Water quality on-line automatic analyzer detection method and system thereof

Abstract

The application discloses a water quality on-line automatic analyzer detection method, which comprises determining a concentration fluctuation range of a target factor on site, and extracting a minimum concentration value A and a maximum concentration value B; based on the minimum concentration value and the maximum concentration value, calculating and obtaining a segmented range of at least three target factors by using a range formula; detecting a target factor of a water sample by using a target factor electrode and obtaining a pre-check concentration value, and selecting a segmented range according to the pre-check concentration value; based on the selected segmented range, analyzing and detecting the water sample to obtain a true concentration value of a water sample detection result; the application can divide multiple sub-ranges according to on-site conditions, select the most suitable range based on the predicted concentration of the target factor, so that the measurement is more accurate, and the application can dynamically select the most suitable sub-range following the concentration fluctuation during multiple detections, so that the situation that the measurement is wrong due to the concentration amplitude exceeding the range range when only one range is used can be avoided.

Description

Technical Field

[0001] This invention relates to the field of water quality testing technology, and in particular to a method and system for online automatic water quality analyzer. Background Technology

[0002] Currently, online automatic water quality analyzers are widely used in the monitoring of surface water, domestic sewage, and industrial wastewater discharge. However, due to the large fluctuations in actual water samples, the concentration data of the target factor in the actual water sample fluctuates greatly during each test, which may exceed the current range. Therefore, a single range is insufficient to meet the needs of online water quality monitoring.

[0003] In existing technologies, blind testing is typically used to select the switching range before testing the water sample. This approach requires testing a single water sample twice, which not only wastes reagents and time but also increases testing costs and generates a large amount of waste liquid, violating the principles of environmental protection and energy conservation. Online water quality monitoring is a real-time dynamic process that reflects changes in water quality. Therefore, testing the same water sample twice cannot effectively reflect the current dynamic changes in water quality, and the monitoring of water quality changes cannot be well unified, resulting in a certain lag and a certain vacuum in water quality monitoring. Moreover, with only two ranges to switch between, generally only a small range and a large range can be selected, leading to a practical reason for large deviations in measurement accuracy. Summary of the Invention

[0004] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0005] In view of the problems existing in the prior art, the present invention is proposed.

[0006] Therefore, the technical problem to be solved by the present invention is that in the prior art, when testing water samples, a blind test is first performed to select the range and then the selected range is used for testing, which easily leads to cost waste. Moreover, two tests are required to obtain a result for a water sample. The concentration fluctuation of the target factor will cause the test accuracy of the selected range to be low and have no reference value.

[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a method for detecting water quality using an online automatic analyzer, which includes determining the concentration fluctuation range of the target factor on site and extracting the minimum concentration value A and the maximum concentration value B;

[0008] Based on the minimum concentration value and the maximum concentration value, the segmented ranges of at least three target factors are calculated and obtained using the range formula, wherein the minimum value of the multiple segmented ranges is less than the minimum concentration value, and the maximum value is greater than the maximum concentration value.

[0009] The target factor of the water sample is detected by the target factor electrode and a pre-detection concentration value is obtained. A segmented range is selected based on the pre-detection concentration value. The minimum value of the segmented range is less than the pre-detection concentration value, and the maximum value of the segmented range is greater than the pre-detection concentration value.

[0010] The water sample is analyzed and tested based on the selected segmented measurement range to obtain the true concentration value of the water sample test results.

[0011] As a preferred embodiment of the online automatic water quality analyzer detection method of the present invention, the method further includes: calculating the difference between the actual concentration value and the pre-detection concentration value, comparing the difference with a first preset value, and if the difference is greater than the first preset value, then returning to calibrate the target factor electrode.

[0012] As a preferred embodiment of the online automatic water quality analyzer detection method of the present invention, it further includes: preset n detection times, when the set time is reached, detecting the pre-detection concentration value and the actual concentration value of the target factor and storing and recording the pre-detection concentration value, the actual concentration value and the difference;

[0013] Set the allowable number of errors m, which is less than or equal to the number of detection times n. If the difference obtained in each detection time is greater than the second preset value, the count is incremented by 1. When the count reaches the allowable number of errors m, the standby calibration program is started. The standby calibration program is used to calibrate the target factor electrode when the analyzer is in standby mode.

[0014] As a preferred embodiment of the online automatic water quality analyzer detection method of the present invention, the step of "calculating and obtaining the segmented ranges of at least three target factors using the range formula" specifically includes:

[0015] The lower limit concentration value of the first segment range is set to 0, and the upper limit concentration value K of the first segment range is calculated and obtained:

[0016] ;

[0017] Where T is a preset multiple;

[0018] The second segmented range is determined based on the first segmented range, and multiple segmented ranges are determined according to the setting rules of the second segmented range:

[0019] ;

[0020] ;

[0021] in, This is the lower limit concentration value of the nth segment range; This is the upper limit concentration value of the (n-1)th segment range; This represents the upper limit concentration value of the nth segment range; n ≥ 2 and n is a positive integer; H is the preset percentage; H is the preset multiple.

