Industrial online chromatograph based on flame photometric detector

Abstract

The invention relates to the technical field of chromatographic instruments, in particular to an industrial online chromatographic instrument 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 chromatographic instrument and outputting a chromatogram after the working of the chromatographic instrument; the server is used for comparing the properties and contents of the components on the chromatograms, uploading the corresponding chromatograms and storing the chromatograms in the database; wherein 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 a sensor and a detector arranged on the chromatograph and storing the acquired data; the sample injection control module is used for acquiring the sample injection frequency, the sample injection temperature and the sample injection amount of the sample and determining the sample injection condition of the sample under the combined control of the six-way valve and the ten-way valve; according to the opening and closing rate of the valve under the sample introduction condition, the sample introduction stability index of the sample is set; and the working efficiency of the chromatograph is improved.

Description

Technical Field

[0001] The invention relates to the technical field of chromatographs, in particular to an industrial online chromatograph based on a flame photometric detector. Background Art

[0002] Traditional chromatography systems usually rely on offline analysis in a laboratory environment, which has obvious limitations in industrial applications. Real-time monitoring and control are required in industrial environments to ensure the stability of the production process and the consistency of product quality. Industrial online chromatographs based on flame photometric detectors (FPDs) can achieve real-time and continuous sample analysis and provide high-precision data support. However, existing online chromatographs still face challenges in injection control, separation control, and signal processing, such as: how to ensure the repeatability and consistency of each injection, how to optimize the carrier gas flow rate and sampling time to improve separation, how to ensure 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 number CN117451906A discloses a gas chromatograph processing system for hydrogen energy detection, including: a processing device, the processing device is connected to a hydrogen flame ionization detector and a sample ring, the processing device is used to monitor the response signal of the hydrogen flame ionization detector and the consumption of the sample to be tested in the sample ring, and the response signal and the consumption are periodically collected according to the synchronous clock timing to form a periodic data packet, and the speed change of the sample to be tested carried in the carrier gas entering the hydrogen flame ionization detector is obtained in real time through the periodic data packet. The present invention inputs the carrier gas and the sample to be tested into the sample ring in sequence, and each sample tube makes the sample to be tested have different advancement speeds when advancing the sample to be tested, so that the speed change of the sample to be tested at different advancement speeds entering the hydrogen flame ionization detector can be obtained.

[0004] The prior art describes how to perform processing according to a hydrogen flame ionization detector. However, the prior art processing method cannot identify the system set up for the current chromatograph and detect the corresponding conditions of the chromatograph during the actual execution process to verify the differences produced by the chromatograph analysis, resulting in unreliable final analysis results and reducing the efficiency and accuracy of the chromatograph. Summary of the invention

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is: an industrial online chromatograph based on a flame photometer, including: a control platform and a server; the control platform is used to control the working condition of the chromatograph and output the chromatogram after the chromatograph is working; the server is used to compare the properties and contents of each component on the chromatogram, and upload the corresponding chromatogram and store it in a database.

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

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

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

[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 the separation stability index.

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

[0011] The chromatographic analysis module is used to identify the chromatogram output by the chromatograph, determine the difference value of the chromatogram calculation at different temperatures, and set the chromatograph control strategy.

[0012] The beneficial effects of the present invention are as follows: 1. The present invention sets an injection stability index by accurately controlling the opening and closing rates of the six-way valve and the ten-way valve, combining a comprehensive evaluation of injection frequency, temperature and quantity, thereby improving injection stability and ensuring the accuracy and reliability of the analysis results.

[0013] 2. The present invention ensures the best separation degree by adjusting the carrier gas flow rate and sampling time, and sets separation stability index to optimize the separation effect.

[0014] 3. The present invention monitors and optimizes the amplitude, pressure and hysteresis rate of the output electrical signal, sets signal control indicators, and improves signal instructions.

[0015] 4. The present invention realizes iterative analysis of difference values ​​at different temperatures through grouping, deviation calculation and re-grouping of chromatogram information, thereby obtaining difference indicators, and selecting the optimal control strategy based on these indicators, making the entire analysis process highly automated, reducing the possibility of human intervention, and improving work efficiency and data consistency. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The present invention is further described below in conjunction with the accompanying drawings and embodiments.

