Silicate detection method based on colorimetric-chemiluminescence combination

Abstract

The invention relates to a silicate detection method based on colorimetric-chemiluminescence combination. The method comprises the following steps: establishing a standard curve of a colorimetric-chemiluminescence combination instrument based on a dosing mode; calibrating the colorimetric-chemiluminescence combined instrument based on the standard curve; and measuring the silicate concentration based on a calibrated colorimetric-chemiluminescence combined instrument. The invention further discloses a corresponding system and device, the device comprises a sample injection cup (1), a heater (2), a light source (3), a light-emitting vessel (4), a photomultiplier tube (5), a solution containing assembly and a data collecting and processing module, the sample injection cup is connected with the heater, an outlet of the heater is connected with the light-emitting vessel, the light source is turned on to irradiate the light-emitting vessel with monochromatic light to form transmission light absorbed by the developing solution, and the transmission light is transmitted to the photomultiplier tube (5). After the light source is turned off, the solution reacts with the detected water sample to form radial light, the transmission light and / or the radial light are received by the photomultiplier, are amplified and converted into electric signals and then are transmitted to the data acquisition and processing module; the solution containing assembly is connected with the light-emitting vessel.

Description

Technical Field

[0001] The present invention relates to the technical field of calibration of analytical instruments, and in particular to a silicate detection method based on colorimetry-chemiluminescence combination. Background Art

[0002] The treatment and monitoring of boiler water in thermal power plants is crucial, directly impacting the safe operation of the boiler, energy efficiency, and the overall economic benefits of the power plant. Silicate content in boiler water is a key indicator of boiler water quality. Currently, most thermal power plants and the semiconductor industry use silicate analyzers based on the molybdenum blue colorimetric principle to measure silicate ion concentration. This process requires manual addition of a certain amount of reagent, followed by a chemical color reaction, followed by measurement using the silicate analyzer. This process has a low degree of automation, long detection times, and significant human influence. Chemiluminescence (heteropolymolybdosilicic acid spectrophotometry) involves the reaction of silicon with molybdate under certain conditions to produce molybdosilicic acid. When reacting with luminol, the resulting molybdosilicic acid produces strong chemiluminescence. The chemiluminescence intensity can be used to directly determine the concentration of the reactants. The luminescence reaction completes within tens of seconds, making it an effective and rapid method for measuring trace amounts of silicate. Chemiluminescence offers the advantages of high sensitivity, the absence of an external excitation light source, and the elimination of background and stray light interference, resulting in low noise.

[0003] Currently, all instruments and equipment for silicate measurement require the construction of a calibration curve based on a standard solution. This standard solution is typically prepared by mixing a high-concentration silicate mother liquor with silicon-free water. However, since absolutely silicon-free water does not exist in reality, the prepared standard solution cannot precisely achieve the known theoretical standard concentration, but rather a relatively defined concentration. This is because so-called silicon-free water is actually water with an extremely low silicate ion concentration, generally required to be no higher than 5μg / L. The silicate ions contained in silicon-free water are referred to as background silica. Therefore, the resulting standard solution concentration is not the theoretical standard solution, but rather the determined standard solution plus the background silica in the water.

[0004] Traditional silicomolybdenum blue colorimetric detection methods can eliminate the influence of background silicon by reverse dosing. However, chemiluminescence is an instantaneous reaction in which silicomolybdenum heteropolyacids oxidize the luminol luminescent reagent, making it impossible to eliminate background silicon by dosing. In summary, the traditional silicomolybdenum blue colorimetric method can eliminate the influence of background silicon, but the measurement time is long, while the chemiluminescence method is fast but cannot eliminate the influence of background silicon.

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

[0006] 1. The chemiluminescence method cannot eliminate the influence of background silicon in water, resulting in a high detection limit and low sensitivity. This is because the chemiluminescence method is based on the reaction of silicate and ammonium molybdate to form silicomolybdic acid. Silicomolybdic acid has oxidative activity and can oxidize luminol to produce chemiluminescence. The silicon content in water is determined by measuring the luminescence intensity. However, this luminescence reaction is instantaneous, and the influence of background silicon cannot be eliminated by adjusting the dosing method.

