A method for detecting silicate based on combination of colorimetric-chemiluminescence

Abstract

The present application relates to a kind of based on colorimetric-chemiluminescence combined silicate detection method, comprising: based on the standard curve of colorimetric-chemiluminescence combined instrument is established by reverse dosing mode;Colorimetric-chemiluminescence combined instrument calibration is carried out based on standard curve;Silicate concentration is measured based on calibrated colorimetric-chemiluminescence combined instrument.It also discloses corresponding system and device, device includes: sample cup (1), heater (2), light source (3), light emitting dish (4), photomultiplier (5), solution holding component and data acquisition processing module, wherein sample cup is connected with heater, the outlet of heater is connected with light emitting dish, open light source to form the transmission light after being colored solution absorption by illuminating monochromatic light to light emitting dish, and after closing light source, the radiation light formed by the reaction of solution and measured water sample, transmission light and / or radiation light are received by photomultiplier, amplified and converted into electrical signal after transmission to data acquisition processing module;Solution holding component is connected with light emitting dish.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of calibration of analytical instruments, and particularly relates to a silicate detection method based on combination of colorimetry and chemiluminescence. BACKGROUND

[0002] The treatment and monitoring of boiler water in thermal power plants is a crucial link, which is directly related to the safe operation of the boiler, energy efficiency and overall economic benefits of the power plant. The silicate content in the boiler water is one of the important indicators for measuring the quality of the boiler water. At present, most thermal power plants and semiconductor industries use silicate analyzers based on the silicomolybdenum blue colorimetric principle as the main detection means for detecting the concentration of silicate ions. During the detection process, a certain amount of reagent needs to be manually added, and after the chemical color reaction occurs, the silicate analyzer is used for measurement. This process has low automation degree, long detection time and large human influence factors. The chemiluminescence method (silicomolybdate photometric method) is an effective method for rapid measurement of trace silicate. The silicomolybdate is generated by the reaction of silicon and molybdate under certain conditions, and when it reacts with luminol, it can produce strong chemical luminescence. The concentration of the reactant can be directly measured by detecting the chemical luminescence intensity, and the luminescence reaction is completed within tens of seconds. The chemiluminescence method has the outstanding advantages of high sensitivity, no need for external excitation light source, avoidance of background light and stray light interference, and reduction of noise.

[0003] At present, all silicate measuring instruments and equipment need to construct a standard curve according to a standard solution. The standard solution is generally prepared by mixing a high-concentration silicate stock solution with silicate-free water. However, there is no absolute sense of silicate-free water in reality, so the prepared standard solution cannot accurately reach the known theoretical standard concentration, but only a relatively certain concentration value. The so-called silicate-free water is actually water with extremely low silicate ion concentration, which is generally required to be not higher than 5 μg / L. The silicate ions contained in the silicate-free water are called background silicate. Therefore, the obtained standard solution concentration is not a theoretical standard solution, but a certain standard solution plus the background silicate in water.

[0004] The traditional silicomolybdenum blue colorimetric detection method can eliminate the influence of background silicate by adding reagents in reverse, but the chemiluminescence method is a transient reaction of silicomolybdate oxidizing luminol reagent, which cannot eliminate the background silicate by adding reagents. In summary, the traditional silicomolybdenum blue colorimetric method can eliminate the influence of background silicate but has a long measurement time, and the chemiluminescence method has fast measurement speed but cannot eliminate the influence of background silicate.

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

[0006] 1、Chemiluminescence method cannot eliminate the influence of background silicon in water, resulting in high lower limit of detection and low detection sensitivity. This is because the Chemiluminescence method is that silicate reacts with ammonium molybdate to generate silicomolybdate, and silicomolybdate has oxidation activity, which can oxidize luminol to produce chemiluminescence, and the content of silicon in water is determined by detecting the light intensity. However, the luminescence reaction is a transient luminescence reaction, and the influence of background silicon cannot be eliminated by adjusting the dosing method.