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

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

[0019] Figure 3 It is a flow chart of the injection control module of an industrial online chromatograph based on a flame photometric detector.

[0020] Figure 4 It is a flow chart of the separation control module of an industrial online chromatograph based on a flame photometric detector.

[0021] Figure 5 It is a flow chart of the output control module of an industrial online chromatograph based on a flame photometric detector. DETAILED DESCRIPTION

[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. If no specific techniques or conditions are specified in the embodiments, the techniques or conditions described in the literature in the art or the product specifications are used.

[0023] See also Figure 1 , Figure 2 The industrial online chromatograph based on flame photometric detector includes: a control platform and a server; the control platform is used to control the working condition of the chromatograph and output the chromatogram after the chromatograph works; the server is used to compare the properties and contents of each component on the chromatogram, and upload the corresponding chromatogram and store it in 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 end of the data acquisition module is connected to the injection control module, the output end of the injection control module is connected to the separation control module, the output end of the separation control module is connected to the output control module, and the output end of the output control module is connected to the chromatographic analysis module.

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

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

[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 the separation stability index.

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

[0029] The chromatographic analysis module is used to identify the chromatogram output by the chromatograph, determine the difference value of the chromatogram calculation at different temperatures, and set the chromatograph control strategy.

[0030] The data collected by the sensor or detector is shown below.

[0031] Pressure sensor: used to monitor the pressure of the gas during the injection process, ensuring that the sample enters the column at the correct pressure. This is critical to maintaining a consistent injection volume.

[0032] Temperature Sensor: If a heated inlet is used, a temperature sensor is required to monitor and maintain the proper injection temperature to avoid sample decomposition or condensation.

[0033] Column Oven Temperature Sensor: Chromatographic columns are usually located in a temperature-controlled environment, called a column oven. Temperature sensors are used to accurately measure and control the temperature in this environment, as temperature changes can affect separation efficiency.

[0034] Flow sensor: used to monitor the flow rate of carrier gas, such as helium and nitrogen, to ensure constant and accurate flow conditions, which is very important for obtaining good separation results.

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

[0036] Flame ionization detector: Very sensitive for the total amount of organic compounds, often used in conjunction 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 to prevent impurities from affecting the analysis results.

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

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

[0040] Vibration sensor: used to monitor the working status of mechanical parts inside the 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 aging of electrical components.

[0042] In one embodiment of the present invention, in addition to identifying the injection frequency, injection temperature and injection volume in the injection control module, it is also necessary to judge the working conditions between the various valves in the injection control scenario, as well as the situation of the sample entering each valve. In the present invention, the chromatograph will use a ten-way valve and a six-way valve in combination. At this time, it is necessary to verify the opening and closing rates of the ten-way valve and the six-way valve to ensure that the valves can correspond to the injection frequency when transporting gas; determine the injection frequency, injection temperature and injection volume at different opening and closing rates, and finally judge whether the data of the chromatogram output in this scenario is normal, so as to judge whether the current injection is stable.

[0043] like Figure 3 As shown, the implementation method 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 directly injected into the chromatographic column, which is suitable for thermally stable and volatile samples. It is simple and fast, but has high requirements on the sample.

[0045] Split / Splitless Injection: Part of the sample is introduced into the chromatographic column through the splitter, and the rest is discharged from the system; or all the sample enters the chromatographic column in splitless mode. Suitable for more complex or high-concentration samples, it can reduce contamination and improve sensitivity.

[0046] Headspace sampling: Extract gas samples from the top space of a closed container for analysis, suitable for volatile organic compounds. It avoids direct contact of liquid samples with the instrument and reduces maintenance costs.

[0047] Programmed temperature vaporization injection: The sample gradually vaporizes and enters the chromatographic column during a gradual heating process, which is particularly suitable for mixtures with a wide boiling range. It provides wider applicability and better peak shape.

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

[0049] Microinjection: Use a micro-syringe to precisely control the injection of very small amounts of sample. Suitable for high-precision analysis of trace or precious samples.

[0050] Solid phase microextraction: Utilize fibers coated with a stationary phase to adsorb the target compound, and then directly insert it into the chromatograph for desorption analysis. No solvent is required, the operation is simple, and it is environmentally friendly.