[0007] 2. The measurement time of the molybdenum blue colorimetric method is long and the human error is large. This is because the molybdenum blue colorimetric reaction requires manual addition of multiple samples, which takes a long time to react and causes the measurement time to be too long. Summary of the Invention

[0008] The purpose of the present invention is to provide a method for detecting silicate by combining colorimetry and chemiluminescence, which is a rapid method for detecting silicate without the influence of background silicon. The method adopts a combination of traditional molybdenum blue colorimetry and chemiluminescence, utilizes the reverse dosing method of molybdenum blue colorimetry to calibrate the concentration of silicate ions in ultrapure water, and guides the chemiluminescence method to establish a standard curve that eliminates the influence of background silicon. The proposal of this combined method not only solves the problems of low degree of automation, long detection time, and large human influence factors of the traditional molybdenum blue colorimetry, but also improves the detection sensitivity of the chemiluminescence method, reduces the detection limit, can effectively remove the interference of background factors such as background signals, reduce measurement errors, enhance detection sensitivity, reduce the detection limit, and increase measurement speed. Moreover, the reagents, optical paths, and other parts required for the colorimetry and chemiluminescence methods can be shared, and will not cause excessive cost increases.

[0009] The first aspect of the present invention is to provide a method for detecting silicate based on colorimetry and chemiluminescence, comprising:

[0010] S1, establish the standard curve of colorimetry-chemiluminescence instrument based on the reverse dosing method;

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

[0012] S3, silicate concentration was measured based on a calibrated colorimetric-chemiluminescent instrument.

[0013] Preferably, the S1 includes:

[0014] S11, adding ultrapure water to the colorimetric system by reverse dosing, and then measuring and processing, thereby measuring the voltage value V0 corresponding to the silicate concentration in the ultrapure water;

[0015] S12, preparing a first standard liquid and a second standard liquid of two concentrations, adding the first standard liquid and the second standard liquid to the colorimetric system using a normal dosing process, and then measuring and processing them, thereby measuring the voltage values ​​corresponding to the silicate concentrations in the first standard liquid and the second standard liquid, respectively;

[0016] S13, adding ultrapure water to the chemiluminescence system for measurement, and measuring the voltage value corresponding to the silicate concentration in the ultrapure water to be L0;

[0017] S14, sequentially adding the first standard liquid and the second standard liquid to the chemiluminescence system for measurement, and measuring voltage values ​​corresponding to silicate concentrations in the first standard liquid and the second standard liquid;

[0018] S15, calculating the actual concentrations of the first standard liquid and the second standard liquid configured during the actual calibration process;

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

[0020] S17, based on the background silicon concentration in ultrapure water, the voltage value corresponding to the silicate concentration in the ultrapure water, the actual 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 using the least squares 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] Where: C1 and C2 are the theoretical concentrations of the first standard liquid and the second standard liquid; C ′ 1, C'2 are the actual concentrations of the first standard liquid and the second standard liquid; C0 is the national standard substance of silicate with a certificate; n1, n2 are the dilution coefficients of the first standard liquid and the second standard liquid; X is the background silicon concentration in ultrapure water; the concentration of the standard solution is mg level, and the standard liquid required is ug level. The dilution coefficient can be ignored. The above formula is simplified to formula (3) and formula (4):

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

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

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

[0028]

[0029] Preferably, the standard curve is:

[0030] C=aL+b (6)

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

[0032] Preferably, the S2 includes:

[0033] S21, adding ultrapure water to the sample injection cup (1), heating it with the heater (2) to form an ultrapure water sample, and then sending it to the luminescent dish (4);

[0034] S22, performing a dosing process of dosing, comprising: adding an ammonium ferrous sulfate solution (9) contained in a reagent bottle D to the luminescent dish (4), adding an oxalic acid solution (8) contained in a reagent bottle C after the ultrapure water sample and the ammonium ferrous sulfate solution (9) are mixed and reacted, and then adding an ammonium molybdate solution (6) contained in a reagent bottle A and a sulfuric acid solution (7) contained in a reagent bottle B to form a first color-developing solution;

[0035] S23, the light source (3) emits stable monochromatic light, which is absorbed by the first color-developing solution through the luminescent dish (4) and converted into transmitted light, which 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 which point a 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 to the sample injection cup (1) in sequence, heating them with the heater (2) to form a first standard liquid sample and a second standard liquid sample, and sending the first standard liquid sample and the second standard liquid sample into the luminescent dish (4);

