Industrial on-line chromatograph based on flame photometric detector

Abstract

The application belongs to the technical field of chromatographs, and particularly relates to an industrial online chromatograph based on a flame photometric detector, which comprises a control platform and a server; the control platform is used for controlling the working condition of the chromatograph and outputting a chromatogram after the chromatograph works; the server is used for comparing the properties and contents of each component on the chromatogram and uploading the corresponding chromatogram to a database for storage; the control platform comprises a data acquisition module, a sample injection control module, a separation control module, an output control module and a chromatographic analysis module; the data acquisition module is used for acquiring data of sensors and detectors arranged on the chromatograph and storing the acquired data; the sample injection control module is used for acquiring the sample injection frequency, sample injection temperature and sample injection amount, determining the sample injection condition under the joint control of a six-way valve and a ten-way valve, and setting the sample injection stability index according to the opening and closing rate of the valve under the sample injection condition; and the working efficiency of the chromatograph is improved.

Description

Technical Field

[0001] This invention relates to the field of chromatography technology, specifically to an industrial online chromatograph based on a flame photometric detector. Background Technology

[0002] Traditional chromatographic analysis systems typically rely on offline analysis in laboratory environments, a model with significant limitations in industrial applications. Industrial environments require real-time monitoring and control to ensure the stability of production processes and the consistency of product quality. Industrial online chromatographs based on flame photometric detectors (FPDs) enable real-time, continuous sample analysis and provide high-precision data support. However, existing online chromatographs still face challenges in areas such as injection control, separation control, and signal processing. For example, how to ensure the repeatability and consistency of each injection, how to optimize carrier gas flow rate and sampling time to improve resolution, how to guarantee the quality and stability of the output electrical signal, and how to efficiently process and analyze large amounts of chromatographic data.

[0003] For example, Chinese Patent Publication No. CN117451906A discloses a gas chromatograph processing system for hydrogen energy detection, including: a processing device connected to a flame ionization detector (FID) and a sample loop. The processing device monitors the response signal of the FID and the consumption of the analyte in the sample loop, and periodically collects the response signal and the consumption according to a synchronous clock sequence to form a periodic data packet. This periodic data packet allows real-time acquisition of the velocity variation of the analyte carried by the carrier gas entering the FID. This invention sequentially inputs the carrier gas and the analyte into the sample loop. Each sample tube has a different propulsion velocity during analyte advancement, thus enabling the acquisition of the velocity variation of the analyte entering the FID at different propulsion velocities.

[0004] The prior art describes how to process the data using a hydrogen flame ionization detector. However, the prior art cannot identify the system settings of the current chromatograph and detect the corresponding situation of the chromatograph during actual operation to verify the differences generated by the chromatograph analysis. This leads to unreliable final analysis results and reduces the efficiency and accuracy of the chromatograph. Summary of the Invention

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: an industrial online chromatograph based on a flame photometric detector, comprising: a control platform and a server; the control platform is used to control the operation of the chromatograph and output the chromatogram after the chromatograph has been working; the server is used to compare the properties and contents of each component on the chromatogram and upload the corresponding chromatogram to the database.

[0006] The control platform includes: a data acquisition module, an injection control module, a separation control module, an output control module, and a chromatographic analysis module.

[0007] The data acquisition module is used to collect data from the sensors and detectors set on the chromatograph and store the collected data.

[0008] The sample injection control module is used to acquire the sample injection frequency, injection temperature and injection volume, determine the sample injection status under the combined control of the six-way valve and the ten-way valve, and set the sample injection stability index according to the valve opening and closing rate under the injection status.

[0009] The separation control module is used to analyze the delay between the carrier and the sample, adjust the carrier gas flow rate and sampling time, and set separation stability indicators.

[0010] The output control module is used to monitor the amplitude, pressure, and hysteresis of the output electrical signal, determine the quality of the output signal, and set signal control parameters.

[0011] The chromatography analysis module is used to identify the chromatograms output by the chromatograph, determine the differences in chromatogram values ​​at different temperatures, and set the chromatograph control strategy.

[0012] The beneficial effects of this invention are as follows: First, by precisely controlling the opening and closing rates of the six-way valve and the ten-way valve, and combining a comprehensive evaluation of the injection frequency, temperature, and quantity, this invention sets injection stability indicators, thereby improving injection stability and ensuring the accuracy and reliability of the analytical results.

[0013] Second, this invention optimizes the separation effect by adjusting the carrier gas flow rate and sampling time to ensure optimal separation and by setting separation stability indicators.

