Chromatographic analysis correction method and system for 4,4′-biphenyldiphenol

By setting acquisition intervals and outlier analysis, the outliers in the chromatographic analysis data of 4,4'-brequicin are identified and corrected, which solves the data redundancy and unreliability problems, and improves the accuracy of the analysis results and stability.

CN118937552BActive Publication Date: 2024-12-20HUNAN GUOYUAN NEW MATERIAL TECH CO LTD
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Patent Information

Application Number
CN202411426884.7
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2024-10-14
Publication Date
2024-12-20
Estimated Expiration
2044-10-14

AI Technical Summary

Technical Problem

During the chromatographic analysis of 4,4'-bifenol, there are data redundancy and unreliability problems in the data acquisition process, resulting in deviations in the analysis results and it is difficult to make effective corrections.

Method used

By setting the acquisition interval, collecting chromatograph signal data in real time, identifying outliers, distinguishing bisquicin from interference peaks, conducting peak identification classification and statistical analysis, evaluating the reliability of signal data, and generating correction instructions based on abnormal evaluation values ​​for data Corrected.

Benefits of technology

It improves the accuracy and stability of chromatographic analysis results, effectively distinguishes bisquicin from interference peaks, reduces data redundancy, and ensures the reliability and quality of the analysis results.

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Abstract

The invention discloses a chromatographic analysis correction method and system applied to 4,4′-biphenol, belonging to the technical field of chemical analysis. In the chromatographic analysis of 4,4′-biphenol, too much data acquisition data is prone to redundancy, too little data acquisition data leads to inaccurate analysis, and it is difficult to diagnose the reliability of the data and to determine the correction method. The invention comprises an acquisition module, an analysis module and a correction module. The acquisition module avoids data redundancy while ensuring accuracy and timeliness by reasonably setting the acquisition interval. The analysis module can diagnose data reliability, identify abnormal values ​​of the collected signal data, distinguish target compounds from interference peaks and classify them, statistically analyze and obtain abnormal evaluation values, and the correction module performs targeted correction on the abnormal values ​​according to the analysis results. The system improves the efficiency and accuracy of data acquisition, effectively distinguishes interference peaks, provides a basis for data analysis and correction, and improves the accuracy and stability of the analysis results.
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Description

Technical Field

[0001] The invention belongs to the technical field of chemical analysis, and in particular relates to a chromatographic analysis correction method and system applied to 4,4'-biphenol. Background Art

[0002] 4,4′-Biphenol is an important compound that is widely used in many industries. Accurate chromatographic analysis is crucial to determine the content and purity of 4,4′-biphenol. However, in the actual chromatographic analysis process, it is often affected by a variety of factors, resulting in deviations in the analysis results.

[0003] Accurate chromatographic analysis of 4,4′-biphenol is crucial. However, there are many challenges in the chromatographic analysis of 4,4′-biphenol. Among them, data collection is crucial. Too much data will cause data redundancy, and too little data will cause inaccurate data analysis. In real-time data collection and analysis, it is difficult to diagnose whether the data is reliable. If the results are unreliable, it is unknown how to correct them. For this reason, we propose a chromatographic analysis correction method and system for 4,4′-biphenol. Summary of the invention

[0004] The object of the present invention is to provide a chromatographic analysis correction method and system for 4,4′-biphenol to solve the problems raised in the above background technology.

[0005] To achieve the above object, the present invention provides the following technical solution: a chromatographic analysis correction method for 4,4′-biphenol is applied to:

[0006] S1: The signal data output by the chromatograph is collected in real time by setting the collection interval. The signal data output by the chromatograph includes peak area, chromatographic peak retention time, peak height and is sent to the analysis module;

[0007] S2: Identify outliers on the signal data, distinguish 4,4′-biphenol from interference peaks, classify different types of peaks, analyze the signal data after outlier identification and peak identification classification, and obtain the average value of peak area, average value of chromatographic peak retention time, and average value of peak height. Analyze the standard deviation of each signal data based on the average value of each signal data. Analyze the coefficient of variation corresponding to each signal data based on the standard deviation and average value of each signal data. Finally, perform a comprehensive analysis based on the coefficient of variation of peak area, coefficient of variation of chromatographic peak retention time, and coefficient of variation of peak height to obtain the abnormal evaluation value to evaluate the reliability of the signal data.

