A borate ion on-line detection device and method, and a nuclear power plant loop ion on-line detection system and method

Abstract

This invention discloses an online borate ion detection device and method, and an online ion detection system and method for nuclear power plant circuits. The online borate ion detection device includes: an online sample preparation module for preparing standard sample solutions of different concentrations online; a sample module for delivering and pre-treating the sample to be tested; a sample selection module for selecting standard sample solutions or the sample to be tested and injecting them into the borate detection module; an automatic eluent preparation module for preparing the eluent online and delivering it to the borate detection module for elution; and a borate detection module including an ion exclusion chromatography column, wherein the packing material in the ion exclusion chromatography column is a mixed acidic resin packing material containing both sulfonic acid groups and carboxyl groups. This invention enables rapid, low-limit, and accurate measurement of borate ions, meeting the online detection requirements for different ions, including borate, in different circuits.

Description

Technical Field

[0001] This invention belongs to the field of nuclear engineering technology, specifically relating to an online borate ion detection device and method, and an online ion detection system and method for nuclear power plant loops. Background Technology

[0002] In the primary loop of a nuclear power plant, accurate detection of borate ion concentration and Li + Na + K + Mg 2+ Ca 2+ Zn 2+ NH4 + F - Cl – SO4 2- The concentration of cations and anions is crucial for ensuring the safe and stable operation of nuclear power plants.

[0003] Currently, the monitoring of ion concentration in some nuclear reactor coolants mainly relies on daily manual sampling and offline testing, which is inefficient and poses a significant safety risk of radiation exposure to operators.

[0004] For online monitoring, considering the need for online monitoring of different ions in different loops, setting up only one type of online ion monitor in a single loop often fails to meet practical application requirements. However, current primary loop coolant detection still mainly relies on online monitors for borate ions or anions, and simultaneous online detection of multiple ion types has not yet been achieved. Taking borate ion online detection as an example, commonly used methods include neutron absorption spectrometry, potentiometric titration, and chromatography.

[0005] Neutron absorption spectrometry offers advantages such as a wide detection range and low failure rate, but it relies heavily on the stability of the neutron source, requiring high maintenance standards. Furthermore, it suffers from low measurement accuracy, complex and frequent calibration, and the need for periodic calibration, each of which is time-consuming. Potentiometric titration offers high detection accuracy and a wide measurement range, but suffers from insufficient detection limits, failing to accurately analyze levels below 100 ppm. Compared to neutron absorption and potentiometric titration, chromatography offers unique advantages in boric acid detection. Chromatography achieves efficient separation and accurate determination of boric acid by selecting appropriate chromatographic columns and detectors. However, borate ions are weak acid radicals with a low ionization constant (Pka=9.2), making them highly susceptible to pH fluctuations in the eluent. After passing through a suppressor, the detection signal is low and difficult to distinguish from the matrix signal, resulting in a weak detection signal. Current technologies suffer from unsatisfactory detection limits and measurement accuracy. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to address the above-mentioned shortcomings of the prior art by providing an online borate ion detection device and method, and an online ion detection system and method for nuclear power plant circuits, which can realize rapid, low-limit, and accurate measurement of borate ions and meet the online detection needs of different ions, including borate ions, in different circuits.

[0007] The technical solution of the present invention to solve the above-mentioned technical problems is:

[0008] According to a first aspect of the present invention, an online borate ion detection device is provided, comprising an online calibration sample preparation module, a sample module, a sample selection module, an automatic eluent preparation module, and a borate detection module, wherein:

[0009] The online calibration sample preparation module is used to prepare standard sample solutions of different concentrations online.

[0010] The sample module is used to deliver the sample to be tested and for preprocessing.

[0011] The sample selection module is connected to the online calibration sample preparation module, the sample module, and the borate detection module, respectively, and is used to select the standard sample solution or the sample to be tested and inject it into the borate detection module.

[0012] The automatic rinsing solution preparation module is connected to the borate detection module and is used to prepare the rinsing solution required by the borate detection module online.

[0013] The borate detection module is used to quantitatively detect borate ions in the received standard sample solution or the sample to be tested. The borate detection module includes an ion exclusion chromatography column, and the packing material in the ion exclusion chromatography column is a mixed acid type resin packing material in which sulfonic acid groups and carboxyl groups coexist.

[0014] Optionally, the mixed acid resin filler containing both sulfonic acid groups and carboxyl groups is prepared using the following method:

[0015] S101, mix ester monomer A and ester monomer B, add crosslinking agent and porogen, mix, then add initiator, dissolve, and obtain mixed monomer solution;

[0016] S102, Dissolve the dispersant in water to obtain a dispersant solution;

[0017] S103, the mixed monomer solution is added to the dispersant solution, and resin-based spheres with a hydrophilic polymer network are prepared by suspension polymerization.

[0018] S104, The resin-based spheres are functionalized with sulfonic acid groups to form resin-based spheres with sulfonic acid groups on their surface;

[0019] S105, the resin-based spheres with sulfonic acid groups on the surface are hydrolyzed under alkaline conditions to form a mixed acid type resin filler in which sulfonic acid groups and carboxyl groups coexist.

[0020] Optionally, the ester monomer A is one of glycidyl methacrylate, glycidyl acrylate, diglycidyl phthalate, triglycidyl isocyanurate, diglycidyl adipate, and diglycidyl terephthalate.

[0021] Optionally, the ester monomer B is one of methyl methacrylate, methyl acrylate, hydroxyethyl methacrylate, butyl methacrylate, propyl acrylate, butyl acrylate, α-cyanoacrylate, and phenylpropyl acrylate.

[0022] Optionally, the crosslinking agent is one or any combination of divinylbenzene, ethylene glycol dimethacrylate, triallyl isocyanurate, and glyceryl acrylate.

[0023] Optionally, the pore-forming agent is one or any combination of toluene, n-heptane, isooctane, n-octane, and isooctyl alcohol.

[0024] Optionally, the initiator is one or any combination of benzoyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, dimethylaniline, and di-tert-butyl peroxide.

[0025] Optionally, the dispersant is one or any combination of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylate, and carboxymethyl cellulose.

[0026] Optionally, the online calibration sample preparation module includes a standard sample mother liquor bottle, a first selection valve, a second metering pump, and a dilution container. The first end of the first selection valve is connected to the standard sample mother liquor bottle and the pure water tank, respectively, and its end is connected to the second metering pump. The dilution container is connected to the second metering pump and the sample selection module, respectively.