[0014] Third, this invention improves signal command by monitoring and optimizing the amplitude, pressure and hysteresis rate of the output electrical signal and setting signal control indicators.

[0015] Fourth, this invention achieves iterative analysis of differences at different temperatures by grouping, calculating and regrouping chromatographic information, thereby obtaining difference indicators. Based on these indicators, the optimal control strategy is selected, making the entire analysis process highly automated, reducing the possibility of human intervention, and improving work efficiency and data consistency. Attached Figure Description

[0016] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0017] Figure 1 This is a schematic diagram of an industrial online chromatograph based on a flame photometric detector.

[0018] Figure 2This is a schematic diagram of an industrial online chromatograph based on a flame photometric detector.

[0019] Figure 3 This is a flowchart illustrating the injection control module of an industrial online chromatograph based on a flame photometric detector.

[0020] Figure 4 This is a schematic diagram of the separation control module of an industrial online chromatograph based on a flame photometric detector.

[0021] Figure 5 This is a flowchart illustrating the output control module of an industrial online chromatograph based on a flame photometric detector. Detailed Implementation

[0022] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in the art or in accordance with the product manual.

[0023] See Figure 1 , Figure 2 An industrial online chromatograph based on a flame photometric detector includes: a control platform and a server; the control platform is used to control the operation of the chromatograph and output chromatograms after the chromatograph has been working; the server is used to compare the properties and contents of each component on the chromatogram and upload the corresponding chromatograms to the database.

[0024] The control platform includes: a data acquisition module, an injection control module, a separation control module, an output control module, and a chromatographic analysis module; the output of the data acquisition module is connected to the injection control module, the output of the injection control module is connected to the separation control module, the output of the separation control module is connected to the output control module, and the output of the output control module is connected to the chromatographic analysis module.

[0025] The data acquisition module is used to collect data from the sensors and detectors set on the chromatograph and store the collected data.

[0026] The sample injection control module is used to acquire the sample injection frequency, injection temperature and injection volume, determine the sample injection status under the combined control of the six-way valve and the ten-way valve, and set the sample injection stability index according to the valve opening and closing rate under the injection status.

[0027] The separation control module is used to analyze the delay between the carrier and the sample, adjust the carrier gas flow rate and sampling time, and set separation stability indicators.

[0028] The output control module is used to monitor the amplitude, pressure, and hysteresis of the output electrical signal, determine the quality of the output signal, and set signal control parameters.

[0029] The chromatography analysis module is used to identify the chromatograms output by the chromatograph, determine the differences in chromatogram values ​​at different temperatures, and set the chromatograph control strategy.

[0030] The data collected from the sensors or detectors are shown below.

[0031] Pressure sensor: Used to monitor the gas pressure during sample injection, ensuring that the sample enters the column at the correct pressure. This is crucial for maintaining consistent injection volume.

[0032] Temperature sensor: If a heated injection port is used, a temperature sensor is required to monitor and maintain an appropriate injection temperature to prevent sample decomposition or condensation.

[0033] Column oven temperature sensor: Chromatographic columns are typically located in a temperature-controlled environment called a column oven. Temperature sensors are used to accurately measure and control the temperature within this environment, as temperature variations affect separation efficiency.

[0034] Flow sensor: Used to monitor the flow rate of carrier gas, such as helium or nitrogen, to ensure constant and accurate flow conditions, which is crucial for achieving good separation results.

[0035] Flame photometric detector: This is the core detector of this type of chromatograph, specifically designed to detect compounds containing specific elements such as sulfur and phosphorus. It performs quantitative analysis by analyzing the characteristic spectra produced after combustion.

[0036] Flame ionization detector (FPD): It is very sensitive for the determination of total organic compounds and is often used in combination with FPD to cover a wider range of analytical needs.

[0037] Gas purity sensor: Ensures that the quality of the carrier gas and other auxiliary gases, such as hydrogen and air, meets the requirements and prevents impurities from affecting the analysis results.

[0038] Leak detection sensors: Installed around gas pipelines to detect potential gas leaks and ensure laboratory safety.

[0039] Humidity sensor: In some moisture-sensitive applications, it may be necessary to monitor ambient humidity to avoid its impact on the analysis process.

[0040] Vibration sensor: Used to monitor the working status of internal mechanical components of an instrument. Excessive vibration may be a precursor to equipment failure.

[0041] Electrical parameter sensors, such as current and voltage monitoring, help diagnose power supply problems or the aging of electrical components.