[0008] S3: If the signal data is unreliable, analyze and correct it.

[0009] Preferably, the collection interval is set as follows:

[0010] Prepare multiple identical samples containing 4,4′-biphenyldiphenol, ensure that the concentration and matrix of the samples are consistent, use the same chromatograph, under the same mobile phase, flow rate, and column temperature, analyze these samples, record the time from injection to completion of each analysis, calculate the average of these times, and obtain the average analysis time T. According to the formula: V=1 / T, obtain the chromatographic analysis speed V;

[0011] Select a group of standard samples containing 4,4′-biphenyldiphenol and compounds with similar structures; perform multiple chromatographic analyses on the standard samples using the same chromatographic conditions;

[0012] For each chromatographic analysis, measure the retention time difference Δt and average peak width W between adjacent peaks, calculate the resolution value R = Δt / W for each analysis, and determine the required minimum resolution value Rmin based on the specific needs of the analysis;

[0013] Conduct a series of simulation experiments with different data volumes, record the time t required for the system to process the data and the corresponding data volume d, where the data volume d can be expressed in bytes, and the data processing capacity C = d / t;

[0014] Using the formula: , and obtain the collection interval coefficient I, where K is the preset adjustment coefficient, and a1, a2, and a3 are preset weight coefficients.

[0015] Preferably, the signal data is collected in the following manner:

[0016] Peak area: The data acquisition device continuously monitors the intensity change of the chromatographic signal according to the set acquisition interval. When the change rate of the chromatographic signal intensity continues to increase and then continues to decrease within a period of time, a signal intensity threshold is preset. When the signal intensity exceeds the preset threshold, it is determined that the starting point of the chromatographic peak has been detected; when the signal intensity returns to a level close to the starting level again and the change rate tends to be stable, it is determined that the end point of the chromatographic peak has been detected; the area under the peak is calculated using the trapezoidal integration algorithm to obtain the peak area;

[0017] Chromatographic peak retention time: The data acquisition device records the time from the start of injection according to the acquisition interval, and continuously monitors the chromatographic signal during the acquisition process; when the characteristics of the chromatographic signal match the known standard signal characteristics of 4,4′-biphenol or a specific component, if the signal intensity changes within a specific range and a specific peak shape characteristic appears, it is determined that the chromatographic peak of the specific component is detected, and the time recorded at this time is the chromatographic peak retention time of the component;

[0018] Peak height: During monitoring based on the collection interval, when a chromatographic peak is detected, the signal intensity value corresponding to the maximum value of the chromatographic signal intensity is recorded as the peak height.

[0019] Preferably, the process of identifying outliers on signal data is:

[0020] Based on historical experimental data, determine the reasonable fluctuation range threshold of peak area, the preset range of chromatographic peak retention time, and the peak height threshold range;

[0021] For the collected peak area data, compare it with the peak area fluctuation range threshold. If it exceeds the upper and lower limits of the threshold range, it is marked as a peak area abnormal value; if it falls within the threshold range, it is marked as a peak area qualified value;

[0022] For the chromatographic peak retention time data, it is also compared with the preset range of the chromatographic peak retention time. The data beyond the upper and lower limits of the range are marked as abnormal chromatographic peak retention time values, and the data within the range are marked as qualified chromatographic peak retention time values;

[0023] The peak height data is processed in a similar manner, with those outside the upper and lower limits of the peak height threshold range marked as outliers, and those within the range marked as qualified values.

[0024] Preferably, the process of distinguishing 4,4′-biphenol from interfering peaks and classifying different types of peaks is as follows:

[0025] Based on the machine learning algorithm, the chromatographic peak retention time corresponding to the qualified value of the chromatographic peak retention time is identified, and it is distinguished from the interfering peak by comparing the known retention time range and typical peak shape characteristics of 4,4′-biphenol. At the same time, different types of peaks are classified according to their peak width and symmetry; peaks with narrow peak width and good symmetry are grouped together and marked as narrow symmetrical peaks, while peaks with wide peak width and poor symmetry are classified into another category and marked as wide asymmetric peaks.