[0007] 2、Silicomolybdenum blue colorimetric method has a long measurement time and a large human error, because the silicomolybdenum blue colorimetric reaction needs to manually add multiple samples, and the reaction time is long, resulting in too long measurement time. SUMMARY

[0008] The purpose of the present application is to provide a colorimetric-chemiluminescence combined method for detecting silicate, which is a rapid and background silicon-free silicate detection method. The traditional silicomolybdenum blue colorimetric method and the chemiluminescence method are combined, and the reverse dosing method of the silicomolybdenum blue colorimetric method is used to calibrate the silicate ion concentration in ultrapure water, and the standard curve for eliminating the influence of background silicon in the chemiluminescence method is established. The proposed combined method not only solves the problems of low automation, long detection time and large human influence factors of the traditional silicomolybdenum blue colorimetric method, but also improves the detection sensitivity of the chemiluminescence method, reduces the lower limit of detection, effectively removes the interference of background signal and other base factors, reduces the measurement error, enhances the detection sensitivity, reduces the lower limit of detection, improves the measurement speed, and the reagents, light path and other parts required by the colorimetric method and the chemiluminescence method can be shared, without causing excessive increase in cost.

[0009] The first aspect of the present application provides a silicate detection method based on colorimetric-chemiluminescence combination, comprising:

[0010] S1, establishing a colorimetric-chemiluminescence combined instrument standard curve based on a reverse dosing method;

[0011] S2, calibrating the colorimetric-chemiluminescence combined instrument based on the standard curve;

[0012] S3, measuring the silicate concentration based on the calibrated colorimetric-chemiluminescence combined instrument.

[0013] Preferably, S1 comprises:

[0014] S11, measuring and processing the ultrapure water after adding the ultrapure water to the colorimetric system by the reverse dosing method, so as to measure the voltage value V0 corresponding to the silicate concentration in the ultrapure water;

[0015] S12, configure two concentrations of the first standard liquid and the second standard liquid, and measure and process the first standard liquid and the second standard liquid after the first standard liquid and the second standard liquid are added to the colorimetric system by using a normal dosing process, so as to measure the voltage values corresponding to the silicate concentrations in the first standard liquid and the second standard liquid respectively;

[0016] S13, measure the silicate concentration in the ultrapure water by adding the ultrapure water to the chemiluminescence system, and the voltage value corresponding to the silicate concentration in the ultrapure water is L0;

[0017] S14, measure the silicate concentration in the first standard liquid and the second standard liquid by adding the first standard liquid and the second standard liquid to the chemiluminescence system in turn;

[0018] S15, calculate the true concentrations of the first standard liquid and the second standard liquid configured in the actual calibration process;

[0019] S16, obtain the background silicate concentration in the ultrapure water based on the colorimetric principle;

[0020] S17, based on the background silicate concentration in the ultrapure water, the voltage value corresponding to the silicate concentration in the ultrapure water, the true concentrations of the first standard liquid and the second standard liquid, and the voltage values corresponding to the silicate concentrations in the first standard liquid and the second standard liquid respectively, a standard curve between the silicate concentration and the voltage value is established by using the least square method.

[0021] Preferably, the true concentrations of the first standard liquid and the second standard liquid are calculated as shown in the following formulas (1) and (2):

[0022] C'1=C1+n1C0+(1-n1)X (1)

[0023] C'2=C2+n2C0+(1-n2)X (2)

[0024] In the formulas, C1 and C2 are the theoretical concentrations of the first standard liquid and the second standard liquid; C ′ 1, C'2 are the true concentrations of the first standard liquid and the second standard liquid; C0 is the silicate national standard substance with a certificate; n1 and n2 are the dilution coefficients of the first standard liquid and the second standard liquid; X is the background silicate concentration in the ultrapure water; the standard solution concentration is mg level, the standard liquid to be configured is ug level, and the dilution coefficient can be ignored, so the above formulas are simplified as formulas (3) and (4):

[0025] C'1=C1+X (3)

[0026] C'2=C2+X (4).

[0027] Preferably, the expression of the background silicon concentration X in the ultrapure water is as follows:

[0028]

[0029] Preferably, the standard curve is as follows:

[0030] C = aL + b (6)

[0031] In the formula, C is the concentration of silicate (ug / L); a is the slope obtained by fitting formula; L is the measured voltage value, unit: mV; b is the intercept obtained by least squares fitting.