[0042] In one embodiment of the present invention, in addition to identifying the injection frequency, injection temperature, and injection volume, the injection control module also needs to determine the working status of each valve in the injection control scenario, as well as the sample's entry into each valve. In this invention, the chromatograph uses a combination of ten-way valves and six-way valves. At this time, it is necessary to verify the opening and closing rates of the ten-way valves and six-way valves to ensure that the valves can correspond to the injection frequency when transporting gas; determine the injection frequency, injection temperature, and injection volume under different opening and closing rates; and finally determine whether the output chromatogram data is normal in this scenario, thereby determining whether the current injection is stable.

[0043] like Figure 3 As shown, the implementation of the injection control module includes: obtaining the injection type of the sample and extracting the setting parameters corresponding to the current injection type from the database; the injection types of the sample include: direct injection, split / splitless injection, headspace injection, programmed temperature vaporization injection, online injection, microinjection injection, and solid phase microextraction.

[0044] Direct injection: The sample is injected directly into the chromatographic column, suitable for thermally stable and volatile samples. It is simple and fast, but has high requirements for the sample.

[0045] Split / Splitless Injection: A portion of the sample is introduced into the column via a splitter, while the remainder is discharged from the system; or, in splitless mode, all the sample enters the column. Suitable for more complex or high-concentration samples, this method reduces contamination and improves sensitivity.

[0046] Headspace sampling: This method involves extracting gaseous samples from the top space of a sealed container for analysis, and is suitable for volatile organic compounds. It avoids direct contact between liquid samples and the instrument, reducing maintenance costs.

[0047] Programmed temperature vaporization injection: The sample is gradually vaporized and injected into the column during a stepwise heating process, making it particularly suitable for wide-boiling-range mixtures. It offers broader applicability and better peak shape.

[0048] Online sample introduction: Samples are automatically and continuously introduced into the chromatographic system from the production process or other online monitoring equipment. This enables real-time monitoring, reduces manual intervention, and is suitable for industrial process control.

[0049] Microinjection: Precisely controls the injection of extremely small amounts of sample using a micro-injector. Suitable for high-precision analysis of trace or precious samples.

[0050] Solid-phase microextraction (SPME): This technique utilizes fibers coated with a stationary phase to adsorb target compounds, which are then directly inserted into a chromatograph for desorption analysis. It requires no solvents, is simple to operate, and is environmentally friendly.

[0051] The settings will include the injection type name, default settings, user-defined settings, and history.

[0052] Injection type name: Used to identify different types of injection methods.

[0053] Default settings: Provides a recommended set of initial parameters for each injection type.

[0054] User-defined settings: Allows users to adjust certain parameters according to their actual needs and save them as a new configuration file.

[0055] History Record: Retains parameter settings for each analysis, facilitating review and optimization.

[0056] The injection frequency, injection temperature, and injection volume are obtained from the settings parameters. Different values ​​for injection frequency, injection temperature, and injection volume will be used for different injection types, and these parameters will be adjusted according to user preferences. For example, these values ​​can be adjusted by no more than 10% according to user preferences, or the injection temperature can be adjusted according to the highest temperature at which the sample is processed, ensuring that the sample can fully react with the chromatographic column during injection to complete the sample analysis.

[0057] Under the given settings, identify the valve opening / closing rate of the current sample in the pneumatic paths of the 10-way and 6-way valves. The opening / closing rate is expressed as the ratio of the number of times the valve opens in one complete cycle to the total number of times. This opening / closing rate is usually fixed to a certain value to cooperate with the 10-way and 6-way valves for sample pre-separation, backflushing, and re-injection, thereby completing the input control of the sample.

[0058] The valve opening and closing rate is compared with the injection frequency, injection temperature and injection volume to set injection stability indicators.

[0059] The injection stability index divides the opening and closing rate, injection frequency, injection temperature and injection volume into four sub-values, and combines these four sub-values ​​to obtain the injection stability index.

[0060] For example, the standard deviation and mean of the opening and closing rate are used for judgment; the injection frequency is compared with the set standard injection frequency; the standard deviation and mean temperature of the injection temperature are used for judgment, and the highest value at this time is compared with the acceptable range of the sample; the standard deviation of the injection volume is compared with the standard processing rate, which represents the average processing rate for completing the analysis of the sample. This will compare the rate with the current volume to determine whether the injection volume is appropriate.

[0061] Therefore, the injection stability index can be expressed as follows: obtain the valve opening / closing rate score, injection frequency score, injection temperature score, and injection volume score corresponding to the valve opening / closing rate, injection frequency, injection temperature, and injection volume, respectively, and calculate the injection stability index.