[0027] Optionally, the sample module includes a sample feed line, a first filter, and a degassing device. The first end of the sample feed line is used to introduce the sample to be tested, and the last end is connected to the first filter. The degassing device is connected to the first filter and the sample selection module, respectively.

[0028] Optionally, the automatic rinsing solution preparation module includes a rinsing solution mother liquor bottle, a first metering pump, a pure water pump, a flow meter, and a rinsing solution storage tank. The rinsing solution mother liquor bottle contains rinsing solution mother liquor and is connected to the rinsing solution storage tank via a rinsing solution pipeline. The first metering pump is located on the rinsing solution pipeline. The rinsing solution storage tank is connected to the pure water tank via a pure water pipeline. The pure water pump and the flow meter are sequentially located on the pure water pipeline.

[0029] Optionally, the mother liquor of the rinsing solution is methanesulfonic acid / mannitol or tartaric acid / mannitol.

[0030] According to a second aspect of the present invention, an online detection method for borate ions is also provided, which uses the above-described online borate ion detection device for detection, the steps of which include:

[0031] S201, according to the preset concentration of the standard sample solution, the required volume of ultrapure water and standard stock solution are automatically injected and diluted online using the calibration sample online preparation module to prepare a standard sample solution of the preset concentration.

[0032] S202, the standard sample solution prepared in step S201 is passed through the sample selection module into the borate detection module for quantitative detection to obtain the corresponding conductivity detection value.

[0033] S203, repeat steps S201 and S02 to prepare standard sample solutions of different concentrations, and quantitatively detect borate ions in them to obtain the conductivity detection values ​​of standard sample solutions of different concentrations, and plot calibration curves.

[0034] S204, the sample to be tested is passed into the sample module for pretreatment, and then enters the borate detection module through the sample selection module for quantitative detection to obtain the conductivity detection value of the sample to be tested, form a chromatogram, and perform quantitative calculation according to the calibration curve to obtain the concentration value of borate ions.

[0035] According to a third aspect of the present invention, an online ion detection system for a nuclear power plant loop is also provided, comprising a sample channel selection module and an online ion detection module, wherein:

[0036] The online ion detection module includes multiple online ion detection devices, including the borate ion online detection device described above.

[0037] The sample channel selection module is equipped with multiple sample channel selectors, each of which is connected to an online ion detection device in the online ion detection module. This allows for the selection and matching of different online ion detection devices based on the analytical requirements of ion samples from different nuclear power plant loops.

[0038] Optionally, the system further includes one or more of a sample filtration module, a sample reflux module, a gas-liquid supply module, and a gas-liquid collection module, wherein:

[0039] The sample filtering module is connected to different loops within the nuclear power plant and the sample channel selection module, respectively. It is used to introduce ion samples from different nuclear power plant loops, filter them, and then transport them to the sample channel selection module to select and match the required online ion detection device.

[0040] The sample reflux module is connected to the sample channel selection module and is used to reflux the samples in each loop.

[0041] The gas-liquid supply module is connected to the online ion detection module and is used to provide the gas and liquid required by each online ion detection device.

[0042] The gas-liquid collection module is connected to the online ion detection module and is used for the collection of waste liquid and the emission of waste gas from each online ion detection device.

[0043] Optionally, the online ion detection module includes four or more online ion detection devices, namely an online anion detection device, an online cation detection device, an online zinc ion detection device, and the online borate ion detection device.

[0044] According to a fourth aspect of the present invention, an online ion detection method for a nuclear power plant loop is also provided, which employs the above-described online ion detection system for a nuclear power plant loop, the steps of which include:

[0045] S301 allows users to select and match the required online ion detection device through the sample channel selection module, based on the analysis needs of ion samples from different nuclear power plant loops.

[0046] S302, transport the sample to the required online ion detection device for detection.

[0047] Beneficial effects:

[0048] The borate ion online detection device and method, and the nuclear power plant loop ion online detection system and method of the present invention optimize the device. For example, it uses an ion exclusion chromatography column, corresponding to the ion exclusion chromatography-suppressed conductivity detection method, to determine the borate content. A mixed acidic resin packing material with sulfonic acid groups and carboxyl groups coexisting and exhibiting unique selectivity for boric acid is selected as the chromatographic packing material for the ion exclusion chromatography column. An online calibration sample preparation module is used to automatically prepare and detect the samples required for the calibration curve, completing the plotting of the calibration curve. A sample module and a sample selection module are used to perform degassing, filtration, and other impurity treatment of the samples, and to complete automatic sample injection. An automatic eluent preparation module is used to prepare the eluent required for the boric acid detection module online, which ultimately flows into the boric acid detection module to determine the borate ion content in the sample. This method not only has good reproducibility and is simpler and more convenient to operate, but also has strong radiation resistance and resistance to matrix interference, fast detection speed, good separation, low detection limit, wide measurement range, and high measurement accuracy. Furthermore, it can achieve continuous online monitoring of sample ion content, resulting in higher work efficiency, reduced manual operation, and reduced safety risks to operators from high-irradiation samples.

[0049] Furthermore, by setting up multiple sample channel selectors to match multiple sample pipelines, and configuring various different ion detection channels, including an online borate ion detection device, it can simultaneously receive samples from various sources, such as the primary loop of a nuclear power plant. Based on the online detection requirements of samples from different sources, it can selectively connect to the corresponding ion detection channels, thereby constructing multiple complete online sample detection flow paths that do not interfere with each other, meeting the simultaneous online detection requirements of different ions, including borate ions, in samples from different loops, such as the primary loop of a nuclear power plant. Attached Figure Description

[0050] Figure 1 This is a schematic diagram of the online borate ion detection device in an embodiment of the present invention;

[0051] Figure 2 This is a schematic diagram of the borate detection module in an embodiment of the present invention;

[0052] Figure 3 This is a schematic diagram of the online calibration sample preparation module in an embodiment of the present invention;

[0053] Figure 4 This is a schematic diagram of the sample module and sample selection module in an embodiment of the present invention;

[0054] Figure 5 This is a schematic diagram of the automatic rinsing solution preparation module in an embodiment of the present invention;

[0055] Figure 6 This is a schematic diagram of an online ion detection system for a nuclear power plant loop according to an embodiment of the present invention;

[0056] Figure 7 The spectrum of 0.1 mg / L boric acid test in the embodiments of the present invention;

[0057] Figure 8 The above are superimposed spectra of five different concentrations of boric acid standard samples ranging from 625 mg / L to 10000 mg / L in this embodiment of the invention.

[0058] Figure 9 The standard samples of boric acid with concentrations ranging from 625 mg / L to 10000 mg / L in this embodiment of the invention are used to obtain calibration curves and linearity results for five different concentrations.