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

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

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

[0054] User-defined settings: Allow users to adjust certain parameters according to actual needs and save them as new configuration files.

[0055] History Record: Keep the parameter settings for each analysis for easy review and optimization.

[0056] The sample injection frequency, injection temperature and injection volume are obtained from the setting parameters; different values ​​are used for the setting parameters of different injection types in terms of injection frequency, injection temperature and injection volume, and the setting parameters are adjusted according to different user preferences. For example, these values ​​can be adjusted within a range of no more than 10% according to user preferences, or the injection temperature at this time can be adjusted according to the highest temperature of the sample itself, to ensure that the sample can fully react with the chromatographic column during injection and complete the analysis of the sample.

[0057] Determine the gas path of the current sample in the ten-way valve and the six-way valve under the set parameters, and identify the opening and closing rate of the valve in the gas path. The opening and closing rate is expressed as the ratio of the number of times the valve is opened in a complete cycle to the total number of times. This opening and closing rate is generally fixed to a certain value to cooperate with the ten-way valve and the six-way valve to perform pre-separation, backwashing, re-injection and other operations on the sample to complete the input control of the sample.

[0058] Compare the valve opening and closing rate with the injection frequency, injection temperature and injection volume to set the injection stability index.

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

[0060] For example, use the standard deviation and average value of the opening and closing rate to make a judgment; use the injection frequency to compare with the set standard injection frequency; use the standard deviation and average temperature of the injection temperature to make a judgment, and judge the comparison between the maximum value at this time and the acceptable range of the sample; use the standard deviation of the injection volume to compare with the standard processing speed quantity. The standard processing speed quantity represents the average processing rate for completing the analysis of the sample. This will compare the rate with the current amount to determine whether the injection volume is appropriate.

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

[0062] The valve opening and closing rate score represents the standard deviation of the opening and closing rate around the mean opening and closing rate.

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

[0064] The injection temperature score is calculated by calculating the ratio of the injection temperature standard deviation to the average value, the difference between the maximum injection temperature and the upper limit of the acceptable temperature of the sample, and the ratio of the upper limit of the acceptable temperature of the sample. The maximum value of these two values ​​is taken as the injection temperature score.

[0065] The injection volume score is calculated by calculating the ratio of the injection volume standard deviation to the injection volume average, the difference between the injection volume and the standard speed processing volume, and the ratio of the standard speed processing volume. The two values ​​are added as the injection volume score used.

[0066] The final injection stability metric is expressed as a weighted combination 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 and closing rate score, Sf represents the injection frequency score, ST represents the injection temperature score, SV represents the injection volume score, and w SR represents the weight of the valve opening and closing rate score, w Sf represents the weight of the injection frequency score, w ST represents the weight of the injection temperature score, w SV 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 the sample, determines the sampling time set under the carrier gas flow rate and the injection frequency, injection temperature and injection volume corresponding to the sample at this time, and sets the separation stability index for the current separation process according to the separation degree, baseline noise and peak area repeatability during separation.

[0069] Separation degree: It 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 background signal. Lower baseline noise means better stability.

[0071] Peak area repeatability: evaluates the consistency of the peak area of ​​the same component in multiple analyses. The peak described here is the content of each separated component during the separation operation. At the same time, since impurities are prone to appear during separation, there will be a certain deviation in the baseline of the separation. At the same time, when analyzing the sample, multiple sampling analyses will be performed to obtain multiple different chromatograms. Peak area repeatability is the overlapping area of ​​the same components in multiple chromatograms when combined, so as to judge the relative value between the size of the content calculation of each component.

[0072] When using a chromatograph to analyze a single sample, the input sample will be divided into multiple parts by the chromatograph and tested in turn. In this case, the results output by the chromatograph will contain multiple groups of results. At this time, the differences between these analyses can be compared by comparing the areas of the components obtained in each group to determine the impact of the current sampling time, carrier gas flow rate and other parameters on the final separation effect.