[0037] S25, performing a normal dosing process for colorimetric measurement, comprising: adding an ammonium molybdate solution (6) contained in a reagent bottle A and a sulfuric acid solution (7) contained in a reagent bottle B to the luminescent dish (4), adding an oxalic acid solution (8) contained in a reagent bottle C after a mixed reaction for 5 minutes, and then adding an ammonium ferrous sulfate solution (9) contained in a reagent bottle D after 1 minute, and allowing to stand for 8 minutes to form a second color-developing solution;

[0038] S26, the light source (3) emits stable monochromatic light, the monochromatic light passes through the luminescent dish (4) and is absorbed by the second color-developing solution to become 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 which time the voltage values ​​V1 and V2 corresponding to the silicate concentrations in the first standard liquid C1 and the second standard liquid C2, respectively, are obtained;

[0039] S27, adding ultrapure water, a first standard liquid, and a second standard liquid sequentially into the sample injection cup (1), heating the mixture with the heater 2 to form a mixed sample, and sending the mixed sample into the luminescent dish (4);

[0040] S28, this process is a chemical reaction that produces light by itself, 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 first added to the luminous dish 4, and the ammonium molybdate solution (6) and the sulfuric acid solution (7) are mixed with the mixed sample for 1 minute to form a stable silicomolybdenum heteropoly acid solution, and the alkaline luminol solution (10) contained in the reagent bottle E is added to produce a chemical reaction and emit radiation, which 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 ​​corresponding to the silicate concentrations 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;

[0041] S29, fitting the obtained data with the standard curve through corresponding processing to obtain a calibration standard curve formula, thereby completing the calibration of the colorimetric-chemiluminescent instrument.

[0042] Preferably, the S3 includes:

[0043] S31, confirming that the light source (3) is in an off state, adding the water sample to be tested into the sample injection cup (1), heating it with the heater (2) to form a water sample to be tested, and sending the water sample to be tested into the luminous dish (4);

[0044] S32, first add the ammonium molybdate solution (6) contained in the reagent bottle A and the sulfuric acid solution (7) contained in the reagent bottle B to the luminescent dish 4, the water sample to be tested is mixed with the ammonium molybdate solution (6) and the sulfuric acid solution (7) for 1 minute to form a stable silicomolybdenum heteropoly acid solution, and the alkaline luminol solution (10) contained in the reagent bottle E is added 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 then transmitted to the data acquisition and processing module (11), at this time, the measured voltage value L corresponding to the sample to be tested is obtained, and the silicate concentration C in the sample is calculated according to the standard curve (6).

[0045] The second aspect of the present invention is to provide a silicate detection system based on colorimetry-chemiluminescence, which is used to implement the method of the first aspect, comprising:

[0046] A standard curve establishment module (101) is used to establish a standard curve for a colorimetric-chemiluminescence instrument based on a reverse dosing method;

[0047] A combined calibration module (102), configured to calibrate the colorimetric-chemiluminescent instrument based on the standard curve;

[0048] The concentration measurement module (103) is used to measure the silicate concentration based on a calibrated colorimetric-chemiluminescence instrument.

[0049] The third aspect of the present invention is to provide a silicate detection device based on colorimetry and chemiluminescence, which is used to implement the method of the first aspect, comprising:

[0050] A sampling cup (1), a heater (2), a light source (3), a luminescent dish (4), a photomultiplier tube (5), a solution holding component, and a data acquisition and processing module (11), wherein the sampling cup (1) is connected to the heater (2), 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 absorbed by a color-developing solution, and the light source (3) is turned off to form radiated light generated by the reaction between the solution and the water sample to be tested, the transmitted light and / or the radiated light are received by the photomultiplier tube (5), amplified and converted into electrical signals, and then transmitted to the data acquisition and processing module (11); the solution holding component is connected to the luminescent dish (4).