[0026] Preferably, the process of analyzing abnormal evaluation values ​​is:

[0027] Perform statistical analysis on the signal data after preprocessing and peak identification classification;

[0028] For the peak area parameter, there are n peak area qualified values: , , get the average value of the peak area AJ, and similarly, calculate the average values ​​of the qualified value of the chromatographic peak retention time and the qualified value of the peak height, BJ and CJ respectively;

[0029] For the peak area, use the formula: , get the peak area standard deviation &A; where Aᵢ represents the qualified value of the ith peak area, and similarly, the chromatographic peak retention time standard deviation &B and peak height standard deviation &C can be calculated;

[0030] The coefficient of variation of the peak area βA=&A / AJ, the coefficient of variation of the chromatographic peak retention time βB=&B / BJ, and the coefficient of variation of the peak height βC=&C / CJ; the coefficient of variation of the peak area βA, the coefficient of variation of the chromatographic peak retention time βB, and the coefficient of variation of the peak height βC are substituted into the preset formula: ZP=βA×b1+βB×b2+βC×b3, and the abnormal evaluation value ZP is obtained, wherein b1, b2, and b3 are preset weight coefficients, and the abnormal evaluation value threshold is preset. If the abnormal evaluation value ZP is greater than the preset abnormal evaluation value threshold, a correction instruction is generated;

[0031] Preferably, the processing process of receiving the correction instruction is:

[0032] Extract all data marked as outliers from the analysis module, including peak area outliers, chromatographic peak retention time outliers and peak height outliers, and calculate the peak area outlier mean FZ, chromatographic peak retention time outlier mean SZ, and peak height outlier mean GZ respectively;

[0033] Using the formula: FMZ = (FZ-AJ) / AJ, we can get the peak area abnormal deviation value FMZ. Similarly, we can get the chromatographic peak retention time abnormal deviation value SMZ and the peak height abnormal deviation value GMZ.

[0034] The peak area abnormal deviation value, the chromatographic peak retention time abnormal deviation value and the peak height abnormal deviation value are set to correspond to a preset abnormal deviation threshold value, and the peak area abnormal deviation value FMZ, the chromatographic peak retention time abnormal deviation value SMZ and the peak height abnormal deviation value GMZ are respectively compared with the corresponding preset abnormal deviation threshold value. If a certain abnormal deviation value is greater than its corresponding preset threshold value, it is marked with a specific letter, that is, when the peak area abnormal deviation value is greater than the threshold value, it is marked with letter A, when the chromatographic peak retention time abnormal deviation value is greater than the threshold value, it is marked with letter B, and when the peak height abnormal deviation value is greater than the threshold value, it is marked with letter C;

[0035] Determine whether the abnormal values ​​corresponding to the above deviation values ​​are mainly concentrated in narrow symmetrical peaks or wide asymmetrical peaks; if the peak area abnormal values ​​are mainly concentrated in narrow symmetrical peaks, the letter AN is output, indicating that the peak area abnormality is concentrated in narrow symmetrical peaks; if it is mainly concentrated in wide asymmetrical peaks, the letter AW is output, indicating that the peak area abnormality is concentrated in wide asymmetrical peaks; similarly, if the chromatographic peak retention time abnormality is concentrated in narrow symmetrical peaks, the letter BN is output, and if it is concentrated in wide asymmetrical peaks, the letter BW is output; if the peak height abnormality is concentrated in narrow symmetrical peaks, the letter CN is output, and if it is concentrated in wide asymmetrical peaks, the letter CW is output;

[0036] S35: Establish a correction set {AN, AW, BN, BW, CN, CW}, and each letter represents a correction operation. Bring the letters output in the previous step to this set. If the two match, output the corresponding letters. Outputting the corresponding words means that the corresponding correction operation needs to be performed.

[0037] Preferably, the chromatographic analysis correction system applied to 4,4′-biphenyldiphenol comprises:

[0038] Acquisition module: communicating with a chromatograph suitable for chromatographic analysis of 4,4′-biphenol, and collecting signal data output by the chromatograph in real time by setting an acquisition interval;

[0039] Analysis module: used to analyze the signal data collected by the data acquisition module to determine whether the signal data is stable and reliable;

[0040] Correction module: If the signal data is unstable and unreliable, analysis and correction will be performed based on the abnormal values ​​and peak shapes of the signal data.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) The chromatographic analysis correction method and system applied to 4,4′-biphenol realizes comprehensive monitoring and correction of the chromatographic analysis process by setting up an acquisition module, an analysis module and a correction module; the acquisition module can collect signal data output by the chromatograph in real time to ensure the accuracy and timeliness of the data; the analysis module performs preprocessing, peak recognition classification and statistical analysis on the collected data, and can accurately identify the chromatographic peak of 4,4′-biphenol and evaluate the reliability of the analysis results; the correction module analyzes and corrects the abnormal values ​​according to the results of the analysis module, thereby improving the accuracy and stability of the analysis results.