[0059] Figure 10 The 50 mg / L boric acid standard sample in this embodiment of the invention is shown in the superimposed spectrum of the 10-needle reproducibility test.

[0060] Figure 11 The data are from a 10-needle reproducibility test of a 50 mg / L boric acid standard sample used in this embodiment of the invention.

[0061] In the diagram: 1-Online calibration sample preparation module; 11-Standard stock solution bottle; 12-First selection valve; 13-Second metering pump; 14-Dilution container;

[0062] 2-Sample module; 21-Sample feed line; 22-First filter; 23-Degassing device;

[0063] 3-Sample selection module;

[0064] 4-Automatic rinsing solution preparation module; 41-Rinsing solution mother liquor bottle; 42-First metering pump; 43-Pure water tank; 44-Pure water pump; 45-Flow meter; 46-Rinsing solution storage tank;

[0065] 5-Borate detection module; 51-Ion exclusion chromatography column; 52-Multi-port injection valve; 53-Conductivity detector; 54-Suppressor; 6-Pure water preparation module;

[0066] 100 - Nuclear power plant loop; 200 - Ion detection unit;

[0067] 110 Sample filtration module; 111 Sample tubing; 112 First shut-off valve; 113 First manual shut-off valve; 114 Second filter;

[0068] 120 - Sample channel selection module; 121 - Sample channel selector;

[0069] 130 - Sample reflux module; 131 - Second manual shut-off valve; 132 - Reflux pipeline;

[0070] 210 - Gas-liquid supply module; 211 - Gas source; 212 - First pressure reducing valve; 213 - Third manual shut-off valve; 214 - Demineralized water supply device; 215 - Second shut-off valve; 216 - Ultrapure water system;

[0071] 220 - Online ion detection module; 221 - Third filter; 222 - Online ion detection device; 2231 - Online anion detection device; 2232 - Online cation detection device; 2233 - Online zinc ion detection device; 2234 - Online borate ion detection device;

[0072] 230 - Gas-liquid collection module; 231 - Second pressure reducing valve; 232 - Third shut-off valve; 233 - Plant exhaust pipe; 234 - Plant waste liquid pipe. Detailed Implementation

[0073] To enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0074] In the description of this invention, it should be noted that the terms "above" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience and simplification of 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 this invention.

[0075] In the description of this invention, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the stated features. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0076] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "connection," "setting," "installation," "fixing," etc., 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 direct connection, an indirect connection through an intermediate medium, or a connection within two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0077] It is understood that, without conflict, the various embodiments and features in the embodiments of the present invention can be combined with each other.

[0078] It is understood that, for ease of description, only the parts related to the present invention are shown in the accompanying drawings, while the parts unrelated to the present invention are not shown in the drawings.

[0079] To address the issues of unsatisfactory detection limits and measurement accuracy in traditional chromatographic methods, this invention provides an online borate ion detection device, comprising an online calibration sample preparation module, a sample module, a sample selection module, an automatic eluent preparation module, and a borate detection module. Specifically: the online calibration sample preparation module is used to prepare standard sample solutions of different concentrations online; the sample module is used for delivering and pre-treating the sample to be tested; the sample selection module, connected to the online calibration sample preparation module, the sample module, and the borate detection module respectively, is used to select standard sample solutions or the sample to be tested and inject them into the borate detection module; the automatic eluent preparation module, connected to the borate detection module respectively, is used to prepare the eluent required by the borate detection module online; and the borate detection module is used to quantitatively detect borate ions in the received standard sample solutions or the sample to be tested, and the borate detection module includes an ion-exclusion chromatography column, the packing material of which is a mixed acidic resin packing material containing both sulfonic acid groups and carboxyl groups.

[0080] Furthermore, the present invention also provides an online detection method for borate ions, which uses the above-described online borate ion detection device for detection, and the steps include:

[0081] S201, based on the preset concentration of the standard sample solution, the calibration sample online preparation module automatically injects and dilutes the required volume of ultrapure water and standard stock solution online to prepare a standard sample solution of the preset concentration.

[0082] S202, the standard sample solution prepared in step S201 is entered into the borate detection module through the sample selection module for quantitative detection to obtain the corresponding conductivity detection value.

[0083] S203, repeat steps S201 and S02 to prepare standard sample solutions of different concentrations, and quantitatively detect borate ions in them to obtain the conductivity detection values ​​of standard sample solutions of different concentrations, and plot calibration curves.

[0084] S204, the sample to be tested is passed into the sample module for pretreatment, and then enters the borate detection module through the sample selection module for quantitative detection to obtain the conductivity detection value of the sample to be tested, form a chromatogram, and perform quantitative calculation according to the calibration curve to obtain the concentration value of borate ions.

[0085] Furthermore, the present invention also provides an online ion detection system for a nuclear power plant loop, including a sample channel selection module and an online ion detection module. The online ion detection module includes multiple online ion detection devices, including the borate ion online detection device described above. The sample channel selection module is equipped with multiple sample channel selectors, and each sample channel selector is connected to an online ion detection device in the online ion detection module through a corresponding sample channel. This is used to select and match different online ion detection devices according to the analysis requirements of different nuclear power plant loop ion samples.

[0086] Furthermore, the present invention also provides an online ion detection method for a nuclear power plant circuit, which uses the above-described online ion detection system for a nuclear power plant circuit for detection, and the steps include:

[0087] S301 allows users to select and match the required online ion detection device through the sample channel selection module, based on the analysis needs of ion samples from different nuclear power plant loops.

[0088] S302, transport the sample to the required online ion detection device for detection.

[0089] The borate ion online detection device and method, and the nuclear power plant loop ion online detection system and method of the present invention can achieve rapid, low-limit, and accurate measurement of borate ions, meeting the online detection needs of different ions, including borate ions, in different loops.

[0090] Example 1

[0091] like Figures 1-5 As shown, this embodiment discloses an online borate ion detection device, including an online calibration sample preparation module 1, a sample module 2, a sample selection module 3, an automatic eluent preparation module 4, and a borate detection module 5, wherein:

[0092] The online calibration sample preparation module 1 is used to prepare standard sample solutions of different concentrations online.

[0093] Sample module 2 is used for transporting and pre-processing the sample to be tested;

[0094] The sample selection module 3 is connected at its first end to the online calibration sample preparation module 1 and the sample module 2 respectively, and at its last end to the borate detection module 5. It is used to select the standard sample solution or the sample to be tested and inject it into the borate detection module.

