A calibration system and calibration method for a chemiluminescence instrument

Abstract

The present application relates to a kind of calibration methods for chemiluminescence silicate analyzer, comprising: S1, carries out single-point calibration, comprising: preparation specified concentration silicate standard solution, and obtain original signal value;S2, by multiple calibration stages to chemiluminescence instrument calibration;S1 includes: extract volume X1 of silicate standard solution, concentration C0 ug / L;Extract volume X2 of ultrapure water;Mixing forms specified concentration standard solution;Into chemiluminescence instrument and sequentially add reagent A and reagent B;After waiting, add reagent C, obtain measured voltage V1;S2 includes: first calibration stage, judge V1 whether in a certain range, if yes then enter second calibration stage;If not, adjust until meet;Second calibration stage, take no silicon water and obtain measured voltage V2;Take other concentration silicate standard solution and obtain measured voltage V3;Judge whether |V1-V3|-|V3-V2|≤Voltage fixed threshold value?If meet, then enter third calibration stage;If not, enter fourth calibration stage;Complete calibration.

Description

Technical Field

[0001] This invention relates to the field of calibration technology for analytical instruments, and in particular to a calibration system and calibration method for a chemiluminescence analyzer. Background Technology

[0002] The treatment and monitoring of boiler water in thermal power plants is a crucial aspect, directly impacting boiler safety, energy efficiency, and the overall economic benefits of the power plant. The presence of silicate ions is one of the main causes of boiler scale formation. Silicate scale has a complex chemical composition, primarily consisting of aluminum and iron silicate compounds, which uniformly coat the inner walls of boiler tubes and the low-pressure cylinder blades of the turbine. Because the thermal conductivity of silicate scale is much lower than that of metals, its presence severely affects boiler heat transfer efficiency, leading to heat loss and localized overheating, and in severe cases, even boiler damage. In boiler feedwater treatment, the SiO2 content is typically required to be below 20 μg / L to ensure the purity and stability of the boiler water. If the silicate content in the boiler water is too high, it will not only contaminate the steam, causing precipitates inside the turbine and reducing equipment efficiency, but may also corrode the boiler's metal materials, threatening the safe operation of the boiler.

[0003] Currently, most thermal power plants and the semiconductor industry use silicate analyzers based on the molybdenum blue colorimetric principle as the primary method for detecting silicate ion concentration. The detection process requires manual addition of a certain amount of reagent, followed by a chemical colorimetric reaction, and then measurement using the silicate analyzer. This process has low automation, long detection time, and is greatly affected by human factors. Silicate analyzers based on the chemiluminescence principle offer advantages such as high sensitivity, no need for external excitation light sources, no interference from background or stray light, and low noise, making them an effective method for rapidly analyzing silicate concentration in water.

[0004] Theoretically, the silicate concentration and radiation intensity in chemiluminescence-based silicate detection methods have a linear relationship. However, in actual measurements, this relationship often becomes non-linear, directly affecting the accuracy of silicate measurement. The main reason for this non-linearity is the presence of a large amount of silicate in the sulfuric acid solution used as the reagent. This is because my country's sulfuric acid preparation standards do not specify requirements for silicate concentration, making the silicate concentration in purchased analytical grade and superior grade sulfuric acid solutions uncontrollable. From a measurement principle perspective, the silicate effect introduced by sulfuric acid is a fixed error and does not affect the measurement of calibrated samples. However, it is precisely because of the silicate effect introduced by sulfuric acid that this method cannot be calibrated using traditional range calibration or linear calibration.

[0005] In summary, the existing technology has the following technical defects:

[0006] (1) A certain amount of reagent needs to be manually added to the standard solution. After the chemical color reaction occurs, the standard curve is established by measuring the silicate ion analyzer. Therefore, a lot of manual operation is required in the calibration and measurement process, and it is greatly affected by human factors.

[0007] (2) Sulfuric acid contains an unpredictable amount of silicate ions, which introduces errors in calibration measurements; the difference between the superscript and subscript signals is small during calibration, resulting in a large deviation during retesting;

[0008] (3) There is no calibration method for measuring silicate ions based on the principle of chemiluminescence;

[0009] (4) Traditional silicon meters are slow to calibrate, requiring 15 to 20 minutes for each calibration. Summary of the Invention

[0010] The purpose of this invention is to provide a calibration system and method for a chemiluminescence silicate analyzer, mainly addressing the problems of slow calibration speed and low automation in traditional calibration methods. This method is specifically designed for chemiluminescence silicate analyzers and effectively solves the problem of nonlinear evolution of silicate concentration caused by background silicon in sulfuric acid during the chemiluminescence reaction. This improves the measurement accuracy of the chemiluminescence silicate analyzer and enhances the accuracy of silicate measurement using the chemiluminescence method. By introducing a high-pressure self-adjustment method, the difference between the upper limit standard solution signal value and the silicate-free water signal value is maximized, reducing the uncertainty introduced by calibration. This allows for rapid calibration while maintaining measurement accuracy.