[0062] The valve opening / closing rate score indicates that the standard deviation of the opening / closing rate is at the average value of the opening / closing rate.

[0063] The injection frequency score first calculates the difference between the injection frequency and the set injection frequency, and then divides this difference by the set injection frequency to obtain the injection frequency score used.

[0064] The injection temperature score is calculated by taking the maximum of the following two values: the ratio of the standard deviation of the injection temperature to the mean, the difference between the maximum injection temperature and the upper limit of the acceptable sample temperature, and the ratio of the upper limit of the acceptable sample temperature.

[0065] The injection volume score is calculated by adding the ratio of the standard deviation of the injection volume to the average injection volume, the difference between the injection volume and the standard rate processing volume, and the ratio of the standard rate processing volume.

[0066] The final injection stability index will be expressed as a weighted average of these four scores.

[0067] ISI = w SR ×SR+w Sf ×Sf+w ST ×ST+w SV ×SV; where ISI represents the injection stability index, SR represents the valve opening / closing rate score, Sf represents the injection frequency score, ST represents the injection temperature score, SV represents the injection volume score, and w SR w represents the weight of the valve opening / closing rate score. Sf w represents the weight of the injection frequency score. ST w represents the weight of the injection temperature score. SV This indicates the weight of the injection volume score.

[0068] In one embodiment of the present invention, the separation control module mainly analyzes the delay of the current chromatographic analysis carrier and sample, determines the sampling time set at the current carrier gas flow rate and sample injection frequency, injection temperature and injection volume, and sets separation stability indicators for the current separation process according to the separation degree, baseline noise and peak area repeatability during separation.

[0069] Separation degree: measures the degree of separation between two adjacent peaks and is an important indicator for evaluating the separation effect.

[0070] Baseline noise: reflects the fluctuation of the background signal; lower baseline noise means better stability.

[0071] Peak area repeatability: assesses the consistency of peak areas of the same component across multiple analyses. The peaks described here represent the content of each component separated during the separation process. Since impurities can easily arise during separation, the baseline for separation may deviate. Furthermore, multiple sampling analyses are performed to obtain multiple different chromatograms. Peak area repeatability is the overlapping area of ​​the same component in multiple chromatograms when combined, thus determining the relative values ​​between the calculated content of the component in each analysis.

[0072] When analyzing a single sample using a chromatograph, the input sample is divided into multiple parts by the chromatograph and tested sequentially. In this case, the output of the chromatograph will contain multiple sets of results. The differences between these analyses can be compared by comparing the area of ​​the components obtained in each set, so as to determine the impact of parameters such as sampling time and carrier gas flow rate on the final separation effect.

[0073] In the separation control module, the method for analyzing the delay of the carrier and sample and adjusting the carrier gas flow rate and sampling time is as follows: the delay of the carrier and sample is determined from the pre-selected backup information, and the pre-selected backup information is matched. During the matching process, the carrier gas flow rate and sampling time of the carrier and sample under the corresponding delay conditions are determined. Identification information related to the carrier gas flow rate and sampling time is set. In response to the identification information related to the carrier gas flow rate and sampling time, the identification information related to the carrier gas flow rate and sampling time is regarded as the target identification information, and the average value of the carrier gas flow rate and sampling time corresponding to the target identification information is set as the current carrier gas flow rate and sampling time.

[0074] Pre-selected backup information is data set for the analysis of the current sample. This information is adjusted according to the subject and method of chromatographic analysis, serving as a database for adjusting sample processing at that time. Delays may vary due to various factors, such as the physical characteristics of the carrier and sample, the state of the instrument, and environmental conditions.

[0075] The purpose of matching pre-selected backup information is to find historical data or model predictions that most closely match the current experimental conditions. The matching process may involve comparing multiple dimensions such as experimental conditions, instrument parameters, and sample types.

[0076] In the matched historical data or prediction models, find the carrier gas velocity and sampling time corresponding to the current latency. These values ​​may need to be fine-tuned based on the specific experimental conditions.

[0077] Identify data related to carrier gas flow rate and sampling time. This identification information can be numerical codes, tags, or other forms of metadata. The purpose of the identification information is to facilitate subsequent data management and analysis.

[0078] During the experiment, the system continuously detects and responds to these identification information. When the system identifies identification information related to carrier gas flow rate and sampling time, it treats it as target identification information.

[0079] Extract the corresponding carrier gas velocity and sampling time values ​​from the target identification information. Calculate the average of these values ​​to obtain a more stable and reliable parameter setting. Set the calculated average value as the current carrier gas velocity and sampling time.