[0095] The automatic rinsing solution preparation module 4 is connected to the borate detection module 5. It is used to prepare the rinsing solution required by the borate detection module online and deliver it to the borate detection module 5 to provide the required rinsing solution for the borate detection module 5 to perform rinsing.

[0096] The borate detection module 5 is used to quantitatively detect borate ions in the standard sample solution or the sample to be tested flowing into the sample selection module. The borate detection module 5 includes an ion exclusion chromatography column 51, and the packing material in the ion exclusion chromatography column 51 is a mixed acid type resin packing material in which sulfonic acid groups and carboxyl groups coexist.

[0097] Specifically, the boric acid detection module 5 employs a conductivity suppression method for conductivity detection, utilizing an ion-exclusion chromatography column in conjunction with a suppressor and other components, resulting in higher detection sensitivity and accuracy. This boric acid detection module includes a multi-port injection valve 52, an ion-exclusion chromatography column 51, a suppressor 54, and a conductivity detector 53. The first end of the multi-port injection valve 52 is connected to the sample selection module 3 and the automatic eluent preparation module 4, respectively, while its second end is connected to the ion-exclusion chromatography column 51. Suppressor 54 and conductivity detector 53 are sequentially located at the end of ion exclusion chromatography column 51. The inner diameter of ion exclusion chromatography column 51 ranges from 2.0 to 4.6 mm, the column length ranges from 100 to 250 mm, and the column material is PEEK (polyether ether ketone). Suppressor 54 is used to remove the background conductivity of strong electrolytes in the eluent and improve detection sensitivity. Conductivity detector 53 is used to measure the conductivity change of the eluent to obtain ion concentration information. Finally, the data processing system receives the electrical signal output by conductivity detector 53, forms calibration curves or chromatograms, and performs peak identification and quantitative calculations.

[0098] During operation, the prepared standard sample solution or the sample solution to be tested enters the boric acid detection module 5 through the sample selection module 3. The eluent is automatically prepared online by the eluent automatic preparation module 4, continuously supplying eluent to the device. The sample and eluent enter the subsequent ion exclusion column 51 and suppressor 54 through different channels of the multi-port injection valve 52, and finally enter the conductivity detector 53 for detection. Among them, the chromatographic column is a key component in ion chromatography analysis. This device uses an ion exclusion column 51 and a mixed acidic resin packing material with a modified sulfonic acid group and a carboxyl group as the chromatographic packing material, which can achieve more accurate boric acid ion detection.

[0099] In some preferred embodiments, the mixed acidic resin packing material is uniformly packed into the chromatographic column by a high-pressure homogenization method to ensure the uniformity of the packing material and the resolution and repeatability of the chromatographic column.

[0100] In some embodiments, the mixed acid type resin filler with coexisting sulfonic acid groups and carboxyl groups is prepared by the following method:

[0101] S101, Preparation of mixed monomer solution: Mix ester monomer A and ester monomer B, add crosslinking agent and pore-forming agent, mix, then add initiator, dissolve, and obtain mixed monomer solution.

[0102] In some embodiments, ester monomer A is one of glycidyl methacrylate, glycidyl acrylate, diglycidyl phthalate, triglycidyl isocyanurate, diglycidyl adipate, and diglycidyl terephthalate.

[0103] In some embodiments, ester monomer B is one of methyl methacrylate, methyl acrylate, hydroxyethyl methacrylate, butyl methacrylate, propyl acrylate, butyl acrylate, α-cyanoacrylate, and phenylpropyl acrylate.

[0104] In some preferred embodiments, ester monomer A is glycidyl methacrylate, ester monomer B is methyl methacrylate, and the volume ratio of the two is 1:1.

[0105] In some embodiments, the crosslinking agent is one or a combination of several of divinylbenzene, ethylene glycol dimethacrylate, triallyl isocyanurate, and glyceryl acrylate, preferably ethylene glycol dimethacrylate.

[0106] In some embodiments, the pore-forming agent is one or any combination of toluene, n-heptane, isooctane, n-octane, and isooctyl alcohol, with toluene being preferred.

[0107] In some embodiments, the initiator is one or any combination of several of the following: benzoyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, dimethylaniline, and di-tert-butyl peroxide, with benzoyl peroxide being preferred.

[0108] S102, Preparation of dispersant solution: Dissolve the dispersant in water to obtain a dispersant solution.

[0109] In some embodiments, the dispersant is one or any combination of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylate, and carboxymethyl cellulose, preferably polyvinyl alcohol.

[0110] S103, Preparation of resin-based spheres: The mixed monomer solution obtained in step S101 is added to the dispersant solution obtained in step S102, stirred, and resin-based spheres with a hydrophilic polymer network are prepared by suspension polymerization.

[0111] In some preferred embodiments, nitrogen gas is introduced for 30 minutes before the suspension polymerization reaction begins to maintain a nitrogen atmosphere, the stirring speed is 1500 r / min, the reaction temperature is 80°C, and the reaction time is 18 h.

[0112] S104, Functionalization treatment: The resin-based spheres obtained in step S103 are subjected to sulfonic acid functionalization treatment to form resin-based spheres with sulfonic acid groups on the surface.

[0113] In some embodiments, the sulfonic acid functionalization treatment involves sulfonating the resin-based spheres with a sodium sulfite solution to open the epoxy groups (from ester monomer A) on the surface of the resin-based spheres and convert them into sulfonic acid groups (-SO3H), thereby forming resin-based spheres with sulfonic acid groups on their surface.

[0114] The preferred concentration of sodium sulfite is 0.5 mol / L, the preferred reaction temperature is 45℃, and the preferred reaction time is 3 h. Under these conditions, the reaction is mild, ensuring that the prepared filler does not undergo significant swelling while also ensuring that the reaction proceeds fully to obtain sufficient desired sulfonic acid groups.

[0115] S105, Hydrolysis treatment: The resin-based spheres with sulfonic acid groups on the surface obtained in step S104 are hydrolyzed under alkaline conditions to form a mixed acid type resin filler in which sulfonic acid groups and carboxyl groups coexist.

[0116] In some embodiments, the hydrolysis treatment involves placing resin-based spheres with sulfonic acid groups in an alkaline aqueous solution for hydrolysis, causing the ester groups (from ester monomer B) on the surface of the resin-based spheres with sulfonic acid groups to hydrolyze into carboxyl groups (-COOH), thereby obtaining an ion-rejection chromatography packing material in which sulfonic acid groups and carboxyl groups coexist.