[0011] This invention provides a calibration method for a chemiluminescence silicate analyzer, comprising:

[0012] S1, perform single-point calibration, including: preparing a silicate standard solution of a specified concentration, and obtaining the original signal value based on the silicate standard solution of the specified concentration;

[0013] S2, based on the single-point calibration, the chemiluminescence analyzer is calibrated through multiple calibration stages.

[0014] Preferably, S1 includes:

[0015] S11, quantitatively extract volume X1 of silicate standard solution, wherein the concentration of volume X1 of silicate standard solution is C0 ug / L;

[0016] S12, quantitatively extract a volume of ultrapure water of size X2, wherein X1 + X2 ≥ volume threshold, and

[0017] S13, the silicate standard solution is mixed with the ultrapure water and stirred thoroughly to form a fully mixed standard solution of the specified concentration;

[0018] S14, the standard solution of the specified concentration after thorough mixing is sent into the chemiluminescence analyzer (9), and the first volume of reagent A and the second volume of reagent B are added in sequence;

[0019] S15, after waiting for the reaction to proceed for several tens of seconds, add a third volume of reagent C, and then detect the measurement voltage V1 corresponding to the silicate standard solution of the specified concentration.

[0020] Preferably, reagent A is 2% ammonium molybdate; reagent B is 4% dilute sulfuric acid; and reagent C is an alkaline luminescent agent. The preparation method of reagents A, B, and C includes:

[0021] Prepare reagent A by: adding 800 mL of silica-free water to a 1000 mL volumetric flask, adding 20 g of analytical grade ammonium molybdate, dissolving it completely, and then adding water to bring the volume to 1000 mL.

[0022] Prepare reagent B by: first pouring 800 mL of silica-free water into a 1000 mL volumetric flask, then adding 27 mL of analytical grade concentrated sulfuric acid, and finally adding water to bring the volume to 1000 mL.

[0023] Prepare reagent C by: first pouring 800 mL of silica-free water into a graduated polyethylene reagent bottle, then adding 40 g of analytical grade NaOH granules and 0.2 g of luminescent agent, dissolving them completely, and then adding water to 1000 mL.

[0024] Preferably, S2 includes:

[0025] S21, based on entering the first calibration stage, determine whether V1 is within the threshold range. If V1 is within the threshold range, then enter the second calibration stage; if V1 is not within the threshold range, then adjust the specified concentration until V1 meets the threshold range.

[0026] S22, based on entering the second calibration stage, silica-free water is taken into the chemiluminescence analyzer for measurement, and the corresponding measurement voltage V2 is obtained; any silicate standard solution with a concentration different from the specified concentration within the measurement interval is taken into the chemiluminescence analyzer for measurement, and the corresponding measurement voltage V3 is obtained; at this time, it is determined whether |V1-V3|-|V3-V2|≤ the voltage setpoint threshold?; if it meets the condition that |V1-V3|-|V3-V2|≤ the voltage setpoint threshold, then the third calibration stage is entered, and the third calibration stage is linear calibration; if it does not meet the condition that |V1-V3|-|V3-V2|≤ the voltage setpoint threshold, then the fourth calibration stage is entered.

[0027] S23, based on entering the third calibration stage, perform linear calibration;

[0028] S24, based on entering the fourth calibration stage, perform polynomial calibration;

[0029] S25, the chemiluminescence analyzer is calibrated based on the completion of the linear calibration or the polynomial calibration.

[0030] Preferably, the linear calibration includes two-point linear calibration and three-point linear calibration; wherein,

[0031] The two-point linear calibration is applicable when |V1-V3|-|V3-V2|≤30mV, at which point the system is close to linear. The steps of the two-point linear calibration include:

[0032] (1) Select two concentration points, namely point A and point B. Point A is silica-free water with a concentration of C0 = 0 μg / L and a corresponding voltage V2, which serves as the background signal; point B is a silicate standard solution with a concentration of C1 = 25 μg / L and a corresponding voltage V3.

[0033] (2) Establish the linear equation: the slope of the linear equation is k = (V3 - V2) / (C1 - C0); the intercept is b = V2; the calibration formula is V = k × C + b;

[0034] (3) The linearity of the linear equation was verified based on another standard solution, and the linearity requirement was met based on a deviation of ≤±1μg / L;

[0035] The three-point linear calibration is applicable when |V1-V3|-|V3-V2|≤30mV, at which point the system is close to linear and requires higher calibration accuracy. The steps of the three-point linear calibration include:

[0036] (1) Select three concentration points, namely point A, point B and point C. Point A is silica-free water with a concentration of C0 = 0 μg / L and a corresponding voltage V2, which is used as the background signal; point B is silicate standard solution with a concentration of C1 = 12.5 μg / L and a corresponding voltage V4, which is used as the intermediate point; point C is silicate standard solution with a concentration of C1 = 25 μg / L and a corresponding voltage V3.

