Full-automatic titration system and method based on image and potential fusion discrimination

Abstract

The invention relates to a titration technology, and particularly provides a full-automatic titration system and method based on image and potential fusion discrimination, and the system comprises a titration cup and an electrode; the camera is used for obtaining an image of the titration cup; the processing unit obtains a color characteristic value corresponding to the titration volume according to the image, and outputs a potential value corresponding to the titration volume according to the electrode; the processing unit obtains a first candidate end point according to the color characteristic value and obtains a second candidate end point according to the potential value; and the comparison unit obtains a titration end point according to the first candidate end point and the second candidate end point. The method has the advantages of accurate titration, automation and the like.

Description

Technical Field

[0001] This invention relates to titration technology, and more particularly to a fully automated titration system and method for image and potential fusion-based discrimination. Background Technology

[0002] In the rare earth hydrometallurgical process, real-time and accurate detection of the total rare earth content in the solution is crucial for product quality control. Currently, this mainly relies on manual sampling and offline laboratory titration analysis, which suffers from problems such as long analysis cycles, data lag, large human errors, high labor intensity, and the inability to achieve real-time closed-loop process control.

[0003] Existing online titrators mostly use a single potentiometric or photometric method to determine the endpoint. When titrating rare earth samples, the color change at the reaction endpoint is slow and not sensitive. A single sensor is easily affected by factors such as solution turbidity, bubbles, and electrode drift, leading to endpoint misjudgment, poor repeatability, and low reliability, making it difficult to meet the stringent requirements of industrial online detection. Summary of the Invention

[0004] To address the shortcomings of the existing technical solutions, this invention provides a fully automated titration system based on image and potential fusion discrimination.

[0005] The objective of this invention is achieved through the following technical solution: A fully automated titration system based on image and potential fusion discrimination includes a titration cup and electrodes; it also includes: A camera, used to acquire an image of the titration cup; The calculation unit and the processing unit obtain color feature values ​​corresponding to the titration volume based on the image, and output potential values ​​corresponding to the titration volume based on the electrode. The processing unit obtains a first candidate endpoint based on the color feature value and a second candidate endpoint based on the potential value. The comparison unit obtains the titration endpoint based on a first candidate endpoint and a second candidate endpoint.

[0006] The present invention also aims to provide a fully automated titration method based on image and potential fusion discrimination, which is achieved through the following technical solutions: The titration method according to the titration system of this application includes the following steps: A1. Inject the quantitative sample into the titration cup; A2. Add reagent to the titration cup to adjust the liquid color to purple; A3. Add EDTA standard solution dropwise into the titration cup, and the camera captures an image of the titration cup. The electrode outputs a potential sequence. A4. The processing unit obtains the color feature value corresponding to the titration volume based on the image, and outputs the potential value corresponding to the titration volume based on the potential sequence; A5. The processing unit obtains a first candidate endpoint based on the color feature value and a second candidate endpoint based on the potential value; A6. The comparison unit obtains the titration endpoint based on the first candidate endpoint and the second candidate endpoint.

[0007] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. Significantly improved accuracy and reliability of titration endpoint determination: By cross-validating two signals with different physical principles, namely image (sensitive to color) and potential (sensitive to ion concentration), it effectively avoids misjudgment of a single signal caused by solution turbidity, slow color change, electrode failure or noise interference, making the endpoint determination result extremely reliable. 2. Fully automated and highly efficient: It achieves "one-click" fully automatic operation, greatly reducing manual intervention and operation time, and can achieve 24-hour continuous online monitoring with strong data real-time performance; 3. Strong fault tolerance and self-diagnostic capabilities: The fusion decision-making mechanism itself is a built-in quality checkpoint. When the two signals are inconsistent, the system can automatically identify and handle the anomaly, improving the system's robustness and data reliability. Attached Figure Description

[0008] The disclosure of this invention will become more readily understood with reference to the accompanying drawings. It will be readily understood by those skilled in the art that these drawings are merely illustrative of the technical solutions of this invention and are not intended to limit the scope of protection of this invention. In the drawings: Figure 1 This is a schematic diagram of the fully automated titration system according to the present invention; Figure 2 This is a schematic diagram of the fully automated titration system according to the present invention.