[0073] In the separation control module, the delay of the carrier and the sample is analyzed, and the carrier gas flow rate and the sampling time are adjusted in the following manner: the delay of the carrier and the sample is determined from the pre-selected backup information, and the pre-selected backup information is backed up and matched, the carrier gas flow rate and the sampling time of the carrier and the sample under the corresponding delay conditions are determined during the matching process, identification information related to the carrier gas flow rate and the sampling time is set, and in response to the identification information related to the carrier gas flow rate and the sampling time, the identification information related to the carrier gas flow rate and the sampling time is regarded as the target identification information, and the average value of the corresponding carrier gas flow rate and the sampling time in the target identification information is set as the current carrier gas flow rate and the sampling time.

[0074] The pre-selected backup information is the data content set for the current sample analysis. This content will be adjusted according to the subject and use of the chromatographic analysis, and serves as a database for sample processing adjustments at this time. The delay may vary depending on many factors, such as the physical characteristics of the carrier and sample, the state of the instrument, environmental conditions, etc.

[0075] The purpose of matching the pre-selected backup information is to find the historical data or model prediction that is closest to 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 model, find the carrier gas flow rate and sampling time that correspond to the current delay situation. These values ​​may need to be fine-tuned according to the specific circumstances of the experiment.

[0077] Set identification information for data related to carrier gas flow rate and sampling time. This identification information can be a digital code, label or other form of metadata. The purpose of the identification information is to facilitate subsequent data management and analysis.

[0078] During the experiment, the system will continuously detect and respond to these markers. When the system recognizes markers that are related to the carrier gas flow rate and sampling time, it will treat them as target markers.

[0079] Extract the corresponding carrier gas flow rate 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 flow rate and sampling time.

[0080] This process can be automated through programming. For example, you can use programming languages ​​such as Python and R, combined with a database management system to store and retrieve pre-selected backup information. You can write algorithms to implement the matching process, calculate averages, and update parameter settings.

[0081] The implementation method of setting the separation stability index is as follows: select any two components from the chromatogram, calculate the separation degree, baseline noise ratio and peak area repetition ratio of the two adjacent components; each component is represented by a peak in the chromatogram, the width of the peak is described by time, and the height of the peak is described by the content of the component; the separation degree compares the ratio of the difference in retention time between the two components and the sum of the widths of the corresponding peaks of the two components. The final separation degree will be multiplied by two when output to strengthen the data prominence of the separation degree at this time. The retention time indicates the time from the sample feeding of the current component to the peak of the current component. This time will indicate the corresponding appearance time of the current component.

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

[0083] The peak area repetition ratio is calculated by calculating the average value of the ratio of the peak area corresponding to the current component in multiple tests to the peak area in adjacent tests. The number used to calculate the ratio of the peak area of ​​the current component is selected as the moving average of three adjacent tests. This moving average is used to calculate the ratio value of the current peak area. Finally, the average value of this ratio is taken as the output peak area repetition ratio.

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

[0085] The deviations of adjacent components on the baseline of the chromatogram were compared and the baseline-to-noise ratio was calculated.

[0086] The separation degree, baseline noise ratio and peak area repetition ratio of each component are used to set a mapping parameter curve according to the values ​​of carrier gas flow rate and sampling time. The mapping parameter curve is superimposed with the values ​​corresponding to the separation degree, baseline noise ratio and peak area repetition ratio to obtain a 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 the separation degree, baseline noise ratio and peak area repetition ratio under different carrier gas flow rates and sampling times, and analyzing these three data using regression parameters. This curve will show the change values ​​of the currently identified separation degree, baseline noise ratio and peak area repetition ratio when the carrier gas flow rate and sampling time change.

[0088] Then, the mapping parameter curve is superimposed with the values ​​corresponding to the separation, baseline noise ratio and peak area repetition ratio by superimposing the mapping parameter curves obtained for the separation, baseline noise ratio and peak area repetition ratio at the corresponding carrier gas flow rate and sampling time. The superposition method can obtain a moving average of the values ​​of the separation, baseline noise ratio and peak area repetition ratio on the mapping parameter curve, combine the mapping parameter curves for obtaining the moving average, and finally obtain the separation difference curve, and set the slope of the separation difference curve as the separation stability index. Since there is a certain gap between the values ​​represented by the separation, baseline noise ratio and peak area repetition ratio, it is necessary to adjust the separation, baseline noise ratio and peak area repetition ratio to a numerical range of 0-1, and then superimpose the mapping parameter curves corresponding to the separation, baseline noise ratio and peak area repetition ratio, and finally 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 is necessary 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 according to the maximum and minimum values, as well as other data corresponding to the center point, 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 points corresponding to the amplitude, pressure and hysteresis rate of the electrical signal under the output condition, and determining the key points during 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, and 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 divide the states of amplitude, pressure and hysteresis rate under different values.