[0022] As a preferred embodiment of the online automatic water quality analyzer detection method of the present invention, the specific steps of "analyzing and detecting the water sample based on the selected segmented measurement range to obtain the true concentration value of the water sample detection result" include:

[0023] Quantitative control of water samples and digestion reagents was performed for digestion treatment;

[0024] The digested water sample was quantitatively controlled and subjected to color development and absorbance detection with a colorimetric reagent, and the absorbance value was obtained.

[0025] Based on the calibration curve, the true concentration value of the target factor in the water sample is calculated and output.

[0026] As a preferred embodiment of the online automatic water quality analyzer detection method of the present invention, the specific calculation method for "calculating the difference between the actual concentration value and the pre-detection concentration value" includes:

[0027] .

[0028] The present invention also provides the following technical solution: an online automatic water quality analyzer detection system, including a detection device and a control device, wherein the detection device and the control device are communicatively connected, and the control device is configured to: extract a minimum concentration value A and a maximum concentration value B according to the input concentration fluctuation range, and calculate and obtain segmented ranges of at least three target factors based on the minimum concentration value and the maximum concentration value using a range formula, wherein the minimum value of the multiple segmented ranges is less than the minimum concentration value, and the maximum value is greater than the maximum concentration value;

[0029] The control device controls the detection device to detect the target factor of the water sample using the target factor electrode and obtain the pre-detection concentration value. Based on the pre-detection concentration value, a segmented range is selected, where the minimum value of the segmented range is less than the pre-detection concentration value and the maximum value of the segmented range is greater than the pre-detection concentration value. Based on the selected segmented range, the control device controls the detection device to analyze and detect the water sample to obtain the true concentration value of the water sample detection result.

[0030] As a preferred embodiment of the online automatic water quality analyzer detection system of the present invention, the control device includes a timing module, a counting module, and a range module;

[0031] The timing module is used to preset n detection times. When the set time is reached, it detects the pre-detection concentration value and the actual concentration value of the target factor and stores and records the pre-detection concentration value, the actual concentration value and the difference.

[0032] The counting module is used to set the error allowable number of times m, which is less than or equal to the number of detection times n. If the difference obtained in each detection time is greater than the second preset value, the count is incremented by 1. When the count reaches the error allowable number of times m, the standby calibration program is started. The standby calibration program is used to calibrate the target factor electrode when the analyzer is in standby mode.

[0033] The segmentation module is used to calculate and obtain the segmented ranges of at least three target factors. The lower limit concentration value of the first segmented range is set to 0, and the upper limit concentration value K of the first segmented range is calculated and obtained.

[0034] ;

[0035] Where T is a preset multiple;

[0036] The second segmented range is determined based on the first segmented range, and multiple segmented ranges are determined according to the setting rules of the second segmented range:

[0037] ;

[0038] ;

[0039] in, This is the lower limit concentration value of the nth segment range; This is the upper limit concentration value of the (n-1)th segment range; H represents the upper limit concentration value of the nth segment range; n ≥ 2 and n is a positive integer, and H is a preset multiple. This is the preset percentage.

[0040] As a preferred embodiment of the online automatic water quality analyzer detection system of the present invention, the control device includes a calculation module, which is used to calculate and output the true concentration value of the target factor in the water sample based on the calibration curve;

[0041] The calculation module is also used to calculate the difference between the actual concentration value and the pre-detection concentration value, compare the difference with the first preset value, and if the difference is greater than the first preset value, return to calibrate the target factor electrode.

[0042] The specific calculation method for "calculating the difference between the actual concentration value and the pre-detection concentration value" includes:

[0043] .

[0044] As a preferred embodiment of the online automatic water quality analyzer detection system of the present invention, the detection device includes a pre-detection tank, a digestion tank, a detection tank and a metering device, wherein the pre-detection tank, the digestion tank and the detection tank are interconnected by a multi-way valve;

[0045] The pre-detection pool is equipped with a target factor electrode for detecting the pre-detection concentration value of the water sample.

[0046] The metering device is used to: quantitatively introduce water samples into the digestion tank under the control of the control module, and quantitatively introduce digestion solution into the detection tank under the control of the control module.

[0047] The beneficial effects of this invention are: This invention can automatically divide a large range into multiple sub-ranges according to the on-site conditions, and select the most suitable range based on the predicted concentration of the target factor, thereby making the measurement more accurate. In addition, this invention can dynamically select the most suitable sub-range according to the concentration fluctuation during multiple detections, which can avoid the situation where the concentration range exceeds the range when using a single range, causing measurement errors. Attached Figure Description

[0048] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0049] Figure 1 This is a flowchart of an online automatic water quality analyzer detection method according to one embodiment of the present invention.