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

[0052] The silicate detection method, system, and device based on colorimetry-chemiluminescence combination of the present invention have the following beneficial effects:

[0053] (1) It was the first time to propose the combination of colorimetry and chemiluminescence to eliminate the shortcomings of the two methods;

[0054] (2) The design of the colorimetric-chemiluminescence instrument fully considers the common requirements of colorimetry and chemiluminescence in terms of reagents, optical paths, etc., without causing a significant increase in costs;

[0055] (3) Solve the problem of slow measurement speed of traditional colorimetric method; high detection sensitivity and lower detection limit;

[0056] (4) Solved the problem that chemiluminescence method cannot eliminate the background silicon effect; BRIEF DESCRIPTION OF THE DRAWINGS

[0057] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in related technologies, the following briefly introduces the drawings required for use in the specific embodiments or related technical descriptions. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0058] Figure 1 Schematic diagram of the principle of the silicate detection method based on colorimetry-chemiluminescence provided in an embodiment of the present invention;

[0059] Figure 2 A schematic flow chart of a silicate detection method based on colorimetry-chemiluminescence provided in an embodiment of the present invention;

[0060] Figure 3 Flow chart of step S1 of the silicate detection method based on colorimetry-chemiluminescence provided in an embodiment of the present invention;

[0061] Figure 4 Flowchart of step S3 of the silicate detection method based on colorimetry-chemiluminescence provided in an embodiment of the present invention;

[0062] Figure 5 This is a schematic diagram of the principle architecture of a silicate detection system based on colorimetry and chemiluminescence provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0063] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0064] In the description of the present invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings and are intended solely to facilitate and simplify the description of the present invention. They are not intended to indicate or imply that the devices or components referred to must have, be constructed, or operate in a specific orientation, and therefore should not be construed as limitations on the present 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 the present invention, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood in a broad sense. For example, they may refer to fixed, detachable, or integral connections; mechanical or electrical connections; direct or indirect connections through an intermediate medium; and internal communication between two components. Those skilled in the art will understand the specific meanings of the above terms in the present 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 colorimetry-chemiluminescence, comprising:

[0068] S1, establish the standard curve of colorimetry-chemiluminescence instrument based on the reverse dosing method;

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

[0070] S11, adding ultrapure water to the colorimetric system by reverse dosing, and then measuring and processing, thereby measuring the voltage value V0 corresponding to the silicate concentration in the ultrapure water;

[0071] S12, preparing a first standard liquid and a second standard liquid of two concentrations, adding the first standard liquid and the second standard liquid to the colorimetric system using a normal dosing process, and then measuring and processing them, thereby measuring voltage values ​​V1 and V2 corresponding to the silicate concentrations in the first standard liquid and the second standard liquid, respectively;

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

[0073] S14, sequentially adding the first standard liquid and the second standard liquid to the chemiluminescence system for measurement, wherein the voltage values ​​corresponding to the silicate concentrations in the first standard liquid and the second standard liquid are measured to be L1 and L2, respectively;

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

[0075] Since a certain amount of background silicon is inevitably present in ultrapure water, the actual concentrations of the first standard liquid and the second standard liquid configured in the actual calibration process are calculated as shown in the following formulas (1) and (2):

[0076] C ′ 1=C1+n1C0+(1-n1)X (1)

[0077] C ′ 2=C2+n2C0+(1-n2)X (2)

[0078] Where: C1 and C2 are the theoretical concentrations of the first and second standard liquids; C'1, C ′ 2 is the actual concentration of the first and second standard liquids; C0 is the certified national standard material for silicate; n1 and n2 are the dilution coefficients of the first and second standard liquids; and X is the background silicon concentration in ultrapure water. Typically, the concentration of the standard solution is in the mg level, and the required standard liquid is in the ug level. Therefore, the dilution coefficient is small, and the above equation can be simplified to equations (3) and (4):

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

[0080] C ′ 2=C2+X (4);

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

[0082]

[0083] S17, based on the background silicon concentration X in the ultrapure water, the voltage value L0 corresponding to the silicate concentration in the ultrapure water, the actual concentration C of the first standard liquid and the second standard liquid ′ 1, C'2, the voltage values ​​L1 and L2 corresponding to the silicate concentration in the first standard liquid and the second standard liquid, the relationship between silicate concentration and voltage value (X, L0)(C'1, L1)(C ′ 2, L2) standard curve:

[0084] C=aL+b (6)

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

[0086] Beneficial effects of step S1: By establishing a standard curve for eliminating the influence of background silicon by the chemiluminescence method, the influence of background silicon in ultrapure water on calibration is eliminated, the accuracy of detection is improved, the detection limit is reduced, and the detection sensitivity is enhanced.