[0093] The signal control indicator sets the key points according to the values ​​of amplitude, pressure and hysteresis rate to obtain a graph under multiple values. For example, the implementation method of the signal control indicator includes: connecting the key points according to the calculation sequence of the amplitude, pressure and hysteresis rate of the electrical signal, and obtaining a connection graph about the amplitude, a connection graph about the pressure, and a connection graph about the hysteresis rate respectively.

[0094] The amplitude represents the maximum value or peak strength of the electrical signal output by the detector; regarding the connection graph of the amplitude, the key points will be connected according to the value of the amplitude at the key points, and finally the key points will form a graph.

[0095] Pressure usually refers to the pressure parameter related to the carrier gas or mobile phase. When obtaining the pressure, the carrier gas pressure, the detector inlet pressure, and the pressure difference at both ends of the chromatographic column are used to represent it. The connection graph of pressure will connect the pressure values ​​represented by these three pressures to obtain a connection graph of pressure combined at the key points.

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

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

[0098] The area ratio and represents the connection graph about amplitude, the connection graph about pressure and the connection graph about hysteresis rate. After calculating the area, the sum of the ratios of the areas of the three graphs and the average values ​​of the corresponding areas in the historical data is used as the signal control indicator at this time. This value will represent the specific situation of the chromatograph under stable working state and the numerical values ​​reflected by the system under these circumstances.

[0099] In one embodiment of the present invention, in the chromatography analysis module, the deviation of the chromatogram during calculation is mainly processed, the contents causing the deviation of the chromatogram are identified, and these contents are compared to find the deviation value that can cause the current chromatogram to appear at different temperatures. The state of the chromatograph is fed back through the deviation value to select the control strategy for the chromatograph at this time. This strategy is to minimize the deviation of the current chromatogram as much as possible and complete the control of the chromatograph according to the corresponding content.

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

[0101] Obtain the difference index of the chromatogram information in the newly divided adjacent groups, retrieve the difference index according to the working status of the chromatograph, obtain the target category corresponding to the chromatogram information, call the preset control strategy corresponding to the target category in the database, and judge whether the preset control strategy and the target category are consistent with the working status of the chromatograph. When they are consistent, set the preset control strategy corresponding to the current target category as the chromatograph control strategy; when they are inconsistent, retrieve the adjacent strategy information of the preset control strategy, and use the average value set in the adjacent strategy information as the chromatograph control strategy.

[0102] The deviation of the above-mentioned chromatogram information is the retention time deviation, peak area deviation, peak height deviation, separation deviation, and baseline noise deviation of each component in the chromatogram. These values ​​are divided into multiple groups according to different values ​​to obtain newly divided groups. Then, the difference values ​​at different temperatures are calculated to calculate the difference values ​​corresponding to temperature, retention time, peak area, and separation. The difference index will be expressed as follows: according to the different difference values ​​corresponding to temperature, retention time, peak area, and separation, three curves are set to construct temperature-retention time curve, temperature-separation curve, and temperature-peak area curve; in these three curves, the temperature value is used as the horizontal axis, the retention time, peak area, and separation are used as the vertical axis, and the average slope value of the temperature-retention time curve, the temperature-separation curve, and the temperature-peak area curve is used as the difference index corresponding to the chromatogram information. The average slope value represents that after the slope values ​​of the three curves are obtained separately, the average slope value is used as the difference index.

[0103] The above-mentioned target category is a category containing corresponding difference indicators. The target category is used to classify the current chromatogram information into a specific category. These categories are set according to the difference indicators. The preset control strategy contains information when the chromatograph is in operation, such as column temperature setting, 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 for adjusting the settings.

[0104] In the present invention, the control platform controls the working conditions of the chromatograph, including starting, stopping, and pausing the chromatographic analysis process, adjusting various operating parameters such as temperature, flow rate, etc., and monitoring the status of the chromatograph, and then processes the data from the detector, generates and displays the chromatogram for the user to view and analyze.