[0050] Figure 2 This is a flowchart of water sample analysis and testing according to one embodiment of the present invention.

[0051] Figure 3 This is a structural block diagram of the control device according to one embodiment of the present invention.

[0052] Figure 4 This is a schematic diagram of the connection structure of the detection device in one embodiment of the present invention.

[0053] Figure 5 This is a calibration curve of the COD target factor under different ranges in one embodiment of the present invention.

[0054] Figure 6 This is a calibration curve of the ammonia nitrogen target factor under different ranges in one embodiment of the present invention.

[0055] Figure 7 This is a calibration curve of the fluoride target factor under different ranges in one embodiment of the present invention. Detailed Implementation

[0056] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0057] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0058] Secondly, the term "one embodiment" or "implementation method" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0059] Reference Figure 1 As shown, one embodiment of the present invention provides a method for online automatic water quality analyzer detection. This method is used to detect water quality and can detect the concentration of target factors in a water sample. Specific steps include:

[0060] S1: Determine the concentration fluctuation range of the target factor on site, and extract the minimum concentration value A and the maximum concentration value B;

[0061] S2: Based on the minimum concentration value and the maximum concentration value, calculate and obtain the segmented ranges of at least three target factors using the range formula, wherein the minimum value of the multiple segmented ranges is less than the minimum concentration value, and the maximum value is greater than the maximum concentration value;

[0062] S3: Detect the target factor of the water sample using the target factor electrode and obtain the pre-detection concentration value. Select a segmented range based on the pre-detection concentration value. The minimum value of the segmented range is less than the pre-detection concentration value, and the maximum value of the segmented range is greater than the pre-detection concentration value.

[0063] S4: Analyze and test the water sample based on the selected segmented range to obtain the true concentration value of the water sample test results.

[0064] Specifically, in step S1, the concentration fluctuation range of the target factor at the site can be determined by manual measurement using a coarse measuring device or by estimating the concentration range based on the site environment. Thus, a large range is selected during the first preliminary measurement for subsequent measurements. After selection, multiple segmented ranges are determined in step S2 to more accurately measure the concentration.

[0065] In step S2, at least three segmented ranges are set, and the upper limit of the last segmented range must be greater than the upper limit of the concentration range estimated based on the on-site environment, so as to avoid the situation where the concentration exceeds the segmented range when it reaches the maximum value, thus causing inaccurate measurement.

[0066] It should be noted that in step S2, the segmented range setting is automatically generated by the control device based on the estimated concentration range through program code and then stored in the memory of the control device.

[0067] In step S3, the target factor electrode is used to preliminarily predict the concentration. Since the time of each test is different, the target factor fluctuates and therefore there is a certain range of fluctuation in each test. The required segmented range is determined by the pre-detection concentration value measured by the target factor electrode, so that the subsequent analyzer detection can be more accurate. This solves the problem that if a large range is used in the current technology, the detection results will be inaccurate. Moreover, the preliminary prediction of the target factor does not affect the subsequent detection of the analyzer, and the actual detection only needs to be performed once.

[0068] In one embodiment of the present invention, the method further includes calculating the difference between the actual concentration value and the pre-detection concentration value, comparing the difference with a first preset value, and if the difference is greater than the first preset value, then returning to calibrate the target factor electrode.

[0069] In this way, the target factor electrode can be calibrated in real time based on the actual detected concentration and the pre-detected concentration value, so that the target factor electrode can be closer to the actual concentration when initially estimating the concentration, avoiding the problem of inaccurate selected range.

[0070] It should be noted that the target factor electrode calibration process is as follows: the instrument automatically draws distilled water and a standard solution of a certain concentration into the pre-test cell 11 for calibration. Specifically, distilled water is drawn into the pre-test cell 11, the measurement signal value is recorded, then the distilled water is drained, a standard solution of a certain concentration is added, the measurement signal value is recorded, then the pre-test cell 11 is emptied and rinsed with distilled water. Then, a linear function relationship is established between the concentration of the calibrated distilled water and standard solution and the measurement signal value to calibrate the electrode.

[0071] Furthermore, each segment range can also be calibrated using the above method.

[0072] Furthermore, the specific calculation method for "calculating the difference between the actual concentration value and the pre-detection concentration value" includes:

[0073] .

[0074] In an embodiment of the present invention, the first preset value can be set to ±25%, that is, if the difference is greater than ±25%, the system determines that the error is large and needs to be calibrated, and then returns to calibrate the target factor electrode.

[0075] In one embodiment of the present invention, the method further includes presetting n detection times, and when the set time is reached, detecting the pre-detection concentration value and the actual concentration value of the target factor and storing and recording the pre-detection concentration value, the actual concentration value and the difference.