[0117] The preferred alkaline aqueous solution is a 0.5 mol / L sodium hydroxide solution, the preferred reaction temperature is 65°C, and the preferred reaction time is 4 hours. Under these conditions, it can be ensured that the resin-based spheres with sulfonic acid groups can undergo the required hydrolysis reaction, and the number of carboxyl groups can be controlled by controlling the hydrolysis reaction conditions, ensuring that the two groups in the final mixed acid resin filler reach a suitable ratio.

[0118] In this embodiment, the ratio of sulfonic acid groups to carboxyl groups in the mixed acid resin packing is 1:0.5 to 1:1.5, preferably 1:1. Extensive experimental verification has shown that the packing material within this specific ratio range exhibits superior resistance to high radiation and strong matrix interference, enabling the optimization of key parameters such as borate ion exclusion chromatographic behavior (retention time, peak symmetry, and capacity factor).

[0119] The packing material in the ion-exclusion chromatography column of this device possesses both sulfonic acid and carboxylic acid functional groups, and the ratio of different functional groups can be adjusted according to the reaction conditions. It is particularly suitable for the detection of borate ion content in environments such as the primary loop of nuclear power plants, offering high resolution, good accuracy, strong radiation resistance, and resistance to matrix interference, resulting in more precise detection results. Furthermore, the preparation method of the packing material in the ion-exclusion chromatography column of this device is simple to operate, with mild and controllable synthesis conditions and high synthesis efficiency.

[0120] In some embodiments, the online calibration sample preparation module 1 includes a standard sample mother liquor bottle 11, a first selection valve 12, a second metering pump 13, and a dilution container 14. The device may also include a pure water preparation module 6. The first end of the first selection valve 12 is connected to the standard sample mother liquor bottle 11 and the pure water tank 43 in the pure water preparation module 6, respectively, and its end is connected to the first end of the second metering pump 13. The dilution container is connected to the end of the second metering pump 13 and the sample selection module 3, respectively.

[0121] Specifically, ultrapure water from the pure water tank 43 flows through an ultrapure water pipeline, and mother liquor from the standard sample mother liquor bottle 11 flows through a mother liquor pipeline, passing through the first selection valve 12 and the second metering pump 13 respectively, before entering the dilution container 14. The second metering pump 13 can accurately meter and deliver preset volumes of ultrapure water and mother liquor; that is, by adding preset volumes of ultrapure water and mother liquor and mixing them evenly in the dilution container 14, a standard sample solution of the corresponding concentration is obtained. The preparation of multiple standard sample solutions of different concentrations can be achieved by obtaining the required volumes of ultrapure water and mother liquor according to preset concentrations and delivering them to the dilution container 14 respectively. After preparing standard sample solutions of different concentrations online using the calibration sample online preparation module 1, they are injected for testing to achieve the determination of the calibration curve. The operation is simple, convenient, and highly accurate.

[0122] By setting up the online calibration sample preparation module 1 in conjunction with the pure water preparation module 6, the online automatic preparation of standard sample solutions used in the calibration curve can be realized. This eliminates the need for manual operation or manual assistance with the preparation instrument in traditional techniques to prepare and store standard sample solutions before use. This method is highly efficient and reduces storage steps. At the same time, the concentration of the standard sample solution is prepared with high accuracy and good consistency, avoiding the adverse effects of dead volume in the preparation instrument on the concentration accuracy of the solution, and ensuring high detection accuracy in subsequent detection processes.

[0123] By setting up the pure water preparation module 6, ultrapure water can be automatically generated and supplied online, eliminating the need for manual replenishment of ultrapure water tanks, making the operation more convenient. At the same time, it can also ensure the cleanliness of ultrapure water and ensure the accuracy of subsequent ion chromatography detection data.

[0124] In some implementations, the pure water preparation module 6 may be an EDI (electrodeionization) device, but it is not limited thereto.

[0125] In some embodiments, the sample module 2 includes a sample feed line 21, a first filter 22, and a degassing device 23. The first end of the sample feed line 21 is used to introduce the sample to be tested, and its end is connected to the first end of the first filter 22. The degassing device 23 is connected to the end of the first filter 22 and the sample selection module 3, respectively.

[0126] Specifically, the sample selection module 3 includes at least one injection selection valve. The first end of the injection selection valve is connected to the end of the dilution container 14 in the online calibration sample preparation module 1 and the end of the degassing device 23 in the sample module 2, respectively. The end of the injection selection valve is connected to the first end of the boric acid detection module 5.

[0127] The sample solution to be tested enters the first filter 22 through the sample feed line 21. This filter removes particulate matter, suspended solids, and other impurities that may interfere with the analytical results or damage the chromatographic system, ensuring sample purity and thus improving the accuracy and sensitivity of the analysis. By setting up the sample module 2 before sample injection and detection, the pre-treatment of the sample to be tested effectively prevents contamination and reduces the impact of potential impurities in the sample on the detection results. Simultaneously, it also protects the subsequent boric acid detection module 5, maintaining its analytical performance.

[0128] The sample solution flowing out of the first filter 22 enters the degassing device 23 for degassing pretreatment to remove dissolved gases contained in the sample solution, eliminate interference from bubbles, maintain a stable flow rate and pressure during transport, and ensure the accuracy of subsequent ion chromatography analysis and the normal operation of the instrument.

[0129] In some embodiments, the first filter 22 can be a needle sample filter, a microporous membrane or a pretreatment column or other filtration device, and the degassing device 23 can be an online degassing device such as vacuum degassing, membrane degassing or heating degassing.

[0130] In some embodiments, the automatic rinsing solution preparation module 4 includes a rinsing solution mother liquor bottle 41, a first metering pump 42, a pure water pump 44, a flow meter 45, and a rinsing solution storage tank 46. The rinsing solution mother liquor bottle 41 contains rinsing solution mother liquor and is connected to the rinsing solution storage tank 46 through a rinsing solution pipeline. The first metering pump 42 is located on the rinsing solution pipeline. The rinsing solution storage tank 46 is connected to the pure water tank 43 in the pure water preparation module 6 through a pure water pipeline. The pure water pump 44 and the flow meter are sequentially located on the pure water pipeline.

[0131] In some embodiments, the mother liquor of the rinsing solution is methanesulfonic acid / mannitol (i.e., a mixed solution of methanesulfonic acid and mannitol) or tartaric acid / mannitol (a mixed solution of tartaric acid and mannitol).

[0132] Specifically, borate ions can react with polyols (such as mannitol) to form a monovalent complex with a ka=5.14, similar to a monovalent anion. When detected by chromatography, conductivity detection has a strong detection signal and good system stability.