[0032] Preferably, the S2 comprises:

[0033] S21, adding ultrapure water into the sample cup (1), heating by the heater (2) to form an ultrapure water sample into the luminous cup (4);

[0034] S22, performing the reverse dosing process, including: adding the ferrous sulfate solution (9) contained in the reagent bottle D into the luminous cup (4), the ultrapure water sample and the ferrous sulfate solution (9) mixed reaction, then adding the oxalic acid solution (8) contained in the reagent bottle C, and then adding the ammonium molybdate solution (6) contained in the reagent bottle A and the sulfuric acid solution (7) contained in the reagent bottle B to form the first color solution;

[0035] S23, the light source (3) emits stable monochromatic light, the monochromatic light is absorbed by the first color solution through the luminous cup (4) to become transmitted light, the transmitted light is received by the photomultiplier (5), and then converted into an electrical signal after amplification and transmitted to the data acquisition and processing module (11), at this time the voltage value V0 corresponding to the silicate concentration in the ultrapure water is obtained;

[0036] S24, adding the first standard liquid and the second standard liquid into the sample cup (1) in turn, heating by the heater (2) to form the first standard liquid sample and the second standard liquid sample, and then sending the first standard liquid sample and the second standard liquid sample into the luminous cup (4);

[0037] S25, performing the dosing process of normal measurement by colorimetry, including: adding the ammonium molybdate solution (6) contained in the reagent bottle A and the sulfuric acid solution (7) contained in the reagent bottle B into the luminous cup (4), mixing reaction for 5 min, then adding the oxalic acid solution (8) contained in the reagent bottle C, 1 min later, adding the ferrous sulfate solution (9) contained in the reagent bottle D, and then standing for 8 min to form the second color solution;

[0038] S26, the light source (3) emits stable monochromatic light, the monochromatic light is absorbed by the second color developing solution through the light emitting cup (4) to become transmitted light, the transmitted light is received by the photomultiplier (5), and after being amplified and converted into an electric signal, is transmitted to the data acquisition and processing module (11), at this time, voltage values V1 and V2 corresponding to the concentrations of silicate in the first standard liquid C1 and the second standard liquid C2 are obtained respectively;

[0039] S27, the ultrapure water, the first standard liquid and the second standard liquid are sequentially added to the sample cup (1), heated by the heater 2 to form a mixed sample, and the mixed sample is sent into the light emitting cup (4);

[0040] S28, the process is a chemical reaction self-luminous, so the light source 3 needs to be turned off; at this time, the ammonium molybdate solution (6) contained in the reagent bottle A and the sulfuric acid solution (7) contained in the reagent bottle B are added to the light emitting cup 4, the ammonium molybdate solution (6) and the sulfuric acid solution (7) are mixed with the mixed sample to react for 1 min to form a stable silicomolybdate heteropoly acid solution, the basic luminol solution (10) contained in the reagent bottle E is added, a chemical reaction is generated and emits radiation light, the radiation light is received by the photomultiplier (5), after being amplified and converted into an electric signal, is transmitted to the data acquisition and processing module (11), at this time, voltage values L1 and L2 corresponding to the concentrations of silicate in the first standard liquid and the second standard liquid are obtained respectively, and voltage value L0 corresponding to the concentration of silicate in the ultrapure water is obtained;

[0041] S29, the obtained data is fitted by corresponding processing of the standard curve to obtain a calibration standard curve formula, so that the calibration of the colorimetric-chemiluminescence combined instrument is completed.

[0042] Preferably, the S3 comprises:

[0043] S31, confirming that the light source (3) is in the off state, adding the water sample to be measured into the sample cup (1), heating the water sample to be measured by the heater (2) to form a water sample to be measured, and sending the water sample to be measured into the light emitting cup (4);

[0044] S32, the ammonium molybdate solution (6) contained in the reagent bottle A and the sulfuric acid solution (7) contained in the reagent bottle B are added to the light emitting cup 4, the water sample to be measured is mixed with the ammonium molybdate solution (6) and the sulfuric acid solution (7) to react for 1 min to form a stable silicomolybdate heteropoly acid solution, the basic luminol solution (10) contained in the reagent bottle E is added, a chemical reaction is generated and emits radiation light, the radiation light is received by the photomultiplier (5), after being amplified and converted into an electric signal, is transmitted to the data acquisition and processing module (11), at this time, the measurement voltage value L corresponding to the sample to be measured is obtained, and the concentration C of silicate in the sample is calculated according to the standard curve (6).

[0045] A second aspect of the present invention provides a silicate detection system based on colorimetric-chemiluminescence coupling for implementing the method of the first aspect, comprising:

[0046] The standard curve establishment module (101) is used to establish the standard curve of the colorimetric-chemiluminescence analyzer based on the reverse dosing method;

[0047] A calibration module (102) is used for calibrating the colorimetric-chemiluminescence analyzer based on the standard curve;

[0048] Concentration measurement module (103) for measuring silicate concentration based on a calibrated colorimetric-chemiluminescence analyzer.