[0076] The error allowable count value m and the second preset value are set. The error allowable count value m is less than or equal to the number of detection times n. If the difference obtained in each detection time is greater than the second preset value, the count is incremented by 1. When the count reaches the error allowable count value m, the standby calibration program is started. The standby calibration program is used to calibrate the target factor electrode when the analyzer is in standby mode.

[0077] It should be noted that accurate detection of the target factor requires multiple tests. By setting n detection times in the program, a round of detection is performed at each detection time, for a total of n times. The data from the n tests may fluctuate.

[0078] In this way, after n tests, the data becomes more accurate, avoiding inaccurate data caused by system errors.

[0079] In this embodiment, the second preset value can be set to ±20%. That is, if the data error of m out of n detections exceeds ±20%, although it does not exceed ±25%, the target factor electrode will not be adjusted in real time. However, if the error exceeds ±20% m times, the system error can be considered to be relatively large. After the system is in standby mode, the program executes the automatic calibration command. Specifically, when the number of times reaches m, the standby calibration mode is started. When the standby command is detected, the calibration mode is triggered, the standby command is exited, and the calibration command is executed to calibrate the target factor electrode.

[0080] This allows the system to automatically calibrate while in standby mode, saving time spent on manual adjustments.

[0081] In one embodiment of the present invention, the step of "calculating and obtaining the segmented range of at least three target factors using the range formula" specifically includes:

[0082] The lower limit concentration value of the first segment range is set to 0, and the upper limit concentration value K of the first segment range is calculated and obtained:

[0083] ;

[0084] Where T is a preset multiple;

[0085] The second segmented range is determined based on the first segmented range, and multiple segmented ranges are determined according to the setting rules of the second segmented range:

[0086] ;

[0087] ;

[0088] in, This is the lower limit concentration value of the nth segment range; This is the upper limit concentration value of the (n-1)th segment range; This represents the upper limit concentration value of the nth segment range; n ≥ 2 and n is a positive integer; H is the preset percentage; H is the preset multiple.

[0089] Specifically, the formula: The first segment range is determined by the minimum concentration value A within the concentration fluctuation range, which is 0~ ;formula Used to determine the segmented range of the next segment based on the segmented range of the previous segment. ~ .

[0090] in, It can be set to 80%; T can be a constant of 5; H can be a constant of 4.

[0091] In one embodiment of the present invention, "selecting segmented ranges based on the pre-detection concentration value" can compare the pre-detection concentration value with n segmented ranges respectively. Specifically, the pre-detection concentration value is compared with the upper limit concentration value and the lower limit concentration value of each segmented range to determine whether the pre-detection concentration value is greater than the lower limit concentration value of the segmented range and less than the upper limit concentration value of the segmented range.

[0092] When the pre-detection concentration value is included in both segmented ranges, that is, when the pre-detection concentration value is included in the k-th segmented range and the (k+1)-th segmented range, the pre-detection concentration value is compared with the upper limit concentration value of the k-th segmented range and the lower limit concentration value of the (k+1)-th segmented range. If the difference between the pre-detection concentration value and the upper limit concentration value of the k-th segmented range is greater than the difference between the pre-detection concentration value and the lower limit concentration value of the (k+1)-th segmented range, the k-th segmented range is selected; otherwise, the (k+1)-th segmented range is selected.

[0093] In one embodiment of the present invention, reference is made to Figure 2As shown, the specific steps of "analyzing and detecting the water sample based on the selected segmented measurement range to obtain the true concentration value of the water sample detection result" include:

[0094] S4.1: Quantitatively control the water sample and digestion reagent for digestion treatment; specifically, the metering device 15 controls the quantitative entry of the water sample into the digestion tank, and then quantitatively adds the digestion reagent to the water sample for digestion reaction.

[0095] S4.2: Quantitatively control the digested water sample and colorimetric reagent to perform color development and absorbance detection and obtain the absorbance detection value; specifically, the digestion solution in the digestion tank is quantitatively added to the detection tank through the metering device 15, and then the colorimetric reagent is quantitatively added to perform color development and absorbance detection to obtain the final detection result.

[0096] S4.3: Based on the calibration curve, calculate and output the true concentration value of the target factor in the water sample; specifically, substitute the indicated value of the detection cell into the calibration curve to obtain the final true concentration value.

[0097] It should be noted that the calibration curve is used to output the concentration value according to the result of the detection cell, and the calibration curve is different for different ranges and different target factors. Therefore, the corresponding calibration curve needs to be entered into the system in advance. Figures 5-7 As shown, the corresponding calibration curve is input in advance according to the divided range, and the value of the corresponding curve is output according to the test result during system testing.

[0098] The result of the detection cell is the absorbance, and the concentration value is obtained based on the absorbance.

[0099] In one embodiment, the calibration curve can be automatically analyzed based on the system analysis module to obtain calibration curve functions for different ranges. By substituting the absorbance into the obtained function, the concentration value can be calculated.

