Automatic sample preparation device and method of nuclear power station effluent sample strontium-90

Abstract

The invention belongs to the field of chemical analysis of nuclear power plants, and relates to an automatic sample preparation device and method for an effluent sample strontium-90 of a nuclear power plant, the device comprises a water sample treatment module, a water sample preparation module and a water sample column passing module, the sample preparation module is used for carrying out strontium-90 enrichment, precipitation, solid-liquid separation and purification on a water sample and preparing a solid-liquid mixture of the sample; the sample drying constant weight module is used for extracting, weighing and drying a single filter paper, and drying, weighing and storing a sample; the liquid dispatching module is used for dispatching liquid; the pH detection module is used for pH monitoring; the mechanical cooperation device is used for cooperative operation of filter paper transfer and sample transfer; the central control box is used for controlling the water sample treatment module, the water sample preparation module, the water sample column passing module, the sample preparation module, the sample drying constant weight module, the liquid dispatching module, the pH detection module and the mechanical cooperation device. According to the invention, the strontium-90 can be automatically prepared from an environment water sample with relatively low activity concentration and liquid radioactive effluents of nuclear facilities.

Description

Technical Field

[0001] The invention belongs to the field of nuclear power plant chemical analysis, and in particular relates to a device and method for automatically preparing strontium-90 samples from nuclear power plant effluent. Background Art

[0002] Strontium-90 (i.e. 90 Strontium-90 is a fission product of uranium-235 and plutonium-239, mainly derived from nuclear weapon explosions and nuclear reactors. In nuclear power plant reactors, it may enter the reactor's primary circuit due to defects or damage in the fuel cladding, and be discharged into the environment with liquid radioactive effluents. Strontium-90 is a pure beta radioactive nuclide with a half-life of 28.8 years. It is a highly toxic nuclide. Because of its long physical half-life and biological half-life and its long-term deposition in the hematopoietic skeletal system, it replaces calcium and causes radiation sickness (such as leukemia). Therefore, strontium-90 is the most harmful among the radioactive strontium isotopes; at the same time, its daughter yttrium-90 (i.e. 90 The high-energy beta rays produced by Y) can also cause serious damage to the bone marrow.

[0003] Strontium-90 (Sr-90) is one of the most important radionuclides in environmental monitoring and monitoring of liquid radioactive effluents from nuclear facilities. Monitoring the activity concentration of Sr-90 in the surrounding environment and liquid radioactive effluents of nuclear facilities can confirm whether there are any abnormal emissions from nuclear facility operations. It can also be used to assess the potential radiation impact of radioactive material releases from nuclear facilities on the public. Existing techniques generally employ di-(2-ethylhexyl)phosphoric acid extraction chromatography (HJ 815-2016), using a proportional counter for measurement. This analytical method suffers from cumbersome analytical steps and long analysis times. To reduce analytical costs, the development of a rapid and economical method for analyzing Sr-90 in water is essential. 3M (Mumbai, India) has introduced a solid-phase extraction disk (SPE) for the determination of Sr-90 in groundwater samples. Its simple, rapid operation and the use of chemical reagents are essential. However, this solid phase extraction piece is only suitable for treating water bodies with high strontium-90 activity concentration, and is not suitable for treating environmental water samples with low strontium-90 activity concentration and liquid radioactive effluent samples from nuclear facilities.

[0004] At present, there is no automated sample preparation device for measuring strontium-90 in liquid radioactive effluents at home and abroad. In order to improve the efficiency of sample analysis and reduce the potential health and safety hazards to personnel during the sample preparation process, it is necessary to develop an automated sample preparation device for measuring strontium-90 in liquid radioactive effluents, so as to facilitate the measurement of strontium-90 in liquid radioactive effluents from nuclear power plants. Summary of the Invention

[0005] The purpose of the present invention is to provide a device and method for automatically preparing strontium-90 from nuclear power plant effluent samples. The device can automatically prepare strontium-90 from environmental water samples with relatively low activity concentrations and liquid radioactive effluents from nuclear facilities, thereby improving experimental efficiency.

[0006] The technical solution for achieving the purpose of the present invention is as follows:

[0007] A device for automatically preparing strontium-90 from a nuclear power plant effluent sample, the device comprising:

[0008] Water sample processing module, used for enriching and precipitating strontium-90 in water samples;

[0009] The water sample preparation module is used to separate the strontium-90 precipitate from the water sample into solid and liquid to obtain a strontium-90 nitric acid solution, thereby reducing the total amount of liquid that passes through the column later;

[0010] The water sample column module is used to separate and purify the water sample to obtain strontium-90 and yttrium-90 analytical solutions;

[0011] The sample preparation module is used to prepare the solid-liquid mixture of the sample after the reaction with the yttrium-90 analytical solution and perform solid-liquid separation;

[0012] Sample drying and constant weight module, used for single sheet extraction, weighing, filter paper drying, sample drying, sample weighing, and sample storage;

[0013] Liquid scheduling module, used for liquid scheduling in water sample treatment, water sample preparation, water sample column flow, and sample preparation processes;

[0014] pH detection module, used for water sample treatment, water sample preparation and pH monitoring during sample preparation;

[0015] Mechanical coordination device, used for coordinated operation of filter paper transfer during sample preparation and sample transfer during sample drying and constant weight;

[0016] Central control box, used to control the water sample processing module, water sample preparation module, water sample column module, sample preparation module, sample drying and constant weight module, liquid scheduling module, pH detection module, and mechanical coordination device;

[0017] The equipment column frame is used to install the water sample treatment module, water sample preparation module, water sample column module, sample preparation module, sample drying and constant weight module, liquid scheduling module, pH detection module, mechanical coordination device and central control box.