[0049] A third aspect of the present invention provides a silicate detection device based on colorimetric-chemiluminescence coupling for implementing the method of the first aspect, comprising:

[0050] The sample container (1), heater (2), light source (3), luminescent dish (4), photomultiplier tube (5), solution holding assembly, and data acquisition and processing module (11) are provided. The sample container (1) is connected to the heater (2), and the outlet of the heater (2) is connected to the luminescent dish (4). The light source (3) is turned on to irradiate the luminescent dish (4) with monochromatic light to form transmitted light that is absorbed by the colorimetric solution. The light source (3) is turned off to form radiated light by the reaction between the solution and the water sample being tested. The transmitted light and / or the radiated light are received by the photomultiplier tube (5), amplified and converted into an electrical signal, and then transmitted to the data acquisition and processing module (11). The solution holding assembly is connected to the luminescent dish (4).

[0051] Preferably, the solution holding assembly includes a reagent bottle A for holding ammonium molybdate solution (6), a reagent bottle B for holding sulfuric acid solution (7), a reagent bottle C for holding oxalic acid solution (8), a reagent bottle D for holding ferrous ammonium sulfate solution (9), and a reagent bottle E for holding alkaline luminol solution (10), all arranged in parallel.

[0052] The silicate detection method, system, and apparatus based on colorimetric-chemiluminescence coupling of the present invention have the following beneficial effects:

[0053] (1) The first proposal was to combine colorimetric and chemiluminescence methods to eliminate the shortcomings of each method;

[0054] (2) The design of the colorimetric-chemiluminescence coupled instrument fully considers the common requirements of colorimetry and chemiluminescence in terms of reagents, optical path and other aspects, and does not cause a significant increase in cost;

[0055] (3) It solves the problem of slow measurement speed in traditional colorimetric methods; it has high detection sensitivity and a lower detection limit.

[0056] (4) It solves the problem that chemiluminescence cannot eliminate the influence of background silicon; Attached Figure Description

[0057] 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.

[0058] Figure 1 This is a block diagram illustrating the principle of the silicate detection method based on colorimetric-chemiluminescence coupling provided in this embodiment of the invention.

[0059] Figure 2 This is a schematic diagram of the silicate detection method based on colorimetric-chemiluminescence coupling provided in an embodiment of the present invention;

[0060] Figure 3 This is a flowchart of step S1 of the silicate detection method based on colorimetric-chemiluminescence coupling provided in an embodiment of the present invention;

[0061] Figure 4 This is a flowchart of step S3 of the silicate detection method based on colorimetric-chemiluminescence coupling provided in an embodiment of the present invention;

[0062] Figure 5 This is a schematic diagram of the silicate detection system based on colorimetric-chemiluminescence coupling provided in an embodiment of the present invention. Detailed Implementation

[0063] 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.

[0064] 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.

[0065] 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.

[0066] Example 1

[0067] like Figure 1 and 2 As shown, this embodiment provides a silicate detection method based on colorimetric-chemiluminescence coupling, including:

[0068] S1, Establish the standard curve for the colorimetric-chemiluminescence immunoassay system based on the reverse dosing method;

[0069] like Figure 3 As shown, in a preferred embodiment, S1 includes:

[0070] S11, ultrapure water is added to the colorimetric system by reverse addition of chemicals and then measured and processed to obtain the voltage value V0 corresponding to the silicate concentration in ultrapure water.

[0071] S12, prepare two standard liquids of two concentrations, first and second standard liquids, add the first and second standard liquids to the colorimetric system using the normal dosing procedure, and then measure and process them to obtain the voltage values ​​V1 and V2 corresponding to the silicate concentrations in the first and second standard liquids, respectively.

[0072] S13, ultrapure water was added to the chemiluminescence system for measurement, and the voltage value corresponding to the silicate concentration in the ultrapure water was measured to be L0;

[0073] S14, the first standard liquid and the second standard liquid are added to the chemiluminescence system in sequence for measurement, and the voltage values ​​corresponding to the silicate concentration in the first standard liquid and the second standard liquid are measured to be L1 and L2, respectively.