[0009] In the attached diagram, 11-sampling pump, 12-quantitative pump, 13-titration pump, 14-waste pump, 21-tipping cup, 22-electrode, 31-camera, 41-stirring unit, 51-multi-channel directional valve, 61-sampling circuit. Detailed Implementation

[0010] Figures 1-2The following description illustrates optional embodiments of the invention to teach those skilled in the art how to implement and reproduce the invention. Some conventional aspects have been simplified or omitted to teach the technical solutions of the invention. Those skilled in the art should understand that variations or substitutions derived from these embodiments will be within the scope of the invention. Those skilled in the art should understand that the following features can be combined in various ways to form multiple variations of the invention. Therefore, the invention is not limited to the optional embodiments described below, but is defined only by the claims and their equivalents.

[0011] Example 1

[0012] This embodiment presents a fully automated titration system based on image and potential fusion discrimination, such as... Figure 1 As shown, the system includes: The sampling pump 11 is installed on the sampling circuit 61, and the inlet and outlet of the sampling circuit 61 are both connected to the sample.

[0013] The sampling circuit 61, the metering pump 12, the titration cup 21 and the reagent bottle are respectively connected to the ports of the multi-channel directional valve 51.

[0014] The titration pump 13 is used to add a quantitative reagent to the titration cup 21, and the electrode 22 is disposed inside the titration cup 21.

[0015] The stirring unit 41 is used to stir the mixture in the titration cup 21.

[0016] Camera 31 acquires an image of the titration cup 21.

[0017] The calculation unit obtains the color feature value corresponding to the titration volume based on the image, and outputs the potential value corresponding to the titration volume based on the electrode 21.

[0018] The processing unit obtains a first candidate endpoint based on the color feature value and a second candidate endpoint based on the potential value.

[0019] The comparison unit obtains the titration endpoint based on the first and second candidate endpoints, thereby obtaining the accurate titration volume.

[0020] To obtain accurate color feature values, the color feature values ​​are further obtained as follows: The region at the center of titration cup 21 is selected as the region of interest from each frame of the image.

[0021] The region is converted from the RGB color space to the HSV color space.

[0022] Obtain the color feature value corresponding to the titration volume v .

[0023] N is the total number of pixels in the region, and Hi is the hue value of the i-th pixel in the region.

[0024] To obtain an accurate potential value, the potential value is further obtained in the following way: The potential sequence {Et} output by the electrode is filtered by moving average to obtain the potential value corresponding to the titration volume v. .

[0025] m is the size of the sliding window, m = 2k + 1, k is the window radius, which is a positive odd number, and E v+j It is the original potential value at the j-th point near the titration volume v.

[0026] To obtain accurate candidate endpoints, the titration volume V1 corresponding to the maximum difference between adjacent color feature values ​​is further selected as the first candidate endpoint, and the titration volume V2 corresponding to the maximum difference between adjacent potential values ​​is selected as the second candidate endpoint.

[0027] To obtain an accurate titration endpoint, the titration endpoint is further obtained as follows: Calculate δV = |V1−V2|; If δV≤τ, where τ is the threshold value of 20μL-100μL, the titration endpoint is reached, and the titration volume V0=(V1+V2) / 2.

[0028] If δT>τ, the measurement is abnormal, and the system will remeasure.

[0029] This embodiment presents a fully automated titration method based on image and potential fusion discrimination, such as... Figure 2 As shown, the titration method includes the following steps: A1. Use metering pump 12 to quantify the sample and inject it into titration cup 21.

[0030] A2. Add reagents to the titration cup, such as sulfosalicylic acid and xylenol orange indicator in sequence, and adjust the sample to purple by adding hexamethylenetetramine solution.

[0031] A3. Using the titration pump 13, EDTA standard solution is precisely added to the titration cup 21, the camera 31 obtains an image of the titration cup 21, and the electrode 22 outputs a potential sequence.

[0032] A4. The processing unit obtains the color feature value corresponding to the titration volume based on the image, and outputs the potential value corresponding to the titration volume based on the potential sequence.