[0037] (2) Perform piecewise linear fitting, including:

[0038] In the low concentration range of 0–12.5 μg / L, the slope in the fitting formula is k1 = (V4 - V2) / 12.5; the slope is b1 = V2.

[0039] In the high concentration range of 12.5–25 μg / L, the slope in the fitting formula is k2 = (V3-V4) / 12.5; the slope is b2 = V4-k2×12.5.

[0040] (3) Calculate the concentration, including:

[0041] If the sample voltage V≤V4, the concentration is calculated using the low-segment formula C=(V-b1) / k1;

[0042] If the sample voltage V > V4, the concentration is calculated using the high-level formula C = (V - b2) / k2.

[0043] Preferably, the polynomial calibration method includes three-point polynomial calibration; wherein, the applicable condition for the three-point polynomial calibration is |V1-V3|-|V3-V2|>30mV, at which point the system exhibits nonlinearity, and the steps of the three-point polynomial calibration include:

[0044] (1) Measure the voltage at three concentration points, where: point A is silica-free water with a concentration of C0 = 0 μg / L, corresponding to voltage V2, which serves as the background signal; point B is silicate standard solution with a concentration of C1 = 12.5 μg / L, corresponding to voltage V4, which serves as the intermediate point; and point C is silicate standard solution with a concentration of C1 = 25 μg / L, corresponding to voltage V3.

[0045] (2) Based on the voltage fitting of three concentration points, the quadratic polynomial V = a·C is obtained. 2 +b·C+c;

[0046] The fitting is obtained by solving the following system of equations and solving for the coefficients a, b, and c in matrix form. The system of equations includes:

[0047] V2=a·0 2 +b·0+c

[0048] V4 = a·(12.5) 2 +b·(12.5)+c

[0049] V3=a·(25) 2 +b·(25)+c

[0050] (3) Input the sample voltage V, solve the quadratic equation to back-calculate the concentration C, and then the calibration is completed;

[0051] The applicable condition for the multi-point polynomial calibration is |V1-V3|-|V3-V2|>30mV, at which point the system exhibits nonlinearity. The steps of the multi-point polynomial calibration include:

[0052] (1) Add at least 4 calibration points;

[0053] (2) Fit high-order polynomials based on the least squares method, calculate coefficients through regression analysis to ensure the minimum residual;

[0054] (3) Input the sample voltage V, solve the cubic equation to back-calculate the concentration C and verify the accuracy. The calibration is completed after the deviation between the back-calculated concentration at each point and the actual concentration is ≤ ±0.5 μg / L.

[0055] Preferably, the multi-point polynomial calibration includes adding corresponding calibration points to improve accuracy. Adding corresponding calibration points includes selecting an additional point concentration, wherein selecting the additional point concentration includes: densifying the density in the nonlinear significant region.

[0056] The method for adding corresponding calibration points includes:

[0057] Complete the initial three-point calibration (0 / 12.5 / 25 μg / L);

[0058] Measure the solution at M additional points in sequence and record the M voltage values;

[0059] Refit the polynomial with M+3 points and automatically upgrade it to an M+2 degree polynomial.

[0060] A second aspect of the present invention provides a calibration system for a chemiluminescence silicate analyzer, for implementing the method of the first aspect, comprising:

[0061] A single-point calibration module is used to perform single-point calibration, including: preparing a silicate standard solution of a specified concentration, and obtaining the original signal value based on the silicate standard solution of the specified concentration;

[0062] The chemiluminescence analyzer calibration module is used to calibrate the chemiluminescence analyzer through multiple calibration stages based on the single-point calibration.

[0063] A third aspect of the present invention provides an electronic device including a processor and a memory, the memory storing a plurality of instructions, the processor being configured to read the instructions and execute the method as described in the first aspect.

[0064] A fourth aspect of the present invention provides a computer-readable storage medium storing a plurality of instructions which can be read by a processor and executed as described in the first aspect.

[0065] The calibration method and system for a chemiluminescence silicate analyzer of the present invention have the following beneficial effects:

[0066] (1) It has the functions of superscript self-judgment and high voltage adjustment, which can effectively widen the signal difference between superscript and superscript, and improve measurement repeatability and measurement accuracy.

[0067] (2) The three-point polynomial calibration method has a fast calibration speed and high measurement accuracy of ±1ug / L; multi-point calibration can improve the accuracy to ±0.75ug / L.

[0068] (3) Adding multiple calibration points can further improve measurement accuracy.

[0069] (4) Linear judgment mechanism to eliminate the influence of different background silicate content values ​​of sulfuric acid and automatically select the optimal calibration method.