[0074] S15, Calculate the actual concentrations of the first and second standard liquids configured during the actual calibration process;

[0075] Since ultrapure water inevitably contains a certain amount of background silicon, the actual concentrations of the first and second standard liquids prepared in the actual calibration process are calculated as shown in equations (1) and (2) below:

[0076] C ′ 1=C1+n1C0+(1-n1)X (1)

[0077] C ′ 2=C2+n2C0+(1-n2)X (2)

[0078] In the formula: C1 and C2 are the theoretical concentrations of the first and second standard liquids; C'1, C ′ 2 represents the actual concentration of the first and second standard liquids; C0 represents the certified national standard material for silicate; n1 and n2 represent the dilution coefficients of the first and second standard liquids; X represents the background silica concentration in ultrapure water. Typically, the standard solution concentration is in the mg range, while the required standard liquid concentration is in the μg range. Therefore, the dilution coefficient is relatively small, and the above formula can be simplified to formulas (3) and (4):

[0079] C'1=C1+X (3);

[0080] C ′ 2 = C² + X (4);

[0081] S16, the expression for the background silicon concentration X in ultrapure water, based on the colorimetric principle, is as follows:

[0082]

[0083] S17, based on the background silicon concentration X in ultrapure water, the voltage value L0 corresponding to the silicate concentration in ultrapure water, and the true concentrations C of the first and second standard liquids. ′ 1, C'2, The voltage values ​​L1 and L2 corresponding to the silicate concentrations in the first and second standard liquids are established using the least squares method to establish the relationship between silicate concentration and voltage value (X, L0)(C'1, L1)(C ′ Standard curve of L2):

[0084] C = aL + b (6)

[0085] In the formula: C is the silicate concentration (ug / L); a is the slope obtained from the fitting formula; L is the measured voltage value in mV; b is the intercept obtained from the least squares fitting.

[0086] The beneficial effects of step S1 are as follows: By establishing a standard curve for eliminating the influence of background silicon using chemiluminescence, the influence of background silicon in ultrapure water on calibration is eliminated, improving the accuracy of detection, lowering the detection limit, and enhancing the detection sensitivity.

[0087] S2, perform colorimetric-chemiluminescence immunoassay calibration based on the standard curve;

[0088] In a preferred embodiment, S2 includes:

[0089] S21, add ultrapure water to sample cup 1, heat it by heater 2 to form an ultrapure water sample and send it into luminescent dish 4;

[0090] S22, the dosing process of adding the drug in reverse includes: adding ferrous ammonium sulfate solution 9 contained in reagent bottle D to the luminescent dish 4; after the ultrapure water sample is mixed and reacted with the ferrous ammonium sulfate solution 9, adding oxalic acid solution 8 contained in reagent bottle C; and then adding ammonium molybdate solution 6 contained in reagent bottle A and sulfuric acid solution 7 contained in reagent bottle B to form the first colorimetric solution.

[0091] S23, the light source 3 emits stable monochromatic light, which is absorbed by the first color development solution after passing through the light-emitting dish 4 and becomes transmitted light. The transmitted light is received by the photomultiplier tube 5, amplified and converted into an electrical signal, and then transmitted to the data acquisition and processing module 11. At this time, the voltage value V0 corresponding to the silicate concentration in the ultrapure water is obtained.

[0092] S24, the first standard liquid and the second standard liquid are added to the injection cup 1 in sequence, and after being heated by the heater 2, the first standard liquid sample and the second standard liquid sample are formed. The first standard liquid sample and the second standard liquid sample are then sent into the luminescent dish 4.

[0093] S25, the dosing procedure for normal colorimetric measurement includes: adding ammonium molybdate solution 6 in reagent bottle A and sulfuric acid solution 7 in reagent bottle B to the luminescent dish 4, mixing and reacting for 5 min, then adding oxalic acid solution 8 in reagent bottle C, and adding ferrous ammonium sulfate solution 9 in reagent bottle D after 1 min, and standing for 8 min to form the second colorimetric solution.

[0094] S26, the light source 3 emits stable monochromatic light, which is absorbed by the second colorimetric solution after passing through the light-emitting dish 4 and becomes transmitted light. The transmitted light is received by the photomultiplier tube 5, amplified and converted into an electrical signal, and then transmitted to the data acquisition and processing module 11. At this time, the voltage values ​​V1 and V2 corresponding to the silicate concentrations in the first standard liquid C1 and the second standard liquid C2 are obtained respectively.