[0105] The control platform directly implements the following functions: The data of the sensors and detectors set on the chromatograph are collected in real time through a high-precision ADC, and the collected data is stored locally for subsequent analysis. The setting parameters of the current injection type are extracted from the database to determine the injection frequency, temperature and amount; the opening and closing rates of the six-way valve and the ten-way valve are controlled according to the setting parameters to ensure that the sample enters the chromatographic system correctly, and the injection stability index is calculated. According to the delay in the pre-selected backup information, the carrier gas flow rate and sampling time are adjusted to optimize the separation effect; by analyzing the peak characteristics of each component in the chromatogram, the separation degree, baseline noise ratio and peak area repetition ratio are calculated, and the separation stability index is set. The amplitude, pressure and hysteresis rate of the output electrical signal are monitored in real time to ensure the signal quality; according to the maximum and minimum values ​​of the electrical signal and their corresponding center points, the key points during output control are set, the calculation sequence is obtained, and the signal control index is obtained. The chromatogram output by the chromatograph is identified and the difference values ​​at different temperatures are calculated; according to the deviation and difference index of the chromatogram information, the optimal chromatograph control strategy is selected.

[0106] The server receives and processes the chromatogram data uploaded by the control platform, compares the properties and contents of each component on the chromatogram, and performs data analysis; the processed chromatogram data is stored in the database for easy historical data query and long-term storage. At the same time, a remote access interface is provided, allowing users to monitor the working status of the chromatograph through the network and perform necessary management and configuration.

[0107] The service directly implements the following functions: receiving chromatogram data from the control platform, including raw data and analysis results; storing the received data in the database to ensure data security and integrity; parsing the chromatogram to identify the retention time and peak area of ​​each component; comparing chromatograms in different batches or time periods to evaluate the properties and content changes of each component. Provide a friendly Web interface, users can access the server through a browser to view chromatograms and related data; provide an API interface to support third-party software or system integration to achieve automated management and data analysis. Real-time monitoring of the working status of the chromatograph, when an abnormal situation is detected, trigger an alarm and notify relevant personnel via email, SMS, etc. Record all operation logs to facilitate problem troubleshooting and responsibility tracing.

[0108] Through the design of the control platform and server, the present invention realizes the comprehensive management and optimization of the industrial online chromatograph based on the flame photometric detector. 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 powerful back-end support system. This division of labor and cooperation not only improves the reliability and stability of the system, but also provides users with a more convenient operation experience.

[0109] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention and they are still covered by 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 working condition of the chromatograph and output the chromatogram after the chromatograph works; The server is used to compare the properties and contents of each component on the chromatogram, and upload the corresponding chromatogram and store it in the database; The control platform includes: data acquisition module, injection control module, separation control module, output control module and chromatographic analysis module; A data acquisition module is used to collect data from sensors and detectors provided on the chromatograph and store the collected data; The injection control module is used to obtain the injection frequency, injection temperature and injection volume of the sample, determine the injection status of the sample under the joint control of the six-way valve and the ten-way valve; and set the injection stability index of the sample according to the opening and closing rate of the valve under the injection status; Separation control module, used to analyze the delay of carrier and sample, adjust the carrier gas flow rate and sampling time, and set the separation stability index; Output control module, used to monitor the amplitude, pressure and hysteresis rate of the output electrical signal, determine the quality of the output signal, and set the signal control index; The chromatographic analysis module is used to identify the chromatogram output by the chromatograph, determine the difference value of the chromatogram calculation at different temperatures, and set the chromatograph control strategy.

2. The industrial online chromatograph based on flame photometry detector according to claim 1, characterized in that: The implementation methods of the injection control module include: Obtaining the injection type of the sample, and extracting setting parameters corresponding to the current injection type from the database; The injection frequency, injection temperature and injection volume of the sample are obtained from the setting parameters; Determine the gas path of the current sample in the ten-way valve and the six-way valve under the set parameters, and identify the opening and closing rate of the valve under the gas path; Compare the valve opening and closing rate with the injection frequency, injection temperature and injection volume to set the injection stability index.