[0133] This device generates a monovalent anion with a higher degree of ionization than boric acid by complexing mannitol and borate. Methylsulfonic acid / mannitol or tartaric acid / mannitol is used as the eluent. An online sample pretreatment module is used to remove matrix interference, allowing the sample to be directly injected. The analytes are then separated by an ion exclusion chromatography column, and finally, borate ions are detected by suppressing conductivity.

[0134] It should be noted that the eluent used in the boric acid detection module 5 of this device is a mixed solution of tartaric acid / mannitol or a mixed solution of methanesulfonic acid / mannitol. Currently, it cannot be automatically generated by an eluent generator like conventional cation detection. In order to ensure the continuous operation of the online instrument, the above-mentioned automatic eluent preparation module 4 is set up to ensure a continuous and stable supply of eluent.

[0135] The automatic rinsing solution preparation module 4 can be implemented in various ways. In this device, the automatic rinsing solution preparation module 4 is implemented by using a first metering pump 42 and a flow meter 45. That is, the rinsing solution mother liquor bottle 41 contains a mixed solution of tartaric acid / mannitol or a mixed solution of methanesulfonic acid / mannitol, which is then mixed with pure water and diluted to obtain the required rinsing solution.

[0136] This embodiment also discloses an online detection method for borate ions, which uses the above-described online borate ion detection device for detection, and the steps include:

[0137] S201, based on the preset concentration of the standard sample solution, the calibration sample online preparation module 1 automatically injects and dilutes the required volume of ultrapure water and standard sample stock solution online to prepare a standard sample solution of the preset concentration.

[0138] S202, the standard sample solution prepared in step S201 is entered into the borate detection module 5 through the sample selection module 3130 for quantitative detection, and the corresponding conductivity detection value is obtained.

[0139] S203, repeat steps S201 and S02 to prepare standard sample solutions of different concentrations, and quantitatively detect borate ions in them to obtain the conductivity detection values ​​of standard sample solutions of different concentrations, and plot calibration curves.

[0140] S204, the sample to be tested, which actually needs to be tested in the environment of nuclear power plant primary loop, etc., is passed into sample module 2 for pretreatment (e.g., filtration, degassing), and then enters borate detection module 5 through sample selection module 3 for quantitative detection, to obtain the conductivity detection value of the sample to be tested, form a chromatogram, and perform quantitative calculation according to the calibration curve to obtain the concentration value of borate ions.

[0141] The following is a detailed description of the online borate ion detection device and method described above in this embodiment, using a specific example. The specific parameters are as follows:

[0142] Eluent flow rate: 1.0 mL / min;

[0143] Eluent: 0.25 mmol / L MSA (methanesulfonic acid) + 60 mmol / L mannitol;

[0144] Suppressor: SHY-NB-5 model suppressor;

[0145] Suppression current: 60mA;

[0146] Chromatographic column: SH-HPIEC-2 model chromatographic column, wherein the chromatographic packing material is prepared in the following manner: S101, preparation of mixed monomer solution: glycidyl methacrylate and methyl methacrylate are mixed at a volume ratio of 1:1, ethylene glycol dimethacrylate is added as a solvent, toluene is added, and after mixing, benzoyl peroxide is added as an initiator and dissolved to obtain a mixed monomer solution; S102, preparation of dispersant solution: polyvinyl alcohol is dissolved in water to obtain a dispersant solution; S103, preparation of resin-based spheres: the mixed monomer solution obtained in step S101 is added to the dispersant solution obtained in step S102, stirred, and resin-based spheres with a hydrophilic polymer network are prepared by suspension polymerization. Before the suspension polymerization reaction begins, nitrogen gas is introduced for 30 minutes to maintain nitrogen... The reaction was carried out under an atmospheric atmosphere with a stirring speed of 1500 r / min, a reaction temperature of 80℃, and a reaction time of 18 h; S104, functionalization treatment: using 0.5 mol / L sodium sulfite, the resin-based spheres obtained in step S103 were functionalized with sulfonic acid groups at a temperature of 45℃ for 3 h to form resin-based spheres with sulfonic acid groups on the surface; S105, hydrolysis treatment: using 0.5 mol / L sodium hydroxide solution, the resin-based spheres with sulfonic acid groups on the surface obtained in step S104 were hydrolyzed under alkaline conditions at a temperature of 65℃ for 4 h to form a mixed acidic resin filler with a 1:1 ratio of sulfonic acid groups to carboxyl groups.

[0147] Column temperature: 30℃;

[0148] Pool temperature: 35℃;

[0149] Injection volume: 10µL.

[0150] Test results as follows Figures 7-11 As shown, the detection limit can reach 0.1 mg / L, which is significantly better than the 100 mg / L of the titration method. The precision of the peak area RSD of 10 needles is within 1%, which is also significantly better than the 2.5% of the neutron method.

[0151] In summary, the online borate ion detection device and method of this embodiment, through optimization of the device (for example, using an ion-exclusion chromatography column, corresponding to the ion-exclusion chromatography-suppressed conductivity detection method to determine the borate content, and selecting a mixed acid type resin packing material with sulfonic acid groups and carboxyl groups coexisting and having unique selectivity for boric acid as the chromatographic packing material for the ion-exclusion chromatography column; using an online calibration sample preparation module to realize the automatic preparation and detection of samples required for calibration curves, and to complete the plotting of calibration curves; using a sample module and a sample selection module to realize the degassing, filtration and other impurity treatment of samples, and to complete automatic sample injection; using an automatic eluent preparation module to prepare the eluent required for the boric acid detection module online, which finally flows into the boric acid detection module to realize the determination of borate ion content in the sample), not only has good reproducibility, simpler and more convenient operation, strong radiation resistance and anti-matrix interference, fast detection speed, good separation, low detection limit, wide measurement range and high measurement accuracy, but also can realize online continuous monitoring of sample ion content, resulting in higher work efficiency, reduced manual operation, and reduced safety risks to operators caused by high-irradiation samples.

[0152] Example 2

[0153] like Figure 6 As shown, this embodiment discloses an online ion detection system for a nuclear power plant loop, including a sample channel selection module 120 and an online ion detection module 220. The online ion detection module 220 includes multiple online ion detection devices 222, including the borate ion online detection device 2234 described in Embodiment 1. The sample channel selection module 120 is equipped with multiple sample channel selectors 121. Each sample channel selector 121 is connected to one or more online ion detection devices 222 in the online ion detection module 220 through a corresponding sample channel, i.e., multiple different ion detection channels are configured to select and match different online ion detection devices 222 according to the analysis requirements of different nuclear power plant loop ion samples. Each online ion detection device 222 is used to perform online detection of different samples in different ion detection channels, thereby meeting the detection requirements of different ions, including borate ions, in samples from different loops such as the primary loop of a nuclear power plant.