[0043] (2) The chromatographic analysis correction method and system applied to 4,4′-biphenol can effectively distinguish the chromatographic peak of 4,4′-biphenol from the interference peak by identifying and classifying the chromatographic peaks. At the same time, different types of peaks are classified according to the peak width and symmetry, providing a more targeted basis for subsequent data analysis and correction.

[0044] (3) The chromatographic analysis correction method and system applied to 4,4′-biphenol can improve the efficiency and accuracy of data acquisition by setting a reasonable acquisition interval and signal acquisition method. The setting of the acquisition interval takes into account the requirements of chromatographic analysis speed, resolution and processing capacity, ensuring that data redundancy is reduced without losing important information.

[0045] (4) The chromatographic analysis correction method and system applied to 4,4′-biphenol can effectively improve the accuracy and reliability of the analysis results by analyzing and correcting the abnormal values. The correction module takes targeted correction measures according to the specific circumstances of the abnormal values, such as adjusting instrument parameters, optimizing sample preparation methods, improving chromatographic conditions, etc., which can effectively solve the problems arising in the analysis process and improve the quality of the analysis results. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 It is a flowchart of the present invention. DETAILED DESCRIPTION

[0047] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Embodiment 1

[0048] See also Figure 1 , the present invention provides a chromatographic analysis correction method and system applied to 4,4′-biphenol, including a collection module, an analysis module, and a correction module;

[0049] S1: The acquisition module is connected to the chromatograph suitable for chromatographic analysis of 4,4′-biphenyldiphenol by communication, and the signal data output by the chromatograph is collected in real time by setting the acquisition interval. The signal data output by the chromatograph includes peak area, chromatographic peak retention time, and peak height, and is sent to the analysis module;

[0050] S11: The collection interval is set as follows:

[0051] S111: Prepare multiple identical samples containing 4,4′-biphenyldiphenol, ensure that the concentration and matrix of the samples are consistent, use the same chromatograph, under the same mobile phase, flow rate, and column temperature, analyze these samples, record the time from injection to completion of each analysis, calculate the average of these times, and obtain the average analysis time T. According to the formula: V=1 / T, obtain the chromatographic analysis speed V;

[0052] S112: Select a group of standard samples containing 4,4′-biphenol and compounds with similar structures, where the selection of these similar compounds should take into account certain similarities with 4,4′-biphenol in terms of chemical properties, molecular weight, polarity, etc.; perform multiple chromatographic analyses on the standard samples using the same chromatographic conditions;

[0053] For each chromatographic analysis, measure the retention time difference Δt and average peak width W of adjacent peaks (the target is the 4,4′-biphenol peak and its adjacent interference peak), calculate the resolution value R=Δt / W for each analysis, and determine the required minimum resolution value Rmin according to the specific needs of the analysis; the minimum resolution value Rmin is not a fixed value, and its value is mainly based on the accuracy requirements of the analysis. The higher the accuracy requirements, the larger the minimum resolution value Rmin.

[0054] S113: Conduct a series of simulation experiments with different data volumes, and record the time t and the corresponding data volume d required for the system to process the data, where the data volume d can be expressed in bytes, and the data processing capacity C = d / t;

[0055] S114: Using the formula: , the acquisition interval coefficient I is obtained, where K is the preset adjustment coefficient, and a1, a2, and a3 are preset weight coefficients; it can be seen from the formula that the greater the analysis speed V, the smaller the acquisition interval, and the higher the resolution requirement, that is, the greater the minimum resolution value Rmin, the smaller the acquisition interval;

[0056] S12: The acquisition method of signal data acquisition is:

[0057] S121: Peak area: The data acquisition device continuously monitors the intensity change of the chromatographic signal according to the set acquisition interval. When the change rate of the chromatographic signal intensity continues to increase within a period of time and then continues to decrease, a signal intensity threshold is preset. When the signal intensity exceeds the preset threshold, it is determined that the starting point of the chromatographic peak is detected; when the signal intensity returns to a level close to the starting level again and the change rate tends to be stable, it is determined that the end point of the chromatographic peak is detected; the area under the peak is calculated using a trapezoidal integration algorithm to obtain the peak area;

[0058] S122: Chromatographic peak retention time: The data acquisition device records the time from the start of injection according to the acquisition interval, and continuously monitors the chromatographic signal during the acquisition process; when the characteristics of the chromatographic signal match the known standard signal characteristics of 4,4′-biphenol or a specific component, if the signal intensity changes within a specific range and a specific peak shape characteristic appears, it is determined that the chromatographic peak of the specific component is detected, and the time recorded at this time is the chromatographic peak retention time of the component;

[0059] S123: When a chromatographic peak is detected during monitoring according to the acquisition interval, the signal intensity value corresponding to the maximum value of the chromatographic signal intensity is recorded as the peak height;

[0060] S2: The analysis module receives the signal data from the acquisition module and performs the following operations:

[0061] S21: Based on historical experimental data, determine the reasonable fluctuation range threshold of the peak area, the preset range of the chromatographic peak retention time, and the peak height threshold range;

[0062] S22: For the collected peak area data, compare it with the peak area fluctuation range threshold. If it exceeds the upper and lower limits of the threshold range, it is marked as a peak area abnormal value; if it falls within the threshold range, it is marked as a peak area qualified value;

[0063] S23: The chromatographic peak retention time data is also compared with the preset range of the chromatographic peak retention time. The data exceeding the upper and lower limits of the range are marked as abnormal chromatographic peak retention time values, and the data within the range are marked as qualified chromatographic peak retention time values;

[0064] S23: The peak height data are processed in a similar manner, and the peak heights exceeding the upper and lower limits of the peak height threshold range are marked as abnormal peak height values, and the peak heights within the range are marked as qualified peak height values;

[0065] S24: Based on the machine learning algorithm, the chromatographic peak retention time corresponding to the qualified value of the chromatographic peak retention time is identified, and the known 4,4′-biphenol retention time range and typical peak shape characteristics are compared to distinguish it from the interference peak. At the same time, different types of peaks are classified according to the peak width and symmetry; peaks with narrow peak width and good symmetry are classified into one category and marked as narrow symmetrical peaks, while peaks with wide peak width and poor symmetry are classified into another category and marked as wide asymmetric peaks;

[0066] S25: performing statistical analysis on the signal data after preprocessing and peak identification and classification;

[0067] For the peak area parameter, there are n peak area qualified values: , , and obtain the average peak area value AJ. Similarly, for the qualified value parameters of the chromatographic peak retention time and the qualified value parameters of the peak height, calculate their average values, BJ and CJ, respectively.

[0068] For the peak area, use the formula: , get the peak area standard deviation &A; where Aᵢ represents the qualified value of the ith peak area, and similarly, the chromatographic peak retention time standard deviation &B and peak height standard deviation &C can be calculated;

[0069] S26: coefficient of variation of peak area βA=&A / AJ, coefficient of variation of chromatographic peak retention time βB=&B / BJ, coefficient of variation of peak height βC=&C / CJ; Substitute the coefficient of variation of peak area βA, coefficient of variation of chromatographic peak retention time βB, and coefficient of variation of peak height βC into the preset formula: ZP=βA×b1+βB×b2+βC×b3, and obtain the abnormal evaluation value ZP, wherein b1, b2, and b3 are preset weight coefficients, and the abnormal evaluation value threshold is preset. If the abnormal evaluation value ZP is greater than the preset abnormal evaluation value threshold, a correction instruction is generated and sent to the correction module; this indicates that there are major problems in the chromatographic analysis data of 4,4′-biphenyldiphenol, and the reliability of the analyzed results is low;

[0070] S3: The correction module performs the following operations based on the results of the analysis module:

[0071] S31: extracting all data marked as outliers from the analysis module, including peak area outliers, chromatographic peak retention time outliers and peak height outliers, and calculating the peak area outlier mean FZ, the chromatographic peak retention time outlier mean SZ, and the peak height outlier mean GZ respectively;

[0072] S32: Use the formula: FMZ = (FZ-AJ) / AJ to obtain the peak area abnormal deviation value FMZ. Similarly, obtain the chromatographic peak retention time abnormal deviation value SMZ and the peak height abnormal deviation value GMZ.