[0080] This process can be automated through programming. For example, programming languages ​​such as Python and R can be used in conjunction with a database management system to store and retrieve pre-selected backup information. Algorithms can be written to implement the matching process, as well as to calculate averages and update parameter settings.

[0081] The separation stability index is set as follows: Select any two components from the chromatogram and calculate the resolution, baseline noise ratio, and peak area repeatability ratio of adjacent components. Each component represents a peak in the chromatogram; the peak width is described by time, and the peak height is described by the component's concentration. The resolution is compared by the ratio of the difference in retention times between two components to the sum of the widths of their corresponding peaks. The final resolution is multiplied by two in the output to emphasize the data. Retention time represents the time from sample injection to the appearance of the peak for the current component. This time indicates the time corresponding to the appearance of the current component.

[0082] The baseline noise ratio is calculated as the ratio of the standard deviation of the baseline noise to the mean of the baseline noise.

[0083] Peak area repetition ratio is calculated by taking the average of the proportions of the peak area of ​​the current component in adjacent tests over multiple tests. This proportion is chosen as the moving average of three adjacent tests. This moving average is used to calculate the proportion of the current peak area. Finally, the average of these proportions is taken as the output peak area repetition ratio.

[0084] like Figure 4 As shown, the final separation stability index will be expressed as follows: obtain the peak corresponding to each component in the chromatogram, and calculate the resolution and peak area repeatability of each component according to the retention time and peak area of ​​each component.

[0085] Compare the deviations of adjacent components on the baseline in the chromatogram and calculate the baseline noise ratio.

[0086] For each component, the resolution, baseline noise ratio, and peak area repetition ratio are set according to the values ​​of carrier gas flow rate and sampling time. The mapping parameter curve is then superimposed with the values ​​corresponding to the resolution, baseline noise ratio, and peak area repetition ratio to obtain the separation difference curve. The separation stability index is set according to the slope value of the separation difference curve.

[0087] The mapping parameter curve is obtained by collecting data on resolution, baseline noise ratio, and peak area repetition ratio under different carrier gas flow rates and sampling times, and then using regression parameter analysis on these three data points. This curve represents the changes in the currently identified resolution, baseline noise ratio, and peak area repetition ratio as the carrier gas flow rate and sampling time change.

[0088] The subsequent method of superimposing the mapping parameter curves with the values ​​corresponding to resolution, baseline noise ratio, and peak area repetition ratio involves superimposing the mapping parameter curves obtained for resolution, baseline noise ratio, and peak area repetition ratio at the corresponding carrier gas flow rate and sampling time. This superposition method involves calculating the moving average values ​​of resolution, baseline noise ratio, and peak area repetition ratio on the mapping parameter curves. Combining the mapping parameter curves with these moving averages yields the final separation difference curve, and the slope of this curve is set as the separation stability index. Since the values ​​represented by resolution, baseline noise ratio, and peak area repetition ratio have certain differences, it is necessary to adjust these values ​​to a range of 0-1 before superimposing the corresponding mapping parameter curves to complete the setting of the separation stability index.

[0089] In one embodiment of the present invention, when the output control module outputs an electrical signal, it needs to determine the specific situation of the electrical signal output, such as obtaining the maximum and minimum values ​​of the output from the electrical signal, and identifying the center point of the electrical signal and other data corresponding to the center point according to the maximum and minimum values, so as to complete the control of the electrical signal output.

[0090] like Figure 5 As shown, the output control module includes the following processing methods: determining the maximum and minimum values ​​when outputting the electrical signal, verifying the center point corresponding to the amplitude, pressure and hysteresis rate of the electrical signal under output conditions, and determining the key points for output control according to multiple center points.

[0091] According to the preset key point determination rules, the calculation sequence of the amplitude, pressure and hysteresis rate of the electrical signal is obtained from the key points. The output of the electrical signal in adjacent time periods is calculated according to the calculation sequence to obtain the signal control index.

[0092] The preset key point determination rule is to cluster the center points and use the cluster centers of the clustered center points as the key points to be used. The selected key points can distinguish the state of amplitude, pressure and hysteresis rate under different values.

[0093] Signal control indicators set key points according to the values ​​of amplitude, pressure, and hysteresis to obtain a graph for multiple values. For example, the implementation of signal control indicators includes connecting key points according to the calculation sequence of amplitude, pressure, and hysteresis of the electrical signal to obtain connection graphs for amplitude, pressure, and hysteresis, respectively.