[0095] S27, ultrapure water, first standard liquid and second standard liquid are added to sample cup 1 in sequence, and after being heated by heater 2, a mixed sample is formed. The mixed sample is then sent into luminescent dish 4.

[0096] S28, this process is a chemical reaction that emits light spontaneously, so the light source 3 needs to be turned off; at this time, first add ammonium molybdate solution 6 from reagent bottle A and sulfuric acid solution 7 from reagent bottle B to the light-emitting dish 4. After the ammonium molybdate solution 6 and the sulfuric acid solution 7 react with the mixed sample for 1 minute, a stable silicomolybdenum heteropoly acid solution is formed. Then add alkaline luminol solution 10 from reagent bottle E to produce a chemical reaction and emit radiation light. The radiation light is received by photomultiplier tube 5, amplified and converted into an electrical signal and transmitted to data acquisition and processing module 11. At this time, the voltage values ​​corresponding to the silicate concentration in the first standard liquid and the second standard liquid are L1 and L2, respectively, and the voltage value corresponding to the silicate concentration in ultrapure water is L0.

[0097] S29, the obtained data is fitted with the corresponding standard curve to obtain the calibration standard curve formula, thereby completing the calibration of the colorimetric-chemiluminescence analyzer.

[0098] The beneficial effect of step S2: After calibration is completed by the above calibration method, the chemiluminescence system will be used as the measurement method, so the process of obtaining the calibration voltage value is consistent with that of the chemiluminescence system.

[0099] S3, based on a calibrated colorimetric-chemiluminescence analyzer, measures silicate concentration.

[0100] like Figure 4 As shown, in a preferred embodiment, S3 includes:

[0101] S31, confirm that the light source 3 is in the off state, add the water sample to be tested into the sample inlet cup 1, and after being heated by the heater 2, form the water sample to be tested, and send the water sample to be tested into the light-emitting dish 4;

[0102] S32, first add ammonium molybdate solution 6 from reagent bottle A and sulfuric acid solution 7 from reagent bottle B to the luminescent dish 4. After the water sample to be tested reacts with the ammonium molybdate solution 6 and sulfuric acid solution 7 for 1 minute, a stable silicomolybdenum heteropoly acid solution is formed. Then add alkaline luminol solution 10 from reagent bottle E to produce a chemical reaction and emit radiation light. The radiation light is received by photomultiplier tube 5, amplified and converted into an electrical signal and transmitted to data acquisition and processing module 11. At this time, the measurement voltage value L corresponding to the sample to be tested is obtained. The silicate concentration C in the sample is calculated according to the standard curve 6.

[0103] Example 2

[0104] like Figure 5 As shown, this embodiment provides a silicate detection system based on colorimetric-chemiluminescence coupling for implementing the method of Embodiment 1, including:

[0105] Standard curve establishment module 101 is used to establish a standard curve for a colorimetric-chemiluminescence analyzer based on the reverse dosing method.

[0106] The coupled calibration module 102 is used to calibrate the colorimetric-chemiluminescence instrument based on the standard curve.

[0107] Concentration measurement module 103 is used to measure silicate concentration based on a calibrated colorimetric-chemiluminescence analyzer.

[0108] Example 3

[0109] See you again Figure 4 This embodiment provides a silicate detection device based on colorimetric-chemiluminescence coupling, comprising:

[0110] The system comprises a sample inlet cup 1, a heater 2, a light source 3, a light-emitting dish 4, a photomultiplier tube 5, a solution container assembly, and a data acquisition and processing module 11. The sample inlet cup 1 is connected to the heater 2, and the outlet of the heater 2 is connected to the light-emitting dish 4. The light source 3 is turned on to irradiate the light-emitting dish 4 with monochromatic light, which is then absorbed by the colorimetric solution and transmitted. The light source 3 is turned off to generate radiated light from the reaction between the solution and the water sample being tested. The transmitted light and / or the radiated light are received by the photomultiplier tube 5, amplified, converted into an electrical signal, and transmitted to the data acquisition and processing module 11. The solution container assembly is connected to the light-emitting dish 4.

[0111] In a preferred embodiment, the solution holding assembly includes a reagent bottle A for holding ammonium molybdate solution 6, a reagent bottle B for holding sulfuric acid solution 7, a reagent bottle C for holding oxalic acid solution 8, a reagent bottle D for holding ferrous ammonium sulfate solution 9, and a reagent bottle E for holding alkaline luminol solution 10, all arranged in parallel.