[0018] The water sample treatment module includes: a water sample treatment reactor, a water sample treatment mechanical stirring device, an electric discharge valve of the water sample treatment reactor, a water sample treatment filtration pump, and a water sample treatment high and low temperature circulation pump; the water sample treatment mechanical stirring device is installed on the top of the water sample treatment reactor, the water sample treatment reactor electric discharge valve is installed at the bottom of the water sample treatment reactor, and the water sample treatment filtration pump and the water sample treatment high and low temperature circulation pump are respectively connected to the water sample treatment reactor.

[0019] The water sample preparation module includes: a water sample preparation sand core funnel, a water sample preparation suction filtration receiving bottle, and a glass bottle receiving rack A; the water sample preparation sand core funnel is installed on the glass bottle receiving rack A, and the water sample preparation suction filtration receiving bottle is connected to the bottom of the water sample preparation sand core funnel.

[0020] The water sample column module includes: a glass bottle receiving rack B, a column peristaltic pump, a column liquid sensor, a column switching valve, a chromatography column, a collecting bottle, a chromatography column base, a chromatography column turntable, a pipeline fixing clamp, a liquid storage bottle, and a water sample column module housing; the chromatography column and the column peristaltic pump are installed on the outside of the water sample column module housing, and the column peristaltic pump is connected to the chromatography column; the column switching valve is installed in the water sample column module housing, and the column switching valve is connected to the chromatography column; the top and bottom ends of the outside of the water sample column module housing are respectively installed with column liquid sensors; the bottom of the water sample column module housing is installed with a chromatography column base through the chromatography column turntable; the collecting bottle and the liquid storage bottle are installed on the outside of the water sample column module housing through the glass bottle receiving rack B, and the collecting bottle and the liquid storage bottle are respectively connected to the chromatography column.

[0021] The sample preparation module includes: a sample preparation reactor, an electric discharge valve of the sample preparation reactor, a sample preparation mechanical stirrer, a filter press component, a filter component, a sample preparation suction filtration receiving bottle, and a sample preparation suction filtration pump; the upper and lower ends of the sample preparation reactor are respectively connected to the sample preparation mechanical stirrer and the electric discharge valve of the sample preparation reactor, the electric discharge valve of the sample preparation reactor is sequentially connected to the filter press component, the filter component, and the sample preparation suction filtration receiving bottle through a pipeline, and the sample preparation suction filtration pump is sequentially connected to the filter press component, the filter component, and the sample preparation suction filtration receiving bottle through a pipeline;

[0022] The filter press assembly includes: a filter press motor, a filter press screw guide rail, a filter press motor screw rod, a filter press slide, a slide bracket, a sample preparation filter inlet, a filter upper pressure valve fixing part, a filter upper pressure valve, a filter upper pressure fixing platform, a spring, and a spring pressure-bearing part; the filter press slide is slidably connected to the filter press screw guide rail, the filter press motor is connected to the filter press motor screw rod, the filter press motor screw rod is transmission-connected to the filter press slide, and the filter upper pressure fixing platform is connected to the filter press slide through the slide bracket; the filter press motor drives the filter press motor screw rod, and then drives the filter press slide to move up and down along the filter press screw guide rail to compress the filter paper; the filter upper pressure valve fixing part is fixedly connected to the upper side of the filter upper pressure fixing platform by fasteners, the filter upper pressure valve and the spring pressure-bearing part are connected to the lower side of the filter upper pressure fixing platform from top to bottom by fasteners, and the spring is arranged on the outside of the filter upper pressure valve; the filter upper pressure valve fixing part and the filter upper pressure valve are provided with a through sample preparation filter inlet;

[0023] The filtration assembly includes: a filter funnel, a funnel holder, and a filter nozzle; the funnel holder is installed on a glass bottle receiving frame A, the filter funnel is installed on the funnel holder, a filter nozzle is connected under the filter funnel, and a sample preparation filter receiving bottle is connected under the filter nozzle.