[0100] One embodiment of the present invention also provides an online automatic water quality analyzer detection system, referring to... Figure 3 As shown, the online automatic water quality analyzer detection system includes a detection device 1 and a control device 2. The detection device 1 and the control device 2 are communicatively connected. The detection device 1 is used to detect water samples, and the control device 2 is used to monitor the results and control the detection process of the water samples.

[0101] The control device 2 is configured to: extract a minimum concentration value A and a maximum concentration value B according to the input concentration fluctuation range, and calculate and obtain the segmented ranges of at least three target factors based on the minimum concentration value and the maximum concentration value using a range formula, wherein the minimum value of the multiple segmented ranges is less than the minimum concentration value, and the maximum value is greater than the maximum concentration value.

[0102] The control device 2 controls the detection device 1 to detect the target factor of the water sample using the target factor electrode and obtain the pre-detection concentration value. Based on the pre-detection concentration value, the control device 2 calls the segmented range, where the minimum value of the segmented range is less than the pre-detection concentration value and the maximum value of the segmented range is greater than the pre-detection concentration value. Based on the selected segmented range, the control device 1 analyzes and detects the water sample to obtain the true concentration value of the water sample detection result.

[0103] In one embodiment of the present invention, the control device 2 includes a timing module 21, a counting module 22, and a range splitting module 23;

[0104] The timing module 21 is used to preset n detection times. When the set time is reached, it detects the pre-detection concentration value and the actual concentration value of the target factor and stores and records the pre-detection concentration value, the actual concentration value and the difference.

[0105] The counting module 22 is used to set the error allowable number of times m, which is less than or equal to the number of detection times n. If the difference obtained in each detection time is greater than the second preset value, the count is incremented by 1. When the count reaches the error allowable number of times m, the standby calibration program is started. The standby calibration program is used to calibrate the target factor electrode when the analyzer is in standby mode.

[0106] The segmentation module 23 is used to calculate and obtain the segmented ranges of at least three target factors. The lower limit concentration value of the first segmented range is set to 0, and the upper limit concentration value K of the first segmented range is calculated and obtained.

[0107] ;

[0108] Where T is a preset multiple;

[0109] The second segmented range is determined based on the first segmented range, and multiple segmented ranges are determined according to the setting rules of the second segmented range:

[0110] ;

[0111] ;

[0112] in, This is the lower limit concentration value of the nth segment range; This is the upper limit concentration value of the (n-1)th segment range; This represents the upper limit concentration value of the nth segment range; n ≥ 2 and n is a positive integer; H is the preset percentage; H is the preset multiple.

[0113] Furthermore, the control device 2 also includes a calculation module 24, which is used to calculate and output the true concentration value of the target factor in the water sample based on the calibration curve;

[0114] The calculation module 24 is also used to calculate the difference between the actual concentration value and the pre-detection concentration value, compare the difference with the first preset value, and if the difference is greater than the first preset value, return to calibrate the target factor electrode.

[0115] The specific calculation method for "calculating the difference between the actual concentration value and the pre-detection concentration value" includes:

[0116] .

[0117] Reference Figure 4 As shown, the detection device 1 includes a pre-inspection tank 11, a digestion tank 12, a detection tank 13, and a metering device 15. The pre-inspection tank 11, the digestion tank 12, and the detection tank 13 are interconnected through a multi-way valve 14.

[0118] The pre-detection pool 11 is equipped with a target factor electrode for detecting the pre-detection concentration value of the water sample.

[0119] The metering device 15 is used to: quantitatively introduce water samples into the digestion tank 12 under the control of the control module, and quantitatively introduce digestion solution into the detection tank 13 under the control of the control module.

[0120] In summary, referring to... Figure 5 As shown, when the online automatic water quality analyzer system using the above-mentioned method was applied to monitor COD values ​​at the wastewater outlet of a pharmaceutical factory, the specific steps and data are as follows:

[0121] First, replace the electrode factor in the pre-detection cell of the online automatic water quality analyzer system with the COD electrode, adjust the light source in the detection cell to the corresponding light source for COD detection, and select COD for both the corresponding program and reagents. The instrument preparation is now complete.

[0122] On-site situation: COD concentration fluctuates greatly, ranging from 15 mg / L to 800 mg / L.

[0123] For the analyzer range selection, the COD electrode range should be selected from 0 to 1000 mg / L.

[0124] The COD analyzer was tested with a total of three measurement ranges. Since the minimum detectable concentration is 15 mg / L, a=15, A=5a=75. Therefore, the first range is 0~75 mg / L. The second range, calculated using the formula 0.8A~4A, where A=75, is 60~300 mg / L. The third range, calculated using the formula 0.8B~C, where B=4A=300, C=4B=1200, is 240~1200 mg / L.