[0073] S33: setting a peak area abnormal deviation value, a chromatographic peak retention time abnormal deviation value and a peak height abnormal deviation value to correspond to a preset abnormal deviation threshold, respectively comparing the peak area abnormal deviation value FMZ, the chromatographic peak retention time abnormal deviation value SMZ and the peak height abnormal deviation value GMZ with the corresponding preset abnormal deviation threshold, if a certain abnormal deviation value is greater than its corresponding preset threshold, it is marked with a specific letter, that is, when the peak area abnormal deviation value is greater than the threshold, it is marked with letter A, when the chromatographic peak retention time abnormal deviation value is greater than the threshold, it is marked with letter B, and when the peak height abnormal deviation value is greater than the threshold, it is marked with letter C;

[0074] S34: Determine whether the abnormal values ​​corresponding to the above deviation values ​​are mainly concentrated in narrow symmetrical peaks or wide asymmetrical peaks; if the peak area abnormal values ​​are mainly concentrated in narrow symmetrical peaks, the letter AN is output, indicating that the peak area abnormality is concentrated in narrow symmetrical peaks; if it is mainly concentrated in wide asymmetrical peaks, the letter AW is output, indicating that the peak area abnormality is concentrated in wide asymmetrical peaks; similarly, if the chromatographic peak retention time abnormality is concentrated in narrow symmetrical peaks, the letter BN is output, and if it is concentrated in wide asymmetrical peaks, the letter BW is output; if the peak height abnormality is concentrated in narrow symmetrical peaks, the letter CN is output, and if it is concentrated in wide asymmetrical peaks, the letter CW is output;

[0075] S35: Establish a correction set {AN, AW, BN, BW, CN, CW}, and each letter represents a correction operation. Bring the letters output in the previous step to this set. If the two match, output the corresponding letter, and the letter represents the correction operation that needs to be performed;

[0076] S36: The correction methods represented by each letter are:

[0077] Correction results represented by AN:

[0078] Check the accuracy of the data acquisition system's response to narrow symmetrical peaks, and adjust the data acquisition frequency and gain to ensure that the signal changes of narrow peaks are accurately captured;

[0079] AW represents the revised results:

[0080] Check whether the sample concentration is too high, causing peak broadening and affecting peak area measurement. If the concentration is too high, dilute the sample appropriately and reanalyze;

[0081] The revised results represented by BN:

[0082] Check the stability and purity of the mobile phase to ensure that it has no effect on the retention time of narrow symmetrical peaks. If there is a problem with the mobile phase, re-prepare the mobile phase and optimize its composition and preparation process;

[0083] BW represents the corrected result:

[0084] Evaluate the effect of column performance on the retention time of wide asymmetric peaks, check the selectivity and efficiency of the column, and if the column is not suitable for separating wide asymmetric peaks, consider replacing a different type of column or adjusting the conditions of the column.

[0085] The revised results of CN representatives are:

[0086] Check the detector's response sensitivity to narrow symmetrical peaks and adjust the detector's parameters, such as gain and wavelength, to improve the accuracy of peak height measurements;

[0087] Correction results for CW representatives:

[0088] Analyze the effect of signal interference on wide asymmetric peak height, take shielding measures or use filters to reduce the effect of interference signals on peak height measurement.