3. The industrial online chromatograph based on flame photometry detector according to claim 2, characterized in that: The injection stability index is expressed as follows: the valve opening and closing rate score, injection frequency score, injection temperature score and injection volume score corresponding to the valve opening and 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 flame photometry detector according to claim 1, characterized in that: Analyze the delay of the carrier and sample, and adjust the carrier gas flow rate and sampling time as follows: Determine the delay conditions of the carrier and the sample from the pre-selected backup information, perform backup matching on the pre-selected backup information, determine the carrier gas flow rate and sampling time of the carrier and the sample under the corresponding delay conditions during the matching process, set identification information related to the carrier gas flow rate and the sampling time, respond to the identification information related to the carrier gas flow rate and the sampling time, regard the identification information related to the carrier gas flow rate and the sampling time as target identification information, and set the average value of the corresponding carrier gas flow rate and sampling time in the target identification information as the current carrier gas flow rate and sampling time.

5. The industrial online chromatograph based on 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 separation degree and peak area repetition ratio of each component in turn according to the retention time and peak area of ​​each component; Compare the deviations of adjacent components on the baseline of the chromatogram and calculate the baseline-to-noise ratio; The separation degree, baseline noise ratio and peak area repetition ratio of each component are used to set a mapping parameter curve according to the values ​​of carrier gas flow rate and sampling time. The mapping parameter curve is superimposed with the values ​​corresponding to the separation degree, baseline noise ratio and peak area repetition ratio to obtain a 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 flame photometric detector according to claim 5, characterized in that: The mapping parameter curve is superimposed with the values ​​corresponding to the resolution, baseline-to-noise ratio, and peak area repetition ratio as follows: The mapping parameter curves of separation, baseline noise ratio and peak area repetition ratio obtained at the corresponding carrier gas flow rate and sampling time are superimposed, and the moving average values ​​of the separation, baseline noise ratio and peak area repetition ratio on the mapping parameter curves are calculated. The mapping parameter curves with the moving average values ​​are combined to obtain the separation difference curve, and the slope of the separation difference curve is set as the separation stability index.

7. The industrial online chromatograph based on 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 points corresponding to the amplitude, pressure and hysteresis rate of the electrical signal under output conditions, and determine the key points of output control according to 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, and 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 flame photometric detector according to claim 7, characterized in that: The implementation methods of signal control indicators include: Connect the key points according to the calculation sequence of the amplitude, pressure and hysteresis rate of the electrical signal, and obtain a connection graph about the amplitude, a connection graph about the pressure and a connection graph about the hysteresis rate respectively; The sum of the area ratios of the connection graph regarding amplitude, the connection graph regarding pressure, and the connection graph regarding hysteresis rate is used as the signal control index.

9. The industrial online chromatograph based on flame photometric detector according to claim 1, characterized in that: The implementation of the chromatographic analysis module includes: Acquire chromatogram information output by the chromatograph, group the current chromatogram information according to the values ​​of the injection stability index, the separation stability index and the signal control index, use each group of chromatogram information to judge the output of the chromatogram, calculate the deviation of each group of chromatogram information, and regroup each group of chromatogram information according to the deviation of the chromatogram information, use the chromatogram information belonging to the same group in the newly divided group, calculate the difference value at different temperatures, and iterate to obtain the difference index corresponding to the chromatogram information; Obtain the difference index of the chromatogram information in the newly divided adjacent groups, retrieve the difference index according to the working status of the chromatograph, obtain the target category corresponding to the chromatogram information, call the preset control strategy corresponding to the target category in the database, and judge whether the preset control strategy and the target category are consistent with the working status of the chromatograph. When they are consistent, set the preset control strategy corresponding to the current target category as the chromatograph control strategy; when they are inconsistent, retrieve the adjacent strategy information of the preset control strategy, and use the average value set in the adjacent strategy information as the chromatograph control strategy.

10. The industrial online chromatograph based on flame photometric detector according to claim 9, characterized in that: The difference index is expressed as: The difference values ​​between temperature and retention time, peak area and separation degree were calculated, and the temperature-retention time curve, temperature-separation degree curve and temperature-peak area curve were constructed according to the different difference values ​​between temperature and retention time, peak area and separation degree. The average values ​​of the slopes of the temperature-retention time curve, the temperature-separation degree curve and the temperature-peak area curve were used as the difference index corresponding to the chromatogram information.

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