[0112] 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. This software product can be stored in a non-volatile storage medium (such as a CD-ROM, USB flash drive, mobile hard drive, etc.) and includes 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.

[0113] 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 method for detecting silicate ions based on colorimetric-chemiluminescence coupling, characterized in that, include: S1, Establishing a standard curve for a colorimetric-chemiluminescence immunoassay system based on a reverse dosing method; including: S11, ultrapure water is added to the colorimetric system using a reverse dosing method, followed by measurement and treatment, to obtain the voltage value corresponding to the silicate concentration in the ultrapure water. ; S12, prepare two standard solutions of different concentrations, namely a first standard solution and a second standard solution. Add the first and second standard solutions to the colorimetric system using the normal dosing procedure, then measure and process them to obtain the voltage values ​​corresponding to the silicate concentrations in the first and second standard solutions, respectively. , ; S13, ultrapure water was added to the chemiluminescence system for measurement, and the voltage value corresponding to the silicate concentration in the ultrapure water was measured. ; S14, the first standard liquid and the second standard liquid are added sequentially to the chemiluminescence system for measurement, and the voltage values ​​corresponding to the silicate concentrations in the first and second standard liquids are measured respectively. , ; S15, Calculate the actual concentrations of the first and second standard liquids configured during the actual calibration process; Since ultrapure water inevitably contains a certain amount of background silicon, the actual concentrations of the first and second standard liquids prepared in the actual calibration process are calculated as shown in equations (1) and (2) below: （1） （2） In the formula: and The theoretical concentrations of the first and second standard liquids; , The actual concentrations of the first and second standard liquids; It is a certified national standard reference material for silicates; , The dilution factor is the ratio of the first standard liquid to the second standard liquid. To find the background silicon concentration in ultrapure water, the above equations are simplified to equations (3) and (4): （3）； （4）； S16, The background silicon concentration in ultrapure water is obtained based on the colorimetric principle. The expression is as follows: （5）； S17, based on the background silicon concentration in ultrapure water Voltage value corresponding to silicate concentration in ultrapure water The true concentrations of the first and second standard liquids , The voltage values ​​corresponding to the silicate concentrations in the first and second standard liquids. , The least squares method was used to establish the relationship between silicate concentration and voltage value (X, () , () , The standard curve of ) （6） In the formula: This represents the silicate concentration, expressed in μg / L. The slope obtained from the fitted formula; The voltage value is measured in mV. The intercept obtained from the least squares fitting; S2, perform colorimetric-chemiluminescence immunoassay calibration based on the standard curve; S3, based on a calibrated colorimetric-chemiluminescence analyzer, measures silicate concentration.

2. The silicate detection method based on colorimetric-chemiluminescence coupling according to claim 1, characterized in that, S2 includes: S21, add ultrapure water to the sample inlet cup (1), heat it through the heater (2) to form an ultrapure water sample, and send it into the luminescent dish (4); S22, the dosing process of adding the drug in reverse includes: adding ferrous ammonium sulfate solution (9) contained in reagent bottle D to the luminescent dish (4), mixing and reacting the ultrapure water sample with the ferrous ammonium sulfate solution (9), adding oxalic acid solution (8) contained in reagent bottle C, and then adding ammonium molybdate solution (6) contained in reagent bottle A and sulfuric acid solution (7) contained in reagent bottle B to form the first colorimetric solution; S23, the light source (3) emits stable monochromatic light, which is absorbed by the first color development solution after passing through the light-emitting dish (4) and becomes transmitted light. The transmitted light is received by the photomultiplier tube (5), amplified and converted into an electrical signal, and then transmitted to the data acquisition and processing module (11). At this time, the voltage value V0 corresponding to the silicate concentration in the ultrapure water is obtained. S24, the first standard liquid and the second standard liquid are added to the injection cup (1) in sequence, and after being heated by the heater (2), the first standard liquid sample and the second standard liquid sample are formed. The first standard liquid sample and the second standard liquid sample are then sent into the luminescent dish (4). S25, the dosing procedure for normal colorimetric measurement includes: adding ammonium molybdate solution (6) in reagent bottle A and sulfuric acid solution (7) in reagent bottle B to the luminescent dish (4), mixing and reacting for 5 min, then adding oxalic acid solution (8) in reagent bottle C, then adding ferrous ammonium sulfate solution (9) in reagent bottle D after 1 min, and then standing for 8 min to form a second colorimetric solution; S26, the light source (3) emits stable monochromatic light, which is absorbed by the second color development solution after passing through the light-emitting dish (4) and becomes transmitted light. The transmitted light is received by the photomultiplier tube (5), amplified and converted into an electrical signal, and then transmitted to the data acquisition and processing module (11). At this time, the voltage values ​​V1 and V2 corresponding to the silicate concentrations in the first standard liquid C1 and the second standard liquid C2 are obtained respectively. S27, ultrapure water, first standard liquid and second standard liquid are added to the injection cup (1) in sequence, and after being heated by heater 2, a mixed sample is formed. The mixed sample is then sent into the luminescent dish (4). S28, this process is a chemical reaction that emits light on its own, so the light source 3 needs to be turned off; at this time, first add the ammonium molybdate solution (6) in reagent bottle A and the sulfuric acid solution (7) in reagent bottle B to the light-emitting dish (4). The ammonium molybdate solution (6) and the sulfuric acid solution (7) react with the mixed sample for 1 minute to form a stable silicomolybdenum heteropoly acid solution. Add the alkaline luminol solution (10) in reagent bottle E to produce a chemical reaction and emit radiation light. The radiation light is received by the photomultiplier tube (5), amplified and converted into an electrical signal and transmitted to the data acquisition and processing module (11). At this time, the voltage values ​​corresponding to the silicate concentration in the first standard liquid and the second standard liquid are L1 and L2 respectively, and the voltage value corresponding to the silicate concentration in ultrapure water is L0. S29, the obtained data is fitted with the corresponding standard curve to obtain the calibration standard curve formula, thereby completing the calibration of the colorimetric-chemiluminescence analyzer.