[0125] COD electrode calibration: Select a COD concentration of 500 mg / L (50% of the range) for calibration;

[0126] Automated analysis system calibration:

[0127] First segment range: 0~75mg / L; calibration is performed using a COD concentration of 60mg / L (80% of the range).

[0128] Second segment range: 60~300mg / L; calibration is performed using a COD concentration of 240mg / L (80% of the range).

[0129] The third range is 240~1200 mg / L; calibration is performed using a COD concentration of 960 mg / L (80% of the range).

[0130] After the water sample enters the online automatic analyzer system, it first enters the pre-testing tank. The COD electrode test value of the water sample is 88.5 mg / L. Based on the electrode test value, the system determines the appropriate parameters and uses the parameters of the second segment range to test the water sample. The test result is 106.72 mg / L, and the output result of 106.72 mg / L is uploaded to the monitoring platform. Next, the system calculates the difference between the electrode test value of 88.5 mg / L and the analyzer's test tank value of 106.72 mg / L. The indication error is -17.07%, which is within ±25%. Therefore, the online automatic analyzer system goes into standby mode, ready to perform the next test at the set time.

[0131] The table below shows the results of 6 COD tests:

[0132]

[0133] For reference Figure 6 As shown, when the online automatic water quality analyzer system using the above-mentioned online automatic water quality analysis method is applied to monitor ammonia nitrogen levels at the wastewater outlet of a food factory, the specific steps and data are as follows:

[0134] First, replace the electrode factor in the pre-detection cell of the online automatic water quality analyzer system with an ammonia nitrogen electrode, adjust the light source in the detection cell to the corresponding light source for ammonia nitrogen detection, and select ammonia nitrogen for both the corresponding program and reagents. The instrument preparation is now complete.

[0135] On-site conditions: Ammonia nitrogen concentration fluctuated significantly, ranging from 1.0 mg / L to 200 mg / L.

[0136] For the analyzer range selection, the ammonia nitrogen electrode range should be selected from 0 to 300 mg / L.

[0137] The ammonia nitrogen analyzer was tested with a total of four measurement ranges. Since the minimum detectable concentration is 1.0 mg / L, a=1, A=5, and a=5, therefore the first range is 0~5 mg / L; the second range, according to the formula 0.8A~4A, A=5, is 4~20 mg / L; the third range, according to the formula 0.8B~C, B=4A=20, C=4B=80, is 16~80 mg / L; and the fourth range, according to the formula 0.8C~D, C=80, D=4C=320, is 64~320 mg / L.

[0138] Ammonia nitrogen electrode calibration: Use an ammonia nitrogen concentration of 150 mg / L (50% of the range) for calibration;

[0139] Automated analysis system calibration:

[0140] First segment range: 0~5mg / L; calibration is performed using an ammonia nitrogen concentration of 4mg / L (80% of the range).

[0141] Second segment range: 4~20 mg / L; calibration is performed using an ammonia nitrogen concentration of 16 mg / L (80% of the range).

[0142] The third range is 16~80 mg / L; calibration is performed using an ammonia nitrogen concentration of 64 mg / L (80% of the range).

[0143] Fourth segment range: 64~320mg / L; calibrated using an ammonia nitrogen concentration of 256mg / L (80% of the range).

[0144] After the water sample enters the online automatic analyzer system, it first enters the pre-testing tank. The ammonia nitrogen electrode test value is 35.7 mg / L. Based on the electrode test value, the system determines the appropriate value and uses the parameters of the third range to test the water sample. The test result is 42.53 mg / L, and this result is uploaded to the monitoring platform. Next, the system calculates the indication error between the electrode detection value of 35.5 mg / L and the analyzer's detection tank value of 42.53 mg / L. The indication error is -16.06%, which is within ±25%. Therefore, the online automatic analyzer system goes into standby mode, ready to perform the next test at the set time.

[0145] The table below shows the results of six ammonia nitrogen tests:

[0146]

[0147] For reference Figure 7 As shown, when the online automatic water quality analyzer system using the above-mentioned online automatic water quality analyzer detection method is applied to monitor fluoride levels at the wastewater outlet of a chemical plant, the specific steps and data are as follows:

[0148] First, replace the electrode factor in the pre-detection cell of the online automatic water quality analyzer system with a fluoride electrode, adjust the light source in the detection cell to the corresponding light source for fluoride detection, and select fluoride for both the corresponding program and reagents. The instrument preparation is now complete.

[0149] On-site conditions: Fluoride concentration fluctuated significantly, ranging from 0.10 mg / L to 25 mg / L.

[0150] For the analyzer range selection, the fluoride electrode range should be selected from 0 to 40 mg / L.