[0033] A5. The processing unit obtains a first candidate endpoint based on the color feature value and a second candidate endpoint based on the potential value.

[0034] A6. The comparison unit obtains the titration endpoint based on the first candidate endpoint and the second candidate endpoint.

[0035] To make the detection more representative, the sample is continuously sampled through the sampling circuit 61, and the quantitative pump 12 quantitatively extracts the sample within the circuit 61 and injects it into the titration cup 21. A measured amount of diluent is injected into titration cup 21.

[0036] Example 2

[0037] Application example of the fully automated titration system and method according to Example 1.

[0038] In this application example, such as Figure 1 As shown, both the metering pump 12 and the titration pump 13 are high-precision syringe pumps. The stirring unit 41 uses a magnetic stirrer, with the stir bar placed inside the titration cup 21.

[0039] like Figure 2 As shown, the fully automated titration method includes the following steps: A1. Using sampling pump 11, the sample continuously passes through sampling circuit 61.

[0040] The multi-channel directional valve 51 switches, and the quantitative pump 12 quantitatively extracts 1.00 mL of sample from the sampling circuit 61 and injects it into the titration cup 21.

[0041] Then, using the multi-channel directional valve 51 to switch, the quantitative pump 12 draws 50 mL of pure water quantitatively and injects it into the titration cup 21 to dilute the sample.

[0042] A2. Using the multi-channel directional valve 51, the metering pump 12 sequentially dispenses 5 mL of sulfosalicylic acid and 0.5 mL of xylenol orange indicator, and injects them into the titration cup 21. Using the titration pump 13, hexamethylenetetramine solution was drawn and added dropwise into the titration cup 21 to adjust the sample to purple.

[0043] A3. Using the titration pump 13, EDTA standard solution is added dropwise to the titration cup 21 at a constant rate, and the camera 31 and electrode 22 are triggered simultaneously. The camera 31 obtains an image of the titration cup 21, and the electrode 22 outputs a potential sequence.

[0044] A4. The processing unit extracts the region at the center of the titration cup 21 from each frame image as the region of interest.

[0045] The region is converted from the RGB color space to the HSV color space.

[0046] Obtain the color feature value corresponding to the titration volume v .

[0047] N is the total number of pixels in the region, and Hi is the hue value of the i-th pixel in the region.

[0048] The processing unit obtains the potential value based on the potential sequence output by electrode 22, specifically in the following manner: The potential sequence {Et} output by the electrode is filtered by moving average to obtain the potential value corresponding to the titration volume v. .

[0049] m is the size of the sliding window, m = 2k + 1, k is the window radius, which is a positive odd number, and E v+j It is the original potential value at the j-th point near the titration volume v.

[0050] A5. The processing unit obtains the first candidate endpoint based on the color feature value, and the titration volume V1 corresponding to the maximum difference between adjacent color feature values ​​is taken as the first candidate endpoint.

[0051] The second candidate endpoint is obtained based on the potential value, and the titration volume V2 corresponding to the maximum difference between adjacent potential values ​​is taken as the second candidate endpoint.

[0052] A6. The comparison unit obtains the titration endpoint based on the first and second candidate endpoints, specifically as follows: Calculate δV = |V1−V2|.

[0053] If δV≤τ, τ=50μL, the titration endpoint is reached, and the titration volume V0=(V1+V2) / 2.

[0054] If δT>τ, the measurement is abnormal, and the system will remeasure.

[0055] The parameters for one titration were: When the titration volume V1 = 12.42 mL, the difference between adjacent color characteristic values ​​was detected to be at its maximum value.

[0056] When the titration volume V2 = 12.38 mL, the difference between adjacent potential values ​​was detected to be at its maximum value.

[0057] The volume difference δV = 0.04 mL < τ = 0.05 mL indicates that the titration endpoint has been reached.

[0058] The system recorded the final volume V = (12.42 + 12.38) / 2 = 12.40 mL.

[0059] The sample concentration is calculated based on volume V and the results are saved. Then, the waste pump 14 is turned on to automatically discharge waste and clean the system with pure water 3 times in preparation for the next test.