3. The silicate detection method based on colorimetric-chemiluminescence coupling according to claim 2, characterized in that, S3 includes: S31, confirm that the light source (3) is in the off state, add the water sample to be tested into the sample cup (1), heat it through the heater (2) to form the water sample to be tested, and send the water sample to be tested into the luminescent dish (4); S32, first add ammonium molybdate solution (6) in reagent bottle A and sulfuric acid solution (7) in reagent bottle B to the luminescent dish 4. The water sample to be tested reacts with the ammonium molybdate solution (6) and the sulfuric acid solution (7) for 1 minute to form a stable silicomolybdenum heteropolyacid solution. Add alkaline luminol solution (10) in reagent bottle E to produce a chemical reaction and emit radiation light. The radiation light is received by photomultiplier tube (5), amplified and converted into an electrical signal and transmitted to data acquisition and processing module (11). At this time, the measurement voltage value L corresponding to the sample to be tested is obtained. The silicate concentration C in the sample is calculated according to the standard curve (6).

4. A silicate detection system based on colorimetric-chemiluminescence coupling, used to implement the method according to any one of claims 1-3, characterized in that, include: The standard curve establishment module (101) is used to establish the standard curve of the colorimetric-chemiluminescence analyzer based on the reverse dosing method; A calibration module (102) is used for calibrating the colorimetric-chemiluminescence analyzer based on the standard curve; Concentration measurement module (103) for measuring silicate concentration based on a calibrated colorimetric-chemiluminescence analyzer.

5. A silicate detection device based on colorimetric-chemiluminescence coupling, used to implement the method according to any one of claims 1-3, characterized in that, include: The sample container (1), heater (2), light source (3), luminescent dish (4), photomultiplier tube (5), solution holding assembly, and data acquisition and processing module (11) are provided. The sample container (1) is connected to the heater (2), and the outlet of the heater (2) is connected to the luminescent dish (4). The light source (3) is turned on to irradiate the luminescent dish (4) with monochromatic light to form transmitted light that is absorbed by the colorimetric solution. The light source (3) is turned off to form radiation light that is generated by the reaction of the solution with the water sample being tested. The transmitted light and / or the radiation light are received by the photomultiplier tube (5), amplified and converted into an electrical signal, and then transmitted to the data acquisition and processing module (11). The solution holding assembly is connected to the luminescent dish (4).

6. The detection device according to claim 5, characterized in that, The solution holding assembly includes a reagent bottle A for holding ammonium molybdate solution (6), a reagent bottle B for holding sulfuric acid solution (7), a reagent bottle C for holding oxalic acid solution (8), a reagent bottle D for holding ferrous ammonium sulfate solution (9), and a reagent bottle E for holding alkaline luminol solution (10), all arranged in parallel.

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