[0151] The fluoride analyzer was used in this study with a total of four measurement ranges. Since the minimum detectable concentration is 0.10 mg / L, a=0.10, A=5a=0.5, therefore the first range is 0~0.5 mg / L; the second range is calculated using the formula: 0.8A~B, A=0.5, therefore the second range is 0.40~2.0 mg / L; the third range is calculated using the formula: 0.8B~C, B=4A=2, C=4B=8, therefore the third range is 1.6~8 mg / L; the fourth range is calculated using the formula: 0.8C~D, C=8, D=4C=32, therefore the fourth range is 6.4~32 mg / L.

[0152] Instrument calibration (recalibrate weekly or if the test deviation exceeds the limit).

[0153] Fluoride electrode calibration: Calibration is performed using an ammonia nitrogen concentration of 20 mg / L (50% of the range);

[0154] Automated analysis system calibration:

[0155] First segment range: 0~0.50 mg / L; calibration is performed using a fluoride concentration of 0.4 mg / L (80% of the range).

[0156] Second segment range: 0.4~2.0 mg / L; calibration is performed using a fluoride concentration of 1.6 mg / L (80% of the range).

[0157] The third range is 1.6~8.0 mg / L; calibration is performed using a fluoride concentration of 6.4 mg / L (80% of the range).

[0158] Fourth range segment: 6.4~32 mg / L; calibrated using a fluoride concentration of 25.6 mg / L (80% of the range).

[0159] After calibration, the online automatic analyzer detection system begins monitoring:

[0160] After the water sample enters the online automatic analyzer system, it first enters the pre-testing tank. The fluoride electrode test value of the water sample is 1.32 mg / L. Based on the electrode test value, the system determines the appropriate value and uses parameters from two measurement ranges to test the water sample. The test result is 1.574 mg / L, and the output result of 1.674 mg / L is uploaded to the monitoring platform. Next, the system calculates the difference between the electrode test value of 1.32 mg / L and the analyzer's test tank value of 1.674 mg / L. The indication error is -21.15%, which is within ±25%. Therefore, the online automatic analyzer system goes into standby mode, ready to perform the next test at the set time.

[0161] The table below shows the results of fluoride testing six times:

[0162]

[0163] It is important to note that the constructions and arrangements of this application shown in several different exemplary embodiments are merely illustrative. Although only a few embodiments are described in detail in this disclosure, those who consult this disclosure will readily understand that many modifications are possible (e.g., changes in the size, dimensions, structure, shape, and proportions of various elements, as well as parameter values ​​(e.g., temperature, pressure, etc.), mounting arrangements, use of materials, color, orientation, etc.) without substantially departing from the novel teachings and advantages of the subject matter described in this application). For example, an element shown as integrally formed may be composed of multiple parts or elements, the position of elements may be inverted or otherwise altered, and the nature or number or position of discrete elements may be changed or altered. Therefore, all such modifications are intended to be included within the scope of the invention. The order or sequence of any process or method steps may be changed or rearranged according to alternative embodiments. In the claims, any "device plus function" clause is intended to cover the structure described herein that performs the function, and not only structurally equivalent but also equivalent in structure. Other substitutions, modifications, alterations, and omissions may be made in the design, operation, and arrangement of the exemplary embodiments without departing from the scope of the invention. Therefore, the present invention is not limited to the specific embodiments, but extends to various modifications that still fall within the scope of the appended claims.

[0164] Furthermore, in order to provide a concise description of exemplary embodiments, not all features of actual embodiments (i.e., those features that are not relevant to the currently considered best mode for carrying out the invention, or those features that are not relevant to implementing the invention) may be omitted.

[0165] It should be understood that numerous specific implementation decisions can be made during the development of any practical implementation, such as in any engineering or design project. Such development efforts may be complex and time-consuming, but for those skilled in the art who benefit from this disclosure, the development effort will be a routine work of design, manufacturing, and production without requiring much experimentation.