[0094] Amplitude represents the maximum value or peak intensity of the electrical signal output by the detector; the connection diagram of amplitude will connect the key points according to the amplitude value at the key points, and the key points will eventually form a diagram.

[0095] Pressure usually refers to the pressure parameter related to the carrier gas or mobile phase. When obtaining pressure, it is represented by the carrier gas pressure, detector inlet pressure, and pressure difference across the column. The pressure connection graph connects the pressure values ​​represented by these three pressures to obtain a connection graph of pressure at key points.

[0096] Hysteresis refers to the delay in system response time, that is, the time interval from a change in input to a change in output. This time interval is used to connect key points according to different time intervals to obtain a connection diagram related to hysteresis.

[0097] The sum of the area ratios of the connection graphs for amplitude, pressure, and hysteresis is used as the signal control index.

[0098] The area ratio represents the sum of the ratios of the areas of the amplitude-related, pressure-related, and hysteresis-related graphs after calculating their areas, to the average area of ​​the corresponding graphs in historical data. This sum is used as the signal control index at this time. This value indicates the specific situation of the chromatograph under stable operating conditions and the numerical values ​​reflected by the system under these conditions.

[0099] In one embodiment of the present invention, the chromatographic analysis module mainly addresses the deviations that occur during the calculation of the chromatogram, identifies the content that causes the deviation of the chromatogram, compares these content to find the deviation values ​​that cause the current chromatogram to appear at different temperatures, and uses the deviation values ​​to provide feedback on the status of the chromatograph to select the control strategy for the chromatograph at this time. This strategy is to minimize the deviation of the current operation of the chromatograph and complete the control of the chromatograph according to the corresponding content.

[0100] The implementation of the chromatographic analysis module includes: acquiring the chromatographic information output by the chromatograph; grouping the current chromatographic information according to the values ​​of the injection stability index, separation stability index, and signal control index; using the chromatographic information of each group to judge the output of the chromatograph; calculating the deviation of the chromatographic information of each group; regrouping the chromatographic information of each group according to the deviation of the chromatographic information; using the chromatographic information of the same group in the newly divided group to calculate the difference value at different temperatures; and iterating to obtain the difference index corresponding to the chromatographic information.

[0101] The system acquires the difference indicators of chromatogram information in the newly divided adjacent groups, retrieves the difference indicators according to the working status of the chromatograph, obtains the target category corresponding to the chromatogram information, calls the preset control strategy corresponding to the target category in the database, and determines whether the preset control strategy is consistent with the working status of the chromatograph for the target category. If they are consistent, the preset control strategy corresponding to the current target category is set as the chromatograph control strategy; if they are inconsistent, the system retrieves the adjacent strategy information of the preset control strategy and uses the average value set in the adjacent strategy information as the chromatograph control strategy.

[0102] The deviations in the chromatogram information mentioned above refer to the deviations in retention time, peak area, peak height, resolution, and baseline noise for each component. These values ​​are divided into multiple groups based on their different values ​​to obtain newly defined groups. Then, the differences at different temperatures are calculated by determining the differences between temperature and retention time, peak area, and resolution. The difference index is represented as follows: Based on the different values ​​of the differences between temperature and retention time, peak area, and resolution, three curves are constructed: a temperature-retention time curve, a temperature-resolution curve, and a temperature-peak area curve. In these three curves, temperature is used as the x-axis, and retention time, peak area, and resolution are used as the y-axis. The average slope of the temperature-retention time curve, temperature-resolution curve, and temperature-peak area curve is used as the difference index corresponding to the chromatogram information. The average slope represents the average of the slope values ​​calculated for each of the three curves, which is then used as the difference index.

[0103] The target categories mentioned above include categories with corresponding differential indicators. Target categories are used to categorize the current chromatogram information into a specific category. These categories are set according to differential indicators. The preset control strategy includes information about the chromatograph during operation, such as column temperature settings, injection port temperature, detector temperature, carrier gas flow rate, injection frequency, and other parameters. The adjacent strategy information is information extracted from several preset control strategies adjacent to the preset control strategy, and the average value of these adjacent strategy information is used as the chromatograph control strategy to be adjusted.

[0104] In this invention, the control platform controls the operation of the chromatograph, including starting, stopping, and pausing the chromatographic analysis process, adjusting various operating parameters such as temperature and flow rate, and monitoring the status of the chromatograph. Then, it processes the data from the detector, generates and displays chromatograms for users to view and analyze.