[0070] (5) No manual intervention is required. After setting the range parameters, the calibration is automatic, and the degree of automation is high. Attached Figure Description

[0071] To more clearly illustrate the technical solutions in the specific embodiments or related technologies of the present invention, the drawings used in the description of the specific embodiments or related technologies will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0072] Figure 1 A flowchart illustrating the calibration method for a chemiluminescence silicate analyzer provided in an embodiment of the present invention;

[0073] Figure 2 This is a schematic diagram of the calibration system structure for implementing a calibration method for a chemiluminescence silicate analyzer, as provided in an embodiment of the present invention.

[0074] Figure 3 This is a schematic diagram of two-point linear calibration error provided in an embodiment of the present invention;

[0075] Figure 4 A schematic diagram of three-point linear calibration error provided in an embodiment of the present invention;

[0076] Figure 5 This is a schematic diagram of the three-point polynomial calibration error provided in an embodiment of the present invention;

[0077] Figure 6 This is a schematic diagram of the full-range 6-point polynomial calibration error provided in an embodiment of the present invention;

[0078] Figure 7 This is a schematic diagram of the electronic device structure provided in an embodiment of the present invention. Detailed Implementation

[0079] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0080] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0081] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0082] Example 1

[0083] like Figure 1 As shown, this embodiment provides a calibration method for a chemiluminescence silicate analyzer, including:

[0084] S1, perform single-point calibration, including: preparing a silicate standard solution of a specified concentration, and obtaining the original signal value based on the silicate standard solution of the specified concentration;

[0085] In a preferred embodiment, S1 includes:

[0086] S11, quantitatively extract volume X1 of silicate standard solution, wherein the concentration of volume X1 of silicate standard solution is C0 ug / L;

[0087] In a preferred embodiment, the silicate standard solution of volume X1 is placed in the first metering pump (1) that has been started;

[0088] S12, quantitatively extract a volume of ultrapure water of size X2, wherein X1 + X2 ≥ volume threshold, and

[0089] S13, the silicate standard solution is mixed with the ultrapure water and stirred thoroughly to form a fully mixed standard solution of the specified concentration;

[0090] S14, the standard solution of the specified concentration after thorough mixing is sent into the chemiluminescence analyzer (9), and the first volume of reagent A and the second volume of reagent B are added in sequence;

[0091] S15, after waiting for the reaction to proceed for several tens of seconds, add a third volume of reagent C, and then detect the measurement voltage V1 corresponding to the silicate standard solution of the specified concentration.

[0092] In a preferred embodiment, reagent A is 2% ammonium molybdate; reagent B is 4% dilute sulfuric acid; and reagent C is an alkaline luminescent agent.

[0093] In this embodiment:

[0094] Prepare reagent A by: adding 800 mL of silica-free water to a 1000 mL volumetric flask, adding 20 g of analytical grade ammonium molybdate, dissolving it completely, and then adding water to bring the volume to 1000 mL.

[0095] Prepare reagent B by: first pouring 800 mL of silica-free water into a 1000 mL volumetric flask, then adding 27 mL of analytical grade concentrated sulfuric acid, and finally adding water to bring the volume to 1000 mL.

[0096] Prepare reagent C by: first pouring 800 mL of silica-free water into a graduated polyethylene reagent bottle, then adding 40 g of analytical grade NaOH granules and 0.2 g of luminescent agent, dissolving them completely, and then adding water to 1000 mL.

[0097] like Figure 2 As shown, taking a 50 ug / L standard solution as an example, step S1 is as follows:

[0098] Start metering pump 1 to quantitatively extract volume X1 of silicate standard solution 2, with a concentration of C0ug / L. Open the three-way valve 3 to inject the silicate standard solution from metering pump 1 into the mixing tank 7. Start metering pump 4 to quantitatively extract volume X2 of ultrapure water 5, ensuring that X1 + X2 ≥ 100ml, and... Open the three-way valve 6 to inject ultrapure water from the metering pump 4 into the mixing tank 7, thereby obtaining a 50 μg / L silicate standard solution. Start the magnetic stirrer 8 to thoroughly stir the solution in the mixing tank 7. Take the 50 μg / L thoroughly mixed silicate standard solution and put it into the chemiluminescence analyzer 9 for measurement. During measurement, first add 0.5-2 mL of reagent A and 0.5-2 mL of reagent B, wait for the reaction for several tens of seconds, and then add 1-3 mL of reagent C. Detect the measurement voltage V1 corresponding to the 50 μg / L silicate standard solution.

[0099] S2, Based on the single-point calibration, the chemiluminescence analyzer is calibrated through multiple calibration stages;

[0100] In a preferred embodiment, S2 includes:

[0101] S21, based on entering the first calibration stage, determine whether V1 is within the threshold range. If V1 is within the threshold range, then enter the second calibration stage; if V1 is not within the threshold range, then adjust the specified concentration until V1 meets the threshold range.