[0087] S2, calibrating the colorimetric-chemiluminescent instrument based on the standard curve;

[0088] As a preferred embodiment, the S2 includes:

[0089] S21, adding ultrapure water to the sample cup 1, heating it with the heater 2 to form an ultrapure water sample which is then fed into the luminescent dish 4;

[0090] S22, performing a dosing process of dosing, including: adding an ammonium ferrous sulfate solution 9 contained in a reagent bottle D to the luminescent dish 4, mixing the ultrapure water sample with the ammonium ferrous sulfate solution 9, and then adding an oxalic acid solution 8 contained in a reagent bottle C, and then adding an ammonium molybdate solution 6 contained in a reagent bottle A and a sulfuric acid solution 7 contained in a reagent bottle B to form a first color-developing solution;

[0091] S23, the light source 3 emits stable monochromatic light, which is absorbed by the first color-developing solution through the luminescent dish 4 and converted into 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, sequentially adding the first standard liquid and the second standard liquid into the sample injection cup 1, heating them with the heater 2 to form a first standard liquid sample and a second standard liquid sample, and feeding the first standard liquid sample and the second standard liquid sample into the luminescent dish 4;

[0093] S25, performing a normal colorimetric measurement dosing process, including: adding an ammonium molybdate solution 6 contained in a reagent bottle A and a sulfuric acid solution 7 contained in a reagent bottle B to the luminescent dish 4, mixing and reacting for 5 minutes, adding an oxalic acid solution 8 contained in a reagent bottle C, and then adding an ammonium ferrous sulfate solution 9 contained in a reagent bottle D after 1 minute, and letting it stand for 8 minutes to form a second color-developing solution;

[0094] S26, the light source 3 emits stable monochromatic light, which is absorbed by the second color-developing solution through the luminescent dish 4 and converted into 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, respectively, are obtained.

[0095] S27, adding ultrapure water, a first standard liquid, and a second standard liquid sequentially into the sample injection cup 1, heating the mixture with the heater 2 to form a mixed sample, and feeding the mixed sample into the luminescent dish 4;

[0096] S28, this process is a chemical reaction of self-luminescence, 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 first added to the luminescent dish 4, and the ammonium molybdate solution 6 and the sulfuric acid solution 7 are mixed with the mixed sample for 1 minute to form a stable silicomolybdenum heteropoly acid solution, and the alkaline luminol solution 10 contained in the reagent bottle E is added to produce a chemical reaction and emit radiated light, which 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 ​​corresponding to the silicate concentrations 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, fitting the obtained data with the standard curve through corresponding processing to obtain a calibration standard curve formula, thereby completing the calibration of the colorimetric-chemiluminescent instrument.

[0098] Beneficial effect of step S2: After the 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, silicate concentration was measured based on a calibrated colorimetric-chemiluminescent instrument.

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

[0101] S31, confirming that the light source 3 is in an off state, adding the water sample to be tested into the sample cup 1, heating it with the heater 2 to form a water sample to be tested, and feeding the water sample to be tested into the luminous dish 4;

[0102] S32, first add 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 luminescent dish 4, the water sample to be tested is mixed with the ammonium molybdate solution 6 and the sulfuric acid solution 7 for 1 minute to form a stable silicomolybdenum heteropolyacid solution, and the alkaline luminol solution 10 contained in the reagent bottle E is added to produce a chemical reaction and emit radiated light, which 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 measured voltage value L corresponding to the sample to be tested is obtained, and 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 colorimetry-chemiluminescence, which is used to implement the method of Example 1, including:

[0105] The standard curve establishment module 101 is used to establish a standard curve for the colorimetric-chemiluminescence instrument based on the reverse dosing method;

[0106] A combined calibration module 102 is used to calibrate the colorimetric-chemiluminescent instrument based on the standard curve;

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

[0108] Example 3

[0109] See again Figure 4 This embodiment provides a silicate detection device based on colorimetry and chemiluminescence, comprising:

[0110] A sampling cup 1, a heater 2, a light source 3, a luminescent dish 4, a photomultiplier tube 5, a solution holding component and a data acquisition and processing module 11, wherein the sampling cup 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 absorbed by the color-developing solution, and the solution reacts with the water sample to form radiated light after the light source 3 is turned off. The transmitted light and / or the radiated light are received by the photomultiplier tube 5, amplified and converted into electrical signals, and then transmitted to the data acquisition and processing module 11; the solution holding component is connected to the luminescent dish 4.