[0105] The control platform directly performs the following functions: It acquires data from sensors and detectors on the chromatograph in real time via a high-precision ADC, storing the acquired data locally for subsequent analysis. It extracts the current injection type's setting parameters from the database to determine the injection frequency, temperature, and volume; controls the opening and closing rates of the six-way and ten-way valves according to the setting parameters to ensure correct sample entry into the chromatographic system and calculates injection stability indicators. Based on the delay information in the pre-selected backup, it adjusts the carrier gas flow rate and sampling time to optimize separation; by analyzing the peak characteristics of each component in the chromatogram, it calculates the resolution, baseline noise ratio, and peak area repeatability ratio, and sets separation stability indicators. It monitors the amplitude, pressure, and hysteresis rate of the output electrical signal in real time to ensure signal quality; based on the maximum and minimum values ​​of the electrical signal and their corresponding center points, it sets key points for output control, obtains the calculation sequence, and derives signal control indicators. It identifies the chromatograms output by the chromatograph and calculates the differences at different temperatures; based on the deviation and difference indicators of the chromatogram information, it selects the optimal chromatograph control strategy.

[0106] The server receives and processes chromatogram data uploaded by the control platform, compares the properties and contents of each component on the chromatogram, and performs data analysis. It stores the processed chromatogram data in a database for easy historical data retrieval and long-term preservation. It also provides a remote access interface, allowing users to monitor the chromatograph's operating status via the network and perform necessary management and configuration.

[0107] The service directly performs the following functions: receiving chromatographic data from the control platform, including raw data and analytical results; storing the received data in a database to ensure data security and integrity; parsing chromatograms to identify the retention time and peak area of ​​each component; and comparing chromatograms from different batches or time periods to assess changes in the properties and content of each component. It provides a user-friendly web interface, allowing users to access the server via a browser to view chromatograms and related data; and offers an API interface to support integration with third-party software or systems for automated management and data analysis. It monitors the chromatograph's operating status in real time, triggering alarms and notifying relevant personnel via email, SMS, etc., when an anomaly is detected. All operation logs are recorded for easy troubleshooting and accountability.

[0108] Through the design of the aforementioned control platform and server, this invention achieves comprehensive management and optimization of industrial online chromatographs based on flame photometric detectors. The control platform is responsible for real-time data acquisition, injection control, separation control, output control, and chromatographic analysis, ensuring the efficient operation of the chromatograph. The server focuses on data storage, analysis, remote monitoring, and management, providing users with a robust backend support system. This division of labor and collaboration not only improves the system's reliability and stability but also provides users with a more convenient operating experience.

[0109] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention, which are still covered within the protection scope of the present invention.

Claims

1. An industrial online chromatograph based on a flame photometric detector, characterized in that, include: Control platform and server; The control platform is used to control the operation of the chromatograph and output the chromatograms after the chromatograph has worked. The server is used to compare the properties and contents of each component on the chromatogram and upload the corresponding chromatograms to the database; The control platform includes: a data acquisition module, an injection control module, a separation control module, an output control module, and a chromatographic analysis module; The data acquisition module is used to collect data from the sensors and detectors set on the chromatograph and store the collected data; The sample injection control module is used to acquire the sample injection frequency, injection temperature and injection volume, determine the sample injection status under the combined control of the six-way valve and the ten-way valve, and set the sample injection stability index according to the valve opening and closing rate under the injection status. The separation control module is used to analyze the delay between the carrier and the sample, adjust the carrier gas flow rate and sampling time, and set the separation stability index. The output control module is used to monitor the amplitude, pressure, and hysteresis of the output electrical signal, determine the quality of the output signal, and set signal control parameters. The chromatography analysis module is used to identify the chromatograms output by the chromatograph, determine the differences in chromatogram values ​​at different temperatures, and set the chromatograph control strategy. The chromatographic analysis module is implemented in the following ways: The chromatogram information output by the chromatograph is acquired. The current chromatogram information is grouped according to the values ​​of the injection stability index, separation stability index, and signal control index. The output of the chromatograph is judged by the chromatogram information of each group, the deviation of the chromatogram information of each group is calculated, and the chromatogram information of each group is regrouped according to the deviation of the chromatogram information. The difference value at different temperatures is calculated by using the chromatogram information of the same group in the newly divided group, and the process is iterated to obtain the difference index corresponding to the chromatogram information. The system acquires the difference indicators of chromatogram information in the newly divided adjacent groups, retrieves the difference indicators according to the working status of the chromatograph, obtains the target category corresponding to the chromatogram information, calls the preset control strategy corresponding to the target category in the database, and determines whether the preset control strategy is consistent with the working status of the chromatograph for the target category. If they are consistent, the preset control strategy corresponding to the current target category is set as the chromatograph control strategy; if they are inconsistent, the system retrieves the adjacent strategy information of the preset control strategy and uses the average value set in the adjacent strategy information as the chromatograph control strategy.