[0102] In a preferred embodiment, the threshold range is 3000mV ≤ V1 ≤ 3200mV. Of course, those skilled in the art can reasonably adjust this threshold range according to the specific instrument and measurement requirements, all of which are within the scope of protection of this invention.

[0103] This process maximizes the difference between superscript and subscript, effectively improving measurement repeatability and accuracy.

[0104] S22, based on entering the second calibration stage, take silica-free water into the chemiluminescence analyzer for measurement, and obtain the corresponding measurement voltage V2; take any silicate standard solution with a concentration different from the specified concentration within the measurement interval into the chemiluminescence analyzer for measurement, and obtain the corresponding measurement voltage V3; at this time, determine whether |V1-V3|-|V3-V2|≤ voltage setpoint threshold?; if it meets the condition that |V1-V3|-|V3-V2|≤ voltage setpoint threshold, then enter the third calibration stage, which is a linear calibration; if it does not meet the condition that |V1-V3|-|V3-V2|≤ voltage setpoint threshold, then enter the fourth calibration stage.

[0105] In a preferred embodiment, the voltage setpoint threshold is 30mV. Of course, those skilled in the art can reasonably adjust the voltage setpoint threshold range according to the specific conditions of the instrument and measurement requirements, all of which are within the protection scope of this invention.

[0106] S23, based on entering the third calibration stage, perform linear calibration;

[0107] S24, based on entering the fourth calibration stage, perform polynomial calibration;

[0108] S25, the chemiluminescence analyzer is calibrated based on the completion of the linear calibration or the polynomial calibration.

[0109] In this embodiment, the specific calibration method is as follows:

[0110] Determine if 3000mV ≤ V1 ≤ 3200mV. If V1 is not within this range, adjust the specified concentration until V1 meets the judgment criterion. This process maximizes the difference between the upper and lower indices, effectively improving measurement repeatability and accuracy. If V1 is within this range, proceed directly to the next calibration stage. Measure the corresponding measurement voltage V2 using a silica-free water sample in the chemiluminescence analyzer. Measure the corresponding measurement voltage V3 using a 25ug / L silicate standard solution (or another standard liquid with a concentration within the measurement range) in the chemiluminescence analyzer. Then determine if |V1-V3|-|V3-V2| ≤ 30mV. If it meets the above formula, perform linear calibration. If it does not meet the above formula, perform polynomial calibration. After performing any calibration method, the calibration is complete.

[0111] The above calibration method comprehensively compares various calibration methods, including two-point linear, three-point linear, three-point polynomial, and multi-point polynomial, selecting the method with the shortest calibration time while ensuring measurement accuracy. The three-point polynomial calibration method guarantees a measurement accuracy of ≤±1ug / L across the entire measurement range and completes calibration within 6 minutes, making it a fast calibration method that meets the needs of on-site measurements. For further improvements in measurement accuracy, calibration points can be added to the above calibration method.

[0112] In a preferred embodiment, the linear calibration includes two-point linear calibration and three-point linear calibration; wherein,

[0113] The two-point linear calibration is applicable when |V1-V3|-|V3-V2|≤30mV, at which point the system is close to linear. The steps of the two-point linear calibration include:

[0114] (1) Select two concentration points, namely point A and point B. Point A is silica-free water with a concentration of C0 = 0 μg / L and a corresponding voltage V2, which serves as the background signal; point B is a silicate standard solution with a concentration of C1 = 25 μg / L and a corresponding voltage V3.

[0115] (2) Establish the linear equation: the slope of the linear equation is k = (V3 - V2) / (C1 - C0); the intercept is b = V2; the calibration formula is V = k × C + b;

[0116] (3) The linearity of the linear equation was verified based on another standard solution. The linearity requirement was met based on a deviation of ≤ ±1 μg / L. In this embodiment, the concentration of the other standard solution was 12.5 μg / L.

[0117] The three-point linear calibration is applicable when |V1-V3|-|V3-V2|≤30mV, at which point the system is close to linear and requires higher calibration accuracy. The steps of the three-point linear calibration include:

[0118] (1) Select three concentration points, namely point A, point B and point C. Point A is silica-free water with a concentration of C0 = 0 μg / L and a corresponding voltage V2, which is used as the background signal; point B is silicate standard solution with a concentration of C1 = 12.5 μg / L and a corresponding voltage V4, which is used as the intermediate point; point C is silicate standard solution with a concentration of C1 = 25 μg / L and a corresponding voltage V3.

[0119] (2) Perform piecewise linear fitting, including:

[0120] In the low concentration range of 0–12.5 μg / L, the slope in the fitting formula is k1 = (V4 - V2) / 12.5; the slope is k1 = V2.