[0154] In some embodiments, the system further includes one or more of a sample filtration module 110, a sample reflux module 130, a gas-liquid supply module 210, and a gas-liquid collection module 230.

[0155] Specifically, this system is divided into two parts: a nuclear power plant loop 100 and an ion detection unit 200. The nuclear power plant loop 100 includes a sample filtering module 110, a sample channel selection module 120, and a sample reflux module 130. The ion detection unit includes a gas-liquid supply module 210, an online ion detection module 220, and a gas-liquid collection module 230. Specifically: the sample filtering module 110 is connected to different loops within the nuclear power plant and the sample channel selection module 120, respectively, to introduce ion samples from different nuclear power plant loops, filter them, and then deliver them to the sample channel selection module 120 for selection and matching of the required online ion detection device; the sample reflux module 130 is connected to the sample channel selection module 120 and is used to reflux samples from each loop; the gas-liquid supply module 210 is connected to the online ion detection module 220 and is used to provide the gas and liquid required by each online ion detection device; the gas-liquid collection module 230 is connected to the online ion detection module 220 and is used for the collection of waste liquid and the emission of waste gas from each online ion detection device.

[0156] In some embodiments, for different sample sources, the sample filtering module 110 includes multiple sample lines 111, each sample line 111 being independent of each other. Each sample line 111 is equipped with a first shut-off valve 112 and a second filter 114 (e.g., a 15μm filter), used to receive samples from different sources and perform real-time filtering of online samples to facilitate subsequent online ion detection. Furthermore, each sample line 111 may selectively be equipped with a first manual shut-off valve 113 to cooperate with the first shut-off valve 112 and the second filter to complete the filtration.

[0157] In some embodiments, the sample reflux module 130 includes a reflux line 132, which is connected to the sample channel selector 121 in the sample channel selection module through multiple reflux branches. Each reflux branch is provided with a second manual shut-off valve 131, which controls the refluxed sample and allows multiple sample lines to be selectively merged into the reflux line 132.

[0158] In some embodiments, the gas-liquid supply module 210 includes a gas purging pipeline and a demineralized water supply pipeline. The gas purging pipeline includes several purging branches, one end of which is connected to a gas source 211 (generally nitrogen), and the other end of which is connected to a specific online ion detection device in the online ion detection module 220. Each purging branch is equipped with a first pressure reducing valve 212 and a third manual shut-off valve 213 for pressure control and flow path control of the gas purging pipeline. The demineralized water supply pipeline includes several demineralization branches, one end of which is connected to a demineralized water supply device 214, and the other end of which is connected to a specific online ion detection device in the online ion detection module 220. Each demineralization branch is equipped with a second shut-off valve 215 and an ultrapure water device 216 for pipeline control and demineralized water purification treatment.

[0159] In some embodiments, considering the significant differences in properties between borate ions and zinc ions and conventional anions and cations, the chromatographic columns used for conventional anion and cation detection cannot accurately detect borate ions and zinc ions. Therefore, this system uses separately prepared and packed chromatographic columns suitable for borate ions and zinc ions. Specifically, the online ion detection module 220 in this system includes four or more online ion detection devices 222, namely an online anion detection device 2231, an online cation detection device 2232, an online zinc ion detection device 2233, and the aforementioned online borate ion detection device 2234, wherein: each ion online detection... The detection devices 222 are connected to the sample channel selectors 121 in the sample channel selection module 120, and are independent of each other without interference. They are used for online detection of anions, cations, borate, and zinc ions, respectively. They can meet the requirements of simultaneous online monitoring of anions, cations, borate, and zinc ions in samples from multiple different loops of different reactor types. However, the gas and liquid supply, waste liquid collection, and waste gas emission can share equipment. Furthermore, each online ion detection device 222 is equipped with a third filter 221 (e.g., a 5μm filter) between itself and the sample channel selector 121 for secondary filtration of the online samples to prevent blockage of the ion detection module.

[0160] In some embodiments, the gas-liquid collection module 230 includes a gas interface pipeline and a waste liquid interface pipeline. Both the gas interface pipeline and the waste liquid interface pipeline are connected to the respective online ion detection devices 222 in the online ion detection module 220, and are used for waste gas emission and waste liquid collection, respectively. Specifically, the gas interface pipeline is connected to the plant exhaust duct 233, and is equipped with a second pressure reducing valve 231 and a third shut-off valve 232. The waste liquid interface pipeline is directly connected to the plant waste liquid pipeline 234.

[0161] This embodiment also discloses an online ion detection method for a nuclear power plant circuit, which uses the above-described online ion detection system for a nuclear power plant circuit, and includes the following steps:

[0162] S301, according to the analysis requirements of ion samples from different nuclear power plant loops, the required online ion detection device 222 is selected and matched through the sample channel selection module 120;

[0163] S302, the sample is transported to the required online ion detection device 222 for detection.

[0164] The nuclear power plant loop ion online detection system and method of this embodiment, since the system includes the borate ion online detection device described in Embodiment 1, has the same effect as Embodiment 1, and will not be described in detail here. Furthermore, by setting multiple sample channel selectors to match multiple sample pipelines and configuring various different ion detection channels, including the borate ion online detection device, it can simultaneously receive samples from various sources, such as the nuclear power plant primary loop. Based on the online detection requirements of samples from different sources, it selectively connects to the corresponding ion detection channels, thereby constructing multiple complete online sample detection flow paths that do not interfere with each other, meeting the simultaneous online detection requirements of different ions, including borate ions, in samples from different loops, such as the nuclear power plant primary loop.

[0165] It is understood that the above embodiments are merely exemplary implementations used to illustrate the principles of the present invention, and the present invention is not limited thereto. For those skilled in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also considered to be within the scope of protection of the present invention.

Claims

1. An online borate ion detection device, characterized in that, It includes an online calibration sample preparation module, a sample module, a sample selection module, an automatic eluent preparation module, and a borate detection module; The online calibration sample preparation module is used to prepare standard sample solutions of different concentrations online. The sample module is used to deliver the sample to be tested and for preprocessing. The sample selection module is connected to the online calibration sample preparation module, the sample module, and the borate detection module, respectively, and is used to select the standard sample solution or the sample to be tested and inject it into the borate detection module. The automatic rinsing solution preparation module is connected to the borate detection module and is used to prepare the rinsing solution required by the borate detection module online. The borate detection module is used to quantitatively detect borate ions in the received standard sample solution or the sample to be tested. The borate detection module includes an ion exclusion chromatography column, and the packing material in the ion exclusion chromatography column is a mixed acid type resin packing material in which sulfonic acid groups and carboxyl groups coexist.