[0060] The parameters for the other titration were: Because a bubble passes through electrode 22, a sharp spike appears in the potential signal, and V2 is calculated to be 9.52 mL.

[0061] The image color changes smoothly, and the calculated V1 = 11.87 mL.

[0062] The volume difference δV=2.35mL>τ=0.05 mL, therefore the comparison unit determines that this result is unreliable.

[0063] The system does not record data and displays a message on the system touchscreen: "Endpoint detection error, re-measuring," before automatically starting a new detection cycle.

Claims

1. A fully automated titration system based on image and potential fusion discrimination, comprising a titration cup and electrodes; characterized in that, The system also includes: A camera, used to acquire an image of the titration cup; The calculation unit and the processing unit obtain color feature values ​​corresponding to the titration volume based on the image, and output potential values ​​corresponding to the titration volume based on the electrode. The processing unit obtains a first candidate endpoint based on the color feature value and a second candidate endpoint based on the potential value. The comparison unit obtains the titration endpoint based on a first candidate endpoint and a second candidate endpoint.

2. The titration system according to claim 1, characterized in that, The color feature value is obtained as follows: The region at the center of the titration cup is selected as the region of interest from each frame of the image; Convert the region from the RGB color space to the HSV color space; Obtain the color feature value corresponding to the titration volume v ; N is the total number of pixels in the region, and Hi is the hue value of the i-th pixel in the region.

3. The titration system according to claim 1, characterized in that, The potential value is obtained as follows: The potential sequence {Et} output by the electrode is filtered by moving average to obtain the potential value corresponding to the titration volume v. ; m is the size of the sliding window, m = 2k + 1, k is the window radius, which is a positive odd number, and E v+j It is the original potential value at the j-th point near the titration volume v.

4. The titration system according to claim 1, characterized in that, The titration volume V1 corresponding to the maximum difference between adjacent color feature values ​​is taken as the first candidate endpoint, and the titration volume V2 corresponding to the maximum difference between adjacent potential values ​​is taken as the second candidate endpoint.

5. The calibration method according to claim 4, characterized in that, The titration endpoint is obtained as follows: Calculate δV = |V1−V2|; If δV≤τ, where τ is the threshold, the titration endpoint is established, and the titration volume V0=(V1+V2) / 2; If δT>τ, the measurement is abnormal, and the system will remeasure.

6. The titration system according to claim 5, characterized in that, τ is 20μL-100μL.

7. The titration system according to claim 1, characterized in that, The titration system further includes: A sampling circuit and a sampling pump, wherein the sampling pump is installed on the sampling circuit; A multi-channel directional valve and a metering pump are provided, wherein the sampling circuit, the metering pump, and the titration cup are connected to the port of the multi-channel directional valve, and the reagent is connected to the multi-channel directional valve. A titration pump for adding a quantitative reagent to the titration cup; A stirring unit is provided for stirring the mixture in the titration cup.

8. The titration method of the system according to any one of claims 1-7, characterized in that, The titration method includes the following steps: A1. Inject the quantitative sample into the titration cup; A2. Add reagent to the titration cup to adjust the liquid color to purple; A3. Add EDTA standard solution dropwise into the titration cup, and the camera captures an image of the titration cup. The electrode outputs a potential sequence. A4. The processing unit obtains the color feature value corresponding to the titration volume based on the image, and outputs the potential value corresponding to the titration volume based on the potential sequence; A5. The processing unit obtains a first candidate endpoint based on the color feature value and a second candidate endpoint based on the potential value; A6. The comparison unit obtains the titration endpoint based on the first candidate endpoint and the second candidate endpoint.

9. The titration method according to claim 8, characterized in that, Sulfosalicylic acid and xylenol orange indicator were added sequentially, and the sample was adjusted to purple by adding hexamethylenetetramine solution.

10. The titration method according to claim 8, characterized in that, The sample is continuously sampled through the sampling circuit, and the quantitative pump quantitatively extracts the sample within the circuit and injects it into the titration cup; A measured amount of diluent is injected into the titration cup.

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