[0111] As a preferred embodiment, the solution holding component 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 sulfate ammonium solution 9, and a reagent bottle E for holding alkaline luminol solution 10, which are arranged in parallel.

[0112] Through the above description of the embodiments, those skilled in the art will clearly understand that the above embodiments can be implemented through software or by using software plus a necessary general-purpose hardware platform. 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, a USB flash drive, a mobile hard disk, etc.) and includes a number of instructions for causing a computer device (such as a personal computer, a server, or a network device) to execute the methods described in 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, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements 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 based on colorimetry-chemiluminescence, characterized in that: include: S1, establish the standard curve of colorimetry-chemiluminescence instrument based on the reverse dosing method; S2, calibrating the colorimetric-chemiluminescent instrument based on the standard curve; S3, silicate concentration was measured based on a calibrated colorimetric-chemiluminescent instrument.

2. The method for detecting silicate based on colorimetry and chemiluminescence according to claim 1, wherein: Said S1 comprises: S11, adding ultrapure water to the colorimetric system by reverse dosing, and then measuring and processing, thereby measuring the voltage value V0 corresponding to the silicate concentration in the ultrapure water; S12, preparing a first standard liquid and a second standard liquid of two concentrations, adding the first standard liquid and the second standard liquid to the colorimetric system using a normal dosing process, and then measuring and processing them, thereby measuring the voltage values ​​corresponding to the silicate concentrations in the first standard liquid and the second standard liquid, respectively; S13, adding ultrapure water to the chemiluminescence system for measurement, and measuring the voltage value corresponding to the silicate concentration in the ultrapure water to be L0; S14, sequentially adding the first standard liquid and the second standard liquid to the chemiluminescence system for measurement, and measuring voltage values ​​corresponding to silicate concentrations in the first standard liquid and the second standard liquid; S15, calculating the actual concentrations of the first standard liquid and the second standard liquid configured during the actual calibration process; S16, based on the colorimetric principle, obtains the background silicon concentration in ultrapure water; S17, based on the background silicon concentration in ultrapure water, the voltage value corresponding to the silicate concentration in the ultrapure water, the actual 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 using the least squares method.

3. A silicate detection method based on colorimetry-chemiluminescence according to claim 2, characterized in that: The actual concentrations of the first standard liquid and the second standard liquid are calculated as shown in the following formulas (1) and (2): C′1=C1+n1C0+(1-n1)X (1) C′2=C2+n2C0+(1-n2)X (2) Where: C1 and C2 are the theoretical concentrations of the first standard liquid and the second standard liquid; C ' 1, C ′ 2 is the actual concentration of the first standard liquid and the second standard liquid; C0 is the national standard substance of silicate with a certificate; n1 and n2 are the dilution coefficients of the first standard liquid and the second standard liquid; X is the background silicon concentration in ultrapure water; the concentration of the standard solution is mg level, and the standard liquid required is ug level. The dilution coefficient can be ignored. The above formula is simplified to formula (3) and formula (4): C ' 1=C1+X (3) C ′ 2=C2+X (4)。 4. The method for detecting silicate based on colorimetry and chemiluminescence according to claim 3, wherein: The expression of the background silicon concentration X in the ultrapure water is as follows:

5. The method for detecting silicate based on colorimetry and chemiluminescence according to claim 4, wherein: The standard curve is: C=aL+b (6) Where: C is the silicate concentration (ug / L); a is the slope obtained by the fitting formula; L is the measured voltage value, in mV; b is the intercept obtained by the least squares fitting.