2. The online borate ion detection device according to claim 1, characterized in that, The mixed acid resin filler containing both sulfonic acid groups and carboxyl groups is prepared by the following method: S101, mix ester monomer A and ester monomer B, add crosslinking agent and porogen, mix, then add initiator, dissolve, and obtain mixed monomer solution; S102, Dissolve the dispersant in water to obtain a dispersant solution; S103, the mixed monomer solution is added to the dispersant solution, and resin-based spheres with a hydrophilic polymer network are prepared by suspension polymerization. S104, The resin-based spheres are functionalized with sulfonic acid groups to form resin-based spheres with sulfonic acid groups on their surface; S105, the resin-based spheres with sulfonic acid groups on the surface are hydrolyzed under alkaline conditions to form a mixed acid type resin filler in which sulfonic acid groups and carboxyl groups coexist.

3. The online borate ion detection device according to claim 2, characterized in that, The ester monomer A is one of glycidyl methacrylate, glycidyl acrylate, diglycidyl phthalate, triglycidyl isocyanate, diglycidyl adipate, and diglycidyl terephthalate.

4. The online borate ion detection device according to claim 2, characterized in that, The ester monomer B is one of methyl methacrylate, methyl acrylate, hydroxyethyl methacrylate, butyl methacrylate, propyl acrylate, butyl acrylate, α-cyanoacrylate, and phenylpropyl acrylate.

5. The online borate ion detection device according to claim 2, characterized in that, The crosslinking agent is one or any combination of divinylbenzene, ethylene glycol dimethacrylate, triallyl isocyanurate, and glyceryl acrylate.

6. The online borate ion detection device according to claim 2, characterized in that, The pore-forming agent is one or any combination of toluene, n-heptane, isooctane, n-octane, and isooctyl alcohol.

7. The online borate ion detection device according to claim 2, characterized in that, The initiator is one or any combination of benzoyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, dimethylaniline, and di-tert-butyl peroxide.

8. The online borate ion detection device according to claim 2, characterized in that, The dispersant is one or any combination of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylate, and carboxymethyl cellulose.

9. The online borate ion detection device according to any one of claims 1-8, characterized in that, The online calibration sample preparation module includes a standard sample stock solution bottle, a first selection valve, a second metering pump, and a dilution container. The first end of the first selection valve is connected to the standard sample mother liquor bottle and the pure water tank respectively, and its end is connected to the second metering pump. The dilution container is connected to the second metering pump and the sample selection module respectively.

10. The online borate ion detection device according to any one of claims 1-8, characterized in that, The sample module includes a sample feed pipeline, a first filter, and a degassing device. The first end of the sample feed pipeline is used to introduce the sample to be tested, and its end is connected to the first filter. The degassing device is connected to the first filter and the sample selection module, respectively.

11. The online borate ion detection device according to any one of claims 1-8, characterized in that, The automatic rinsing solution preparation module includes a rinsing solution mother liquor bottle, a first metering pump, a pure water pump, a flow meter, and a rinsing solution storage tank. The eluent mother liquor bottle contains eluent mother liquor and is connected to the eluent storage tank via an eluent pipeline. The first metering pump is located on the eluent pipeline. The eluent storage tank is connected to the pure water tank via a pure water pipeline. The pure water pump and the flow meter are sequentially located on the pure water pipeline.

12. The online borate ion detection device according to any one of claims 1-8, characterized in that, The mother liquor of the rinsing solution is methanesulfonic acid / mannitol or tartaric acid / mannitol.

13. An online detection method for borate ions, characterized in that, The detection is performed using the online borate ion detection device according to any one of claims 1-12, and the steps include: S201, according to the preset concentration of the standard sample solution, the required volume of ultrapure water and standard stock solution are automatically injected and diluted online using the calibration sample online preparation module to prepare a standard sample solution of the preset concentration. S202, the standard sample solution prepared in step S201 is passed through the sample selection module into the borate detection module for quantitative detection to obtain the corresponding conductivity detection value. S203, repeat steps S201 and S02 to prepare standard sample solutions of different concentrations, and quantitatively detect borate ions in them to obtain the conductivity detection values ​​of standard sample solutions of different concentrations, and plot calibration curves. S204, the sample to be tested is passed into the sample module for pretreatment, and then enters the borate detection module through the sample selection module for quantitative detection to obtain the conductivity detection value of the sample to be tested, form a chromatogram, and perform quantitative calculation according to the calibration curve to obtain the concentration value of borate ions.

14. An online ion detection system for a nuclear power plant loop, characterized in that, It includes a sample channel selection module and an online ion detection module, wherein the online ion detection module includes multiple online ion detection devices, including the borate ion online detection device according to any one of claims 1-12; The sample channel selection module is equipped with multiple sample channel selectors, each of which is connected to an online ion detection device in the online ion detection module. This allows for the selection and matching of different online ion detection devices based on the analytical requirements of ion samples from different nuclear power plant loops.

15. The online ion detection system for nuclear power plant loops according to claim 14, characterized in that, The system also includes one or more of the following: a sample filtration module, a sample reflux module, a gas-liquid supply module, and a gas-liquid collection module; The sample filtering module is connected to different loops within the nuclear power plant and the sample channel selection module, respectively. It is used to introduce ion samples from different nuclear power plant loops, filter them, and then transport them to the sample channel selection module to select and match the required online ion detection device. The sample reflux module is connected to the sample channel selection module and is used to reflux the samples in each loop. The gas-liquid supply module is connected to the online ion detection module and is used to provide the gas and liquid required by each online ion detection device. The gas-liquid collection module is connected to the online ion detection module and is used for the collection of waste liquid and the emission of waste gas from each online ion detection device.

16. The online ion detection system for nuclear power plant loops according to claim 14 or 15, characterized in that, The online ion detection module includes four or more online ion detection devices, namely an online anion detection device, an online cation detection device, an online zinc ion detection device, and an online borate ion detection device.

17. A method for online ion detection in a nuclear power plant loop, characterized in that, The detection is performed using the online ion detection system for the nuclear power plant loop according to any one of claims 14-16, and the steps include: S301 allows users to select and match the required online ion detection device through the sample channel selection module, based on the analysis needs of ion samples from different nuclear power plant loops. S302, transport the sample to the required online ion detection device for detection.

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