[0121] In the high concentration range of 12.5–25 μg / L, the slope in the fitting formula is k2 = (V3-V4) / 12.5; the slope is b2 = V4-k2×12.5.

[0122] (3) Calculate the concentration, including:

[0123] If the sample voltage V≤V4, the concentration is calculated using the low-segment formula C=(V-b1) / k1;

[0124] If the sample voltage V > V4, the concentration is calculated using the high-level formula C = (V - b2) / k2.

[0125] Note: Three-point linearity improves full-range accuracy through segmentation, but calibration time increases to 4–5 minutes.

[0126] In a preferred embodiment, the polynomial calibration method includes three-point polynomial calibration; wherein, the applicable condition for the three-point polynomial calibration is |V1-V3|-|V3-V2|>30mV, at which point the system exhibits nonlinearity, and the steps of the three-point polynomial calibration include:

[0127] (1) Measure the voltage at three concentration points: point A is silica-free water with a concentration of C0 = 0 μg / L, corresponding to voltage V2, which serves as the background signal; point B is a silicate standard solution with a concentration of C1 = 12.5 μg / L, corresponding to voltage V4, which serves as the intermediate point; point C is a silicate standard solution with a concentration of C1 = 25 μg / L, corresponding to voltage V3.

[0128] (2) Based on the voltage fitting of three concentration points, the quadratic polynomial V = a·C is obtained. 2 +b·C+c;

[0129] The fitting is obtained by solving the following system of equations and solving for the coefficients a, b, and c in matrix form. The system of equations includes:

[0130] V2=a·0 2 +b·0+c

[0131] V4 = a·(12.5) 2 +b·(12.5)+c

[0132] V3=a·(25) 2 +b·(25)+c

[0133] (3) Input the sample voltage V, solve the quadratic equation to back-calculate the concentration C, and then the calibration is completed;

[0134] The multi-point polynomial calibration is applicable when |V1-V3|-|V3-V2|>30mV. At this point, the system exhibits nonlinearity and requires higher precision, such as in ultra-low / high concentration ranges. The steps of the multi-point polynomial calibration include:

[0135] (1) Add no less than 4 calibration points. In this embodiment, the added calibration points include: 0 μg / L, 6.25 μg / L, 12.5 μg / L, 18.75 μg / L, and 25 μg / L;

[0136] (2) Fit high-order polynomials based on the least squares method, calculate coefficients through regression analysis to ensure the minimum residual;

[0137] This embodiment commonly uses a quadratic or cubic polynomial: V = a·C 3 +b·C 2 +c·C+d;

[0138] (3) Input the sample voltage V, solve the cubic equation to back-calculate the concentration C and verify the accuracy. The calibration is completed after the deviation between the back-calculated concentration at each point and the actual concentration is ≤ ±0.5 μg / L.

[0139] Time cost: Multi-point calibration takes 8–10 minutes, which is more accurate but time-consuming.

[0140] In a preferred embodiment, the multi-point polynomial calibration includes adding corresponding calibration points to improve accuracy. Adding corresponding calibration points includes selecting the concentration of additional points, wherein selecting the concentration of additional points includes: densifying in nonlinear significant intervals (e.g., 0–5 μg / L or 20–25 μg / L).

[0141] Example: Add two points: 3 μg / L and 22 μg / L.

[0142] The method for adding corresponding calibration points includes:

[0143] Complete the initial three-point calibration (0 / 12.5 / 25 μg / L);

[0144] Measure the solution at M additional points in sequence and record the M voltage values; in this embodiment, for example, add 2 additional points of solution and record the voltages V5 (3 μg / L) and V6 (22 μg / L);

[0145] The polynomial is refitted with M+3 points and automatically upgraded to an M+2 degree polynomial; in this embodiment, for example, the polynomial is refitted with 5 points and automatically upgraded to a 4th degree polynomial.

[0146] By adding calibration points, the accuracy is optimized, and the full-range deviation can be reduced to within ±0.3 μg / L after adding points. However, it is important to note that no more than two points should be added at a time to avoid overfitting. In addition, the calibration time increases by 1–2 minutes for each additional point. The initial voltage V1 must be strictly controlled between 3000–3200 mV to ensure signal sensitivity. |V1-V3|-|V3-V2|>30 mV is the threshold for judging nonlinearity, derived from experimental statistics. Polynomial calibration compensates for the nonlinear superposition of luminescence intensity through a quadratic function, avoiding manual correction of energy transfer (P) and quenching (K).

[0147] Example 2

[0148] This embodiment provides a calibration system for a chemiluminescence silicate analyzer, used to implement the method of Embodiment 1, including:

[0149] A single-point calibration module is used to perform single-point calibration, including: preparing a silicate standard solution of a specified concentration, and obtaining the original signal value based on the silicate standard solution of the specified concentration;

[0150] The chemiluminescence analyzer calibration module is used to calibrate the chemiluminescence analyzer through multiple calibration stages based on the single-point calibration.