[0166] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for detecting water quality using an online automatic analyzer, characterized in that: include, Determine the concentration fluctuation range of the target factor on site, and extract the minimum concentration value A and the maximum concentration value B; Based on the minimum concentration value and the maximum concentration value, the segmented ranges of at least three target factors are calculated and obtained using the range formula, wherein the minimum value of the multiple segmented ranges is less than the minimum concentration value, and the maximum value is greater than the maximum concentration value. The target factor of the water sample is detected by the target factor electrode and a pre-detection concentration value is obtained. A segmented range is selected based on the pre-detection concentration value. The minimum value of the segmented range is less than the pre-detection concentration value, and the maximum value of the segmented range is greater than the pre-detection concentration value. The water sample is analyzed and tested based on the selected segmented measurement range to obtain the true concentration value of the water sample test results; It also includes preset n detection times. When the set time is reached, the pre-detection concentration value and the actual concentration value of the target factor are detected and stored. The error allowable count value m and the second preset value are set. The error allowable count value m is less than or equal to the number of detection times n. If the difference obtained in each detection time is greater than the second preset value, the count is incremented by 1. When the count reaches the error allowable count value m, the standby calibration program is started. The standby calibration program is used to calibrate the target factor electrode when the analyzer is in standby mode. The phrase "calculating and obtaining the segmented range of at least three target factors using the range formula" specifically includes: The lower limit concentration value of the first segment range is set to 0, and the upper limit concentration value K of the first segment range is calculated and obtained: ； Where T is a preset multiple; The second segmented range is determined based on the first segmented range, and multiple segmented ranges are determined according to the setting rules of the second segmented range: ； ； in, This is the lower limit concentration value of the nth segment range; This is the upper limit concentration value of the (n-1)th segment range; H represents the upper limit concentration value of the nth segment range; n ≥ 2 and n is a positive integer, and H is a preset multiple. This is a preset percentage; The specific steps of "analyzing and detecting the water sample based on the selected segmented measurement range to obtain the true concentration value of the water sample detection result" include: Quantitative control of water samples and digestion reagents was performed for digestion treatment; The digested water sample was quantitatively controlled and subjected to color development and absorbance detection with a colorimetric reagent, and the absorbance value was obtained. Based on the calibration curve, the true concentration value of the target factor in the water sample is calculated and output.

2. The method for online automatic water quality analyzer as described in claim 1, characterized in that: It also includes calculating the difference between the actual concentration value and the pre-detection concentration value, comparing the difference with a first preset value, and if the difference is greater than the first preset value, then returning to calibrate the target factor electrode.

3. The method for online automatic water quality analyzer as described in claim 2, characterized in that: The specific calculation method for "calculating the difference between the actual concentration value and the pre-detection concentration value" includes: 。 4. A water quality online automatic analyzer detection system, employing the water quality online automatic analyzer detection method as described in claim 1, the system comprising a detection device and a control device, the detection device and the control device being communicatively connected, characterized in that: The control device is configured to: extract a minimum concentration value A and a maximum concentration value B according to the input concentration fluctuation range, and calculate and obtain the segmented ranges of at least three target factors based on the minimum concentration value and the maximum concentration value using a range formula, wherein the minimum value of the multiple segmented ranges is less than the minimum concentration value, and the maximum value is greater than the maximum concentration value. The control device controls the detection device to detect the target factor of the water sample using the target factor electrode and obtain the pre-detection concentration value. Based on the pre-detection concentration value, the device calls the segmented range, where the minimum value of the segmented range is less than the pre-detection concentration value and the maximum value of the segmented range is greater than the pre-detection concentration value. Based on the selected segmented range, the detection device is controlled to analyze and detect the water sample, and the true concentration value of the water sample detection result is obtained. The control device includes a timing module, a counting module, and a rangefinder module; The timing module is used to preset n detection times. When the set time is reached, it detects the pre-detection concentration value and the actual concentration value of the target factor and stores and records the pre-detection concentration value, the actual concentration value and the difference. The counting module is used to set the error allowable number of times m, which is less than or equal to the number of detection times n. If the difference obtained in each detection time is greater than the second preset value, the count is incremented by 1. When the count reaches the error allowable number of times m, the standby calibration program is started. The standby calibration program is used to calibrate the target factor electrode when the analyzer is in standby mode. The segmentation module is used to calculate and obtain the segmented ranges of at least three target factors. The lower limit concentration value of the first segmented range is set to 0, and the upper limit concentration value K of the first segmented range is calculated and obtained. ； Where T is a preset multiple; The second segmented range is determined based on the first segmented range, and multiple segmented ranges are determined according to the setting rules of the second segmented range: ； ； in, This is the lower limit concentration value of the nth segment range; This is the upper limit concentration value of the (n-1)th segment range; This represents the upper limit concentration value of the nth segment range; n ≥ 2 and n is a positive integer; H is the preset percentage; H is the preset multiple.

5. The online automatic water quality analyzer detection system as described in claim 4, characterized in that: The control device includes a calculation module, which is used to calculate and output the true concentration value of the target factor in the water sample based on the calibration curve. The calculation module is also used to calculate the difference between the actual concentration value and the pre-detection concentration value, compare the difference with the first preset value, and if the difference is greater than the first preset value, return to calibrate the target factor electrode. The specific calculation method for "calculating the difference between the actual concentration value and the pre-detection concentration value" includes: 。 6. The online automatic water quality analyzer detection system as described in claim 4, characterized in that: The detection device includes a pre-detection tank, a digestion tank, a detection tank, and a metering device, wherein the pre-detection tank, the digestion tank, and the detection tank are interconnected by a multi-way valve; The pre-detection pool is equipped with a target factor electrode for detecting the pre-detection concentration value of the water sample. The metering device is used to: quantitatively introduce water samples into the digestion tank under the control of the control module, and quantitatively introduce digestion solution into the detection tank under the control of the control module.

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