[0089] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. Chromatographic analysis correction method for 4,4′-biphenylene glycol, Features: S1: The signal data output by the chromatograph is collected in real time by setting the collection interval. The signal data output by the chromatograph includes peak area, chromatographic peak retention time, peak height and is sent to the analysis module; The collection interval is set as follows: Prepare multiple identical samples containing 4,4′-biphenyldiphenol, ensure that the concentration and matrix of the samples are consistent, use the same chromatograph, under the same mobile phase, flow rate, and column temperature, analyze these samples, record the time from injection to completion of each analysis, calculate the average of these times, and obtain the average analysis time T. According to the formula: V=1 / T, obtain the chromatographic analysis speed V; Select a group of standard samples containing 4,4′-biphenyldiphenol and compounds with similar structures; perform multiple chromatographic analyses on the standard samples using the same chromatographic conditions; For each chromatographic analysis, measure the retention time difference Δt and average peak width W between adjacent peaks, calculate the resolution value R = Δt / W for each analysis, and determine the required minimum resolution value Rmin based on the specific needs of the analysis; Conduct a series of simulation experiments with different data volumes, record the time t required for the system to process the data and the corresponding data volume d, where the data volume d is expressed in bytes, and the data processing capacity C = d / t; Using the formula: , obtain the collection interval coefficient I, where K is the preset adjustment coefficient, and a1, a2, and a3 are preset weight coefficients; S2: Identify outliers on the signal data, distinguish 4,4′-biphenol from interference peaks, classify different types of peaks, analyze the signal data after outlier identification and peak identification classification, and obtain the average value of peak area, average value of chromatographic peak retention time, and average value of peak height. Analyze the standard deviation of each signal data based on the average value of each signal data. Analyze the coefficient of variation corresponding to each signal data based on the standard deviation and average value of each signal data. Finally, perform a comprehensive analysis based on the coefficient of variation of peak area, coefficient of variation of chromatographic peak retention time, and coefficient of variation of peak height to obtain the abnormal evaluation value to evaluate the reliability of the signal data. S3: If the signal data is unreliable, analyze and correct it.

2. The chromatographic analysis correction method for 4,4′-biphenylene glycol according to claim 1, Features: The acquisition method of signal data acquisition is: Peak area: The data acquisition device continuously monitors the intensity change of the chromatographic signal according to the set acquisition interval. When the change rate of the chromatographic signal intensity continues to increase and then continues to decrease within a period of time, a signal intensity threshold is preset. When the signal intensity exceeds the preset threshold, it is determined that the starting point of the chromatographic peak has been detected; when the signal intensity returns to a level close to the starting level again and the change rate tends to be stable, it is determined that the end point of the chromatographic peak has been detected; the area under the peak is calculated using the trapezoidal integration algorithm to obtain the peak area; Chromatographic peak retention time: The data acquisition device records the time from the start of injection according to the acquisition interval, and continuously monitors the chromatographic signal during the acquisition process; when the characteristics of the chromatographic signal match the known standard signal characteristics of 4,4′-biphenol or a specific component, if the signal intensity changes within a specific range and a specific peak shape characteristic appears, it is determined that the chromatographic peak of the specific component is detected, and the time recorded at this time is the chromatographic peak retention time of the component; Peak height: During monitoring based on the acquisition interval, when a chromatographic peak is detected, the signal intensity value corresponding to the maximum value of the chromatographic signal intensity is recorded as the peak height.

3. The chromatographic analysis correction method for 4,4′-biphenylene glycol according to claim 2, Features: The process of identifying outliers in signal data is as follows: Based on historical experimental data, determine the reasonable fluctuation range threshold of peak area, the preset range of chromatographic peak retention time, and the peak height threshold range; For the collected peak area data, compare it with the peak area fluctuation range threshold. If it exceeds the upper and lower limits of the threshold range, it is marked as a peak area abnormal value; if it falls within the threshold range, it is marked as a peak area qualified value; For the chromatographic peak retention time data, it is also compared with the preset range of the chromatographic peak retention time. The data beyond the upper and lower limits of the range are marked as abnormal chromatographic peak retention time values, and the data within the range are marked as qualified chromatographic peak retention time values; The peak height data are processed in a similar manner, with those outside the upper and lower limits of the peak height threshold range marked as outliers and those within the range marked as qualified values.

4. The chromatographic analysis correction method for 4,4′-biphenylene glycol according to claim 3, Features: The process of distinguishing 4,4′-biphenylene glycol from interfering peaks and classifying different types of peaks is as follows: Based on the machine learning algorithm, the chromatographic peak retention time corresponding to the qualified value of the chromatographic peak retention time is identified, and it is distinguished from the interfering peak by comparing the known retention time range and typical peak shape characteristics of 4,4′-biphenol. At the same time, different types of peaks are classified according to their peak width and symmetry; peaks with narrow peak width and good symmetry are grouped together and marked as narrow symmetrical peaks, while peaks with wide peak width and poor symmetry are classified into another category and marked as wide asymmetric peaks.