[0151] Calibration effect as Figure 3-6 As shown. Among them. Figure 3 This is a schematic diagram of two-point linear calibration error. Figure 4 This is a schematic diagram of the three-point linear calibration error. Figure 5 This is a schematic diagram of the three-point polynomial calibration error. Figure 6 This is a schematic diagram of the full 20% 6-point polynomial calibration error.

[0152] The present invention also provides a memory that stores multiple instructions for implementing the method as described in Embodiment 1.

[0153] like Figure 7 As shown, the present invention also provides an electronic device, including a processor 301 and a memory 302 connected to the processor 301. The memory 302 stores a plurality of instructions, which can be loaded and executed by the processor to enable the processor to perform the method as described in Embodiment 1.

[0154] Through the above description of the embodiments, those skilled in the art can clearly understand that the above embodiments can be implemented by software, or by using software plus necessary general-purpose hardware platforms. Based on this understanding, the technical solutions of the above embodiments can be embodied in the form of a software product, which can be stored in a non-volatile storage medium (such as a CD-ROM, USB flash drive, external hard drive, etc.), including several instructions to cause a computer device (such as a personal computer, server, or network device, etc.) to execute the methods described in the various embodiments of the present invention.

[0155] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A calibration method for a chemiluminescent silicate analyzer, characterized by, The method comprises the following steps: S1, performing single-point calibration, comprising: preparing a silicate standard solution with a specified concentration, and obtaining an original signal value based on the silicate standard solution with the specified concentration; S2, calibrating a chemiluminescence instrument through multiple calibration stages based on the single-point calibration; The S1 comprises: S11, quantitatively extracting a volume X1 of the silicate standard solution, wherein the concentration of the volume X1 of the silicate standard solution is C0 ug / L; S12, quantitatively draw a volume X2 of ultrapure water, wherein X1+X2≥volume threshold is satisfied, and ; S13, mixing the silicate standard solution with the ultrapure water and fully stirring to form a fully mixed standard solution with the specified concentration; S14, feeding the fully mixed standard solution with the specified concentration into the chemiluminescence instrument, and sequentially adding a first volume of a reagent A and a second volume of a reagent B; S15, after waiting for tens of seconds, adding a third volume of a reagent C, and detecting a measured voltage V1 corresponding to the silicate standard solution with the specified concentration; The reagent A is 2% ammonium molybdate, the reagent B is 4% dilute sulfuric acid, and the reagent C is an alkaline luminescent agent; The S2 comprises: S21, based on entering a first calibration stage, judging whether V1 is in a threshold interval range, if V1 is in the threshold interval range, entering a second calibration stage, if V1 is not in the threshold interval range, adjusting the specified concentration until V1 meets the threshold interval range; S22, based on entering the second calibration stage, taking the silicate-free water into the chemiluminescence instrument to measure and obtain a corresponding measured voltage V2, taking any other concentration of the silicate standard solution in a measurement interval and different from the specified concentration into the chemiluminescence instrument to measure and obtain a corresponding measured voltage V3, and judging whether |V1-V3|-|V3-V2|≤voltage fixed value threshold value, if |V1-V3|-|V3-V2|≤voltage fixed value threshold value, entering a third calibration stage, the third calibration stage being linear calibration, if |V1-V3|-|V3-V2|≠voltage fixed value threshold value, entering a fourth calibration stage; S23, based on entering the third calibration stage, performing linear calibration; S24, based on entering the fourth calibration stage, performing polynomial calibration; S25, based on completing the linear calibration or the polynomial calibration, completing calibration of the chemiluminescence instrument.

2. The method for calibrating a chemiluminescent silicate analyzer according to claim 1, wherein, The configuration method of the reagent A, the reagent B and the reagent C comprises: Preparation of the reagent A, comprising: using a 1000 mL volumetric flask, injecting 800 mL of silicate-free water, adding 20 g of analytical pure ammonium molybdate, fully dissolving, and then adding water to 1000 mL; Preparation of the reagent B, comprising: using a 1000 mL volumetric flask, first injecting 800 mL of silicate-free water, then adding 27 mL of analytical pure concentrated sulfuric acid, and adding water to 1000 mL; Preparation of the reagent C, comprising: using a reagent bottle made of polyethylene with a scale, first injecting 800 mL of silicate-free water, then adding 40 g of analytical pure NaOH particles and 0.2 g of luminescent agent, fully dissolving, and then adding water to 1000 mL.