2. The industrial online chromatograph based on a flame photometric detector according to claim 1, characterized in that, The implementation methods of the injection control module include: Obtain the sample injection type and extract the setting parameters corresponding to the current injection type from the database; Obtain the sample injection frequency, injection temperature, and injection volume from the settings parameters; Under certain settings, identify the valve opening / closing rate in the pneumatic paths of the current sample in the ten-way valve and the six-way valve. The valve opening and closing rate is compared with the injection frequency, injection temperature and injection volume to set injection stability indicators.

3. The industrial online chromatograph based on a flame photometric detector according to claim 2, characterized in that, The injection stability index is expressed as follows: the valve opening / closing rate score, injection frequency score, injection temperature score, and injection volume score corresponding to the valve opening / closing rate, injection frequency, injection temperature, and injection volume are obtained respectively, and the injection stability index is calculated.

4. The industrial online chromatograph based on a flame photometric detector according to claim 1, characterized in that, The method for analyzing the delay between the carrier and the sample, and adjusting the carrier gas flow rate and sampling time is as follows: The delay of the carrier and sample is determined from the pre-selected backup information, and the pre-selected backup information is matched. During the matching process, the carrier gas flow rate and sampling time of the carrier and sample under the corresponding delay conditions are determined. Identification information related to the carrier gas flow rate and sampling time is set. In response to the identification information related to the carrier gas flow rate and sampling time, the identification information related to the carrier gas flow rate and sampling time is regarded as the target identification information, and the average value of the carrier gas flow rate and sampling time corresponding to the target identification information is set as the current carrier gas flow rate and sampling time.

5. The industrial online chromatograph based on a flame photometric detector according to claim 1, characterized in that, The separation stability index is expressed as: Obtain the peak corresponding to each component in the chromatogram, and calculate the resolution and peak area repeatability of each component according to the retention time and peak area of ​​each component. Compare the deviations of adjacent components on the baseline in the chromatogram and calculate the baseline noise ratio; For each component, the resolution, baseline noise ratio, and peak area repetition ratio are set according to the values ​​of carrier gas flow rate and sampling time. The mapping parameter curve is then superimposed with the values ​​corresponding to the resolution, baseline noise ratio, and peak area repetition ratio to obtain the separation difference curve. The separation stability index is set according to the slope value of the separation difference curve.

6. The industrial online chromatograph based on a flame photometric detector according to claim 5, characterized in that, The mapping parameter curve is superimposed with the values ​​corresponding to separation, baseline noise ratio, and peak area repetition ratio as follows: The mapping parameter curves obtained at the corresponding carrier gas flow rate and sampling time are superimposed. The moving average values ​​of the resolution, baseline noise ratio and peak area repetition ratio on the mapping parameter curves are calculated. The mapping parameter curves with the calculated moving averages are combined to obtain the separation difference curve. The slope of the separation difference curve is set as the separation stability index.

7. The industrial online chromatograph based on a flame photometric detector according to claim 1, characterized in that, The output control module's processing methods include: Determine the maximum and minimum values ​​of the output electrical signal, verify the center point corresponding to the amplitude, pressure and hysteresis rate of the electrical signal under the output condition, and determine the key points for output control based on multiple center points; According to the preset key point determination rules, the calculation sequence of the amplitude, pressure and hysteresis rate of the electrical signal is obtained from the key points. The output of the electrical signal in adjacent time periods is calculated according to the calculation sequence to obtain the signal control index.

8. The industrial online chromatograph based on a flame photometric detector according to claim 7, characterized in that, The implementation methods of signal control indicators include: The key points are connected according to the calculation sequence of the amplitude, pressure and hysteresis rate of the electrical signal to obtain connection graphs for amplitude, pressure and hysteresis rate respectively. The sum of the area ratios of the connection graphs for amplitude, pressure, and hysteresis is used as the signal control index.

9. The industrial online chromatograph based on a flame photometric detector according to claim 1, characterized in that, The difference index is expressed as: Calculate the differences between temperature and retention time, peak area, and resolution. Construct temperature-retention time curves, temperature-resolution curves, and temperature-peak area curves according to the different values ​​of the differences between temperature and retention time, peak area, and resolution. Use the average slope of the temperature-retention time curve, temperature-resolution curve, and temperature-peak area curve as the difference index corresponding to the chromatogram information.

Images