5. The chromatographic analysis correction method for 4,4′-biphenylene glycol according to claim 4, Features: The process of analyzing abnormal evaluation values ​​is: Perform statistical analysis on the signal data after preprocessing and peak identification classification; For the peak area parameter, there are n peak area qualified values: , , get the average value of the peak area AJ, and similarly, calculate the average values ​​of the qualified value of the chromatographic peak retention time and the qualified value of the peak height, BJ and CJ respectively; For the peak area, use the formula: , get the peak area standard deviation &A; in Indicates the qualified value of the i-th peak area. Similarly, the standard deviation value of the chromatographic peak retention time &B and the standard deviation value of the peak height &C can be calculated; The coefficient of variation of peak area βA=&A / AJ, the coefficient of variation of chromatographic peak retention time βB=&B / BJ, and the coefficient of variation of peak height βC=&C / CJ; substitute the coefficient of variation of peak area βA, the coefficient of variation of chromatographic peak retention time βB, and the coefficient of variation of peak height βC into the preset formula: ZP=βA×b1+βB×b2+βC×b3 to obtain the abnormal evaluation value ZP, where b1, b2, and b3 are preset weight coefficients and the abnormal evaluation value threshold is preset. If the abnormal evaluation value ZP is greater than the preset abnormal evaluation value threshold, a correction instruction is generated.

6. The chromatographic analysis correction method for 4,4′-biphenylene glycol according to claim 5, Features: The processing procedure for receiving the correction instruction is as follows: Extract all data marked as outliers from the analysis module, including peak area outliers, chromatographic peak retention time outliers and peak height outliers, and calculate the peak area outlier mean FZ, chromatographic peak retention time outlier mean SZ, and peak height outlier mean GZ respectively; Using the formula: FMZ = (FZ-AJ) / AJ, we can get the peak area abnormal deviation value FMZ. Similarly, we can get the chromatographic peak retention time abnormal deviation value SMZ and the peak height abnormal deviation value GMZ. The peak area abnormal deviation value, the chromatographic peak retention time abnormal deviation value and the peak height abnormal deviation value are set to correspond to a preset abnormal deviation threshold value, and the peak area abnormal deviation value FMZ, the chromatographic peak retention time abnormal deviation value SMZ and the peak height abnormal deviation value GMZ are respectively compared with the corresponding preset abnormal deviation threshold value. If a certain abnormal deviation value is greater than its corresponding preset threshold value, it is marked with a specific letter, that is, when the peak area abnormal deviation value is greater than the threshold value, it is marked with letter A, when the chromatographic peak retention time abnormal deviation value is greater than the threshold value, it is marked with letter B, and when the peak height abnormal deviation value is greater than the threshold value, it is marked with letter C; Determine whether the abnormal values ​​corresponding to the above deviation values ​​are mainly concentrated in narrow symmetrical peaks or wide asymmetrical peaks; if the peak area abnormal values ​​are mainly concentrated in narrow symmetrical peaks, the letter AN is output, indicating that the peak area abnormality is concentrated in narrow symmetrical peaks; if it is mainly concentrated in wide asymmetrical peaks, the letter AW is output, indicating that the peak area abnormality is concentrated in wide asymmetrical peaks; similarly, if the chromatographic peak retention time abnormality is concentrated in narrow symmetrical peaks, the letter BN is output, and if it is concentrated in wide asymmetrical peaks, the letter BW is output; if the peak height abnormality is concentrated in narrow symmetrical peaks, the letter CN is output, and if it is concentrated in wide asymmetrical peaks, the letter CW is output; S35: Establish a correction set {AN, AW, BN, BW, CN, CW}, and each letter represents a correction operation. Bring the letters output in the previous step to this set. If the two match, output the corresponding letters. Outputting the corresponding words means that the corresponding correction operation needs to be performed.

7. A chromatographic analysis correction system for 4,4′-biphenylene glycol according to any one of claims 1 to 6, It is characterized in that include: Acquisition module: communicating with a chromatograph suitable for chromatographic analysis of 4,4′-biphenol, and collecting signal data output by the chromatograph in real time by setting an acquisition interval; Analysis module: used to analyze the signal data collected by the data acquisition module to determine whether the signal data is stable and reliable; Correction module: If the signal data is unstable and unreliable, analysis and correction will be performed based on the abnormal values ​​and peak shapes of the signal data.