chromatographic peak curve is regarded as the lowest peak height point of the corresponding chromatographic peak curve; The length of the line segment from the peak apex of the chromatographic peak curve of each component in the sample to be tested to the lowest point of the peak height of the corresponding chromatographic peak curve is taken as the reference peak height of the corresponding chromatographic peak curve; Determine the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested; The product of the reference peak height and the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested is taken as the reference peak area of ​​each component.

8. The fully automatic quantitative analysis method of industrial chromatography based on intelligent sensor according to claim 7, characterized in that: Determine the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested, including: The midpoint of the line segment from the peak apex of the chromatographic peak curve of each component in the sample to be tested to the lowest peak height point of the corresponding chromatographic peak curve is regarded as the peak height midpoint of the corresponding chromatographic peak curve; The parallel line passing through the peak midpoint of the chromatographic peak curve of each component in the sample to be tested and corresponding to the drift baseline and the two intersection points of the corresponding chromatographic peak curve are regarded as the two half-peak height position points of the corresponding chromatographic peak curve; The intersection point between the vertical line of the time coordinate passing through each half-peak height position point of the chromatographic peak curve of each component in the sample to be tested and the time coordinate is regarded as the time coordinate projection point of each half-peak height position point of the chromatographic peak curve of each component in the sample to be tested; The distance between the time coordinate projection points of the two half-peak height position points of the chromatographic peak curve of each component in the sample to be tested is taken as the reference half-peak width of the chromatographic peak curve of each component in the sample to be tested.

9. The fully automatic quantitative analysis method of industrial chromatography based on intelligent sensor according to claim 2, characterized in that: S302: Determine the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested, including: In the formula, θ i is the mass fraction of the i-th component in the sample to be tested, R i is the chromatographic peak parameter of the i-th component in the sample to be tested, δ i is the relative correction factor of the i-th component in the sample to be tested to the standard, and n is the total number of components in the sample to be tested.

10. The fully automatic quantitative analysis system of industrial chromatography based on intelligent sensors is characterized by: The method for fully automatic quantitative analysis of industrial chromatography based on an intelligent sensor according to any one of claims 1 to 9 comprises: The chromatographic analysis module is used to perform chromatographic analysis on the sample to be tested based on the intelligent sensor to obtain the chromatographic peak curve of each component in the sample to be tested; A correction factor acquisition module is used to obtain the relative correction factor of each component in the sample to be tested to the standard; The quantitative analysis module is used to obtain the chromatographic peak parameters of each component based on the comprehensive evaluation value of the component peak shape of the sample to be tested, and determine the mass fraction of each component in the sample to be tested based on the chromatographic peak parameters and relative correction factors of each component in the sample to be tested.

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