6. The method for detecting silicate based on colorimetry and chemiluminescence according to claim 5, characterized in that: The S2 includes: S21, adding ultrapure water to the sample injection cup (1), heating it with the heater (2) to form an ultrapure water sample, and then sending it to the luminescent dish (4); S22, performing a dosing process of dosing, comprising: adding an ammonium ferrous sulfate solution (9) contained in a reagent bottle D to the luminescent dish (4), adding an oxalic acid solution (8) contained in a reagent bottle C after the ultrapure water sample and the ammonium ferrous sulfate solution (9) are mixed and reacted, and then adding an ammonium molybdate solution (6) contained in a reagent bottle A and a sulfuric acid solution (7) contained in a reagent bottle B to form a first color-developing solution; S23, the light source (3) emits stable monochromatic light, which is absorbed by the first color-developing solution through the luminescent dish (4) and converted into transmitted light, which 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 which point a voltage value V0 corresponding to the silicate concentration in the ultrapure water is obtained; S24, adding the first standard liquid and the second standard liquid to the sample injection cup (1) in sequence, heating them with the heater (2) to form a first standard liquid sample and a second standard liquid sample, and sending the first standard liquid sample and the second standard liquid sample into the luminescent dish (4); S25, performing a normal dosing process for colorimetric measurement, comprising: adding an ammonium molybdate solution (6) contained in a reagent bottle A and a sulfuric acid solution (7) contained in a reagent bottle B to the luminescent dish (4), adding an oxalic acid solution (8) contained in a reagent bottle C after a mixed reaction for 5 minutes, and then adding an ammonium ferrous sulfate solution (9) contained in a reagent bottle D after 1 minute, and allowing to stand for 8 minutes to form a second color-developing solution; S26, the light source (3) emits stable monochromatic light, the monochromatic light passes through the luminescent dish (4) and is absorbed by the second color-developing solution to become 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 which time the voltage values ​​V1 and V2 corresponding to the silicate concentrations in the first standard liquid C1 and the second standard liquid C2, respectively, are obtained; S27, adding ultrapure water, a first standard liquid, and a second standard liquid sequentially into the sample injection cup (1), heating the mixture with the heater 2 to form a mixed sample, and sending the mixed sample into the luminescent dish (4); S28, this process is a chemical reaction that produces light by itself, 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 first added to the luminous dish 4, and the ammonium molybdate solution (6) and the sulfuric acid solution (7) are mixed with the mixed sample for 1 minute to form a stable silicomolybdenum heteropoly acid solution, and the alkaline luminol solution (10) contained in the reagent bottle E is added to produce a chemical reaction and emit radiation, which 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 ​​corresponding to the silicate concentrations 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, fitting the obtained data with the standard curve through corresponding processing to obtain a calibration standard curve formula, thereby completing the calibration of the colorimetric-chemiluminescent instrument.

7. The method for detecting silicate based on colorimetry and chemiluminescence according to claim 6, characterized in that: The S3 includes: S31, confirming that the light source (3) is in an off state, adding the water sample to be tested into the sample injection cup (1), heating it with the heater (2) to form a water sample to be tested, and sending the water sample to be tested into the luminous dish (4); S32, first add the ammonium molybdate solution (6) contained in the reagent bottle A and the sulfuric acid solution (7) contained in the reagent bottle B to the luminescent dish 4, the water sample to be tested is mixed with the ammonium molybdate solution (6) and the sulfuric acid solution (7) for 1 minute to form a stable silicomolybdenum heteropoly acid solution, and the alkaline luminol solution (10) contained in the reagent bottle E is added 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 then transmitted to the data acquisition and processing module (11), at this time, the measured voltage value L corresponding to the sample to be tested is obtained, and the silicate concentration C in the sample is calculated according to the standard curve (6).

8. A silicate detection system based on colorimetry-chemiluminescence, used to implement the method according to any one of claims 1 to 7, characterized in that: include: A standard curve establishment module (101) is used to establish a standard curve for a colorimetric-chemiluminescence instrument based on a reverse dosing method; A combined calibration module (102), configured to calibrate the colorimetric-chemiluminescent instrument based on the standard curve; The concentration measurement module (103) is used to measure the silicate concentration based on a calibrated colorimetric-chemiluminescence instrument.

9. A silicate detection device based on colorimetry-chemiluminescence, used to implement the method according to any one of claims 1 to 7, characterized in that: include: A sampling cup (1), a heater (2), a light source (3), a luminescent dish (4), a photomultiplier tube (5), a solution holding component, and a data acquisition and processing module (11), wherein the sampling cup (1) is connected to the heater (2), 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 absorbed by a color-developing solution, and the light source (3) is turned off to form radiated light generated by the reaction between the solution and the water sample to be tested, the transmitted light and / or the radiated light are received by the photomultiplier tube (5), amplified and converted into electrical signals, and then transmitted to the data acquisition and processing module (11); the solution holding component is connected to the luminescent dish (4).

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

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