3. A method for calibrating a chemiluminescent silicate analyzer according to claim 2, wherein, The linear calibration comprises two-point linear calibration and three-point linear calibration; wherein, The applicable condition of the two-point linear calibration is that |V1-V3|-|V3-V2|≤30mV, at which time the system is close to linear, and the steps of the two-point linear calibration include: (1) selecting two concentration points, namely point A and point B, wherein point A is silicon-free water with a concentration of C0=0 μg / L, corresponding to voltage V2, as a background signal; and point B is a silicate standard solution with a concentration of C1=25 μg / L, corresponding to voltage V3; (2) establishing a linear equation: V=k×C+b, wherein the slope k of the linear equation is (V3-V2) / (C1-C0); and the intercept b is V2; and the calibration formula is V=k×C+b; (3) verifying the linearity of the linear equation based on another standard solution, and the linearity requirement is met based on a deviation of ≤±1 μg / L; The applicable condition of the three-point linear calibration is that |V1-V3|-|V3-V2|≤30mV, at which time the system is close to linear and higher calibration accuracy is required, and the steps of the three-point linear calibration include: (1) selecting three concentration points, namely point A, point B and point C, wherein point A is silicon-free water with a concentration of C0=0 μg / L, corresponding to voltage V2, as a background signal; point B is a silicate standard solution with a concentration of C1=12.5 μg / L, corresponding to voltage V4, as an intermediate point; and C is a silicate standard solution with a concentration of C1=25 μg / L, corresponding to voltage V3; (2) performing piecewise linear fitting, including: in the low concentration section of 0-12.5 μg / L, the slope k1 in the fitting formula is (V4-V2) / 12.5; and the intercept b1 is V2; in the high concentration section of 12.5-25 μg / L, the slope k2 in the fitting formula is (V3-V4) / 12.5; and the intercept b2 is V4-k2×12.5; (3) calculating the concentration, including: if the sample voltage V≤V4, the concentration is calculated by the low section formula C=(V-b1) / k1; if the sample voltage V>V4, the concentration is calculated by the high section formula C=(V-b2) / k2.

4. The method for calibrating a chemiluminescent silicate analyzer according to claim 3, wherein, The polynomial calibration mode includes three-point polynomial calibration; wherein the applicable condition of the three-point polynomial calibration is |V1-V3|-|V3-V2|>30mV, at which time the system has nonlinearity, and the steps of the three-point polynomial calibration include: (1) measuring three concentration point voltages, wherein: point A is silicon-free water with a concentration of C0=0 μg / L, corresponding to voltage V2, as a background signal; point B is a silicate standard solution with a concentration of C1=12.5 μg / L, corresponding to voltage V4, as an intermediate point; and C is a silicate standard solution with a concentration of C1=25 μg / L, corresponding to voltage V3; (2) Fit a quadratic polynomial V = a-C + b-C + c based on three concentration points 2 voltage The fitting is obtained by solving the following equation group and solving the coefficients a, b and c in the matrix form, and the equation group includes: V2 = a • 0 2 + b • 0 + c V4 = a • (12.5) 2 + b • (12.5) + c V3 = a • (25) 2 + b • (25) + c (3) inputting the sample voltage V, solving the concentration C by the quadratic equation, and then completing the calibration; The applicable condition of the multi-point polynomial calibration is |V1-V3|-|V3-V2|>30mV, at which time the system has nonlinearity, and the steps of the multi-point polynomial calibration include: (1) increasing calibration points of no less than 4 points; (2) fitting high-order polynomial based on least square method, calculating coefficient through regression analysis to ensure minimum residual; (3) inputting sample voltage V, verifying precision after solving cubic equation and inversely calculating concentration C, and completing calibration based on the deviation between each point and actual value ≤±0.5 μg / L to reach precision standard.

5. A method of calibration for a chemiluminescent silicate analyzer according to claim 4, wherein, The multi-point polynomial calibration comprises adding corresponding calibration points for improving precision, and the adding corresponding calibration points comprises selecting an additional point concentration, wherein the selecting an additional point concentration comprises: encrypting in a nonlinear significant interval; The method for adding corresponding calibration points comprises: completing initial three-point calibration (0 / 12.5 / 25 μg / L); sequentially measuring M point solutions, and recording M voltage values; re-fitting M+3 points to a polynomial, and automatically upgrading to an M+2 order polynomial.

6. A calibration system for a chemiluminescent silicate analyzer for carrying out the method according to any one of claims 1 to 5, characterized in that comprise: a single-point calibration module, configured to perform single-point calibration, comprising: preparing a silicate standard solution with a specified concentration, and obtaining an original signal value based on the silicate standard solution with the specified concentration; a chemiluminescence instrument calibration module, configured to calibrate a chemiluminescence instrument through a multi-calibration stage based on the single-point calibration.

7. An electronic device, comprising: comprise a processor and a memory, the memory stores a plurality of instructions, and the processor is configured to read the instructions and perform the method of any one of claims 1-5.

8. A computer-readable storage medium, characterized in that, The computer readable storage medium stores a plurality of instructions, which can be read and executed by the processor to perform the method of any one of claims 1-5.

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