[0024] The sample drying constant weight module includes: a sample drying constant weight device, a sample storage device, and a filter paper extraction device;

[0025] The sample drying constant weight device includes: an electronic balance, an electronic balance fixing part, a filter paper tray, an electronic balance level calibrator, a drying feed port, a drying feed port valve, an imported valve motor, a valve opening sensor, a valve opening sensor port, a valve closing slave sensor, a valve closing slave sensor port, a temperature sensor, an infrared heating tube, a drying component housing fixing part, and a drying component housing; the electronic balance fixing part and the electronic balance level calibrator are installed at the bottom of the electronic balance, a filter paper tray is installed at the top center of the electronic balance, the drying component housing is fixedly installed on the electronic balance through the drying component housing fixing part, the imported valve motor, the temperature sensor, and the infrared heating tube are fixedly installed on the inside of the drying component housing, the valve opening sensor and the valve closing slave sensor are fixed on the top of the drying component housing, the drying feed port, the valve opening sensor port, and the valve closing slave sensor port are provided on the top of the drying component housing, the drying feed port is used to install the filter paper tray, the valve opening sensor port and the valve closing slave sensor port are used to install the valve opening sensor and the valve closing slave sensor to detect the switch valve state;

[0026] The sample storage device includes: a sample storage dish limiting column, a sample storage dish, a storage dish dust cover, a storage motor, a storage slide, a storage bracket fixing part, a storage screw rod, a screw rod motor housing, a storage rack, and a storage sliding tank chain; the sample storage dish limiting column is fixed on the storage rack, and replaceable consumable sample storage dishes and storage dish dust covers are placed on the storage rack; the storage motor, the storage screw rod, and the storage slide are installed on the inner side of the screw rod motor housing, and the storage sliding tank chain is installed above the screw rod motor housing, and an opening is provided above the screw rod motor housing in a direction parallel to the storage screw rod, and the bracket fixing part is installed in the opening, and the storage rack is installed above the storage sliding tank chain; the storage rack is fixed above the storage slide through the storage bracket fixing part, the storage motor is connected to the storage screw rod, and the storage screw rod is transmission-connected to the storage slide; the storage motor drives the storage screw rod to rotate, and the rotation of the storage screw rod drives the storage slide to move, and the movement of the storage slide drives the storage rack to move on the storage sliding tank chain, thereby realizing the movement of the sample storage dish;

[0027] The filter paper extraction device includes: filter paper dust cover fasteners, filter paper dust cover, filter paper conveyor belt, filter paper rack, filter paper box, filter paper outlet, sample storage dish cover rack, sample storage dish limit column, main transmission roller, forward transmission motor, forward transmission wheel, reverse transmission motor, reverse transmission wheel, conveyor belt main motor, filter paper extraction device fixing parts, filter paper extraction device dust cover; forward transmission motor and reverse transmission motor are installed in the filter paper box, and conveyor belt main motor is installed outside the filter paper box. On one side of the extraction device fixing part; the conveyor belt main motor, forward transmission motor, and reverse transmission motor are respectively connected to the main transmission roller, forward transmission wheel, and reverse transmission wheel, and the filter paper conveyor belt is connected to the main transmission roller and the forward transmission wheel; the filter paper extraction device dust cover and the filter paper dust cover are fixed to the roller side of the filter paper extraction device fixing part through the filter paper box and the filter paper dust cover fasteners and the filter paper rack, and the sample storage dish cover rack and the sample storage dish limit column are installed from bottom to top on the top of the filter paper extraction device dust cover.

[0028] The liquid scheduling module includes: a liquid scheduling syringe, a liquid scheduling switching valve, and a water sample peristaltic pump; the liquid scheduling syringe corresponds to the liquid scheduling switching valve up and down, the liquid scheduling syringe discharge port is connected to the central common port of the liquid scheduling switching valve through a closed pipeline, the outer ring output port of the liquid scheduling switching valve is connected to the water sample treatment reactor and the water sample preparation sand core funnel using a closed pipeline, the water sample peristaltic pump is connected to the water sample treatment reactor of the water sample treatment module, the water sample preparation sand core funnel of the water sample preparation module, the chromatographic column of the water sample column module, and the sample preparation reactor of the sample preparation module to add water samples;

[0029] The liquid dispatching syringe includes: a syringe pump slide, a syringe pump clamp, a syringe push rod, a syringe barrel, a syringe fixing part, and a syringe discharge port; the syringe push rod is inserted into the syringe barrel, and the syringe barrel constrains the syringe push rod's freedom so that the syringe push rod only moves up and down, automatically extracting and injecting liquid; a syringe fixing part is provided on the top of the syringe push rod, and the bottom of the syringe barrel is provided at the syringe discharge port; the syringe push rod is fixedly installed under the syringe pump slide by the syringe fixing part, and the syringe barrel is installed under the syringe pump clamp.

[0030] The pH detection module includes: a pH standby pump, a pH standby pump discharge port, a pH standby pump feed port, a pH peristaltic pump, a peristaltic pump discharge port, a pH peristaltic pump feed port, a pH electrode, a pH detection cell, a detection cell feed port, a detection cell discharge port, a detection cell fixture, a pH feed switching valve, a pH discharge switching valve, and a pH detection module housing;

[0031] The pH detection module housing is equipped with a pH standby pump, a pH peristaltic pump, a pH feed switching valve, a pH discharge switching valve, and a detection cell fixture. The pH standby pump is provided with a pH standby pump discharge port and a pH standby pump feed port. The pH peristaltic pump is provided with a peristaltic pump discharge port and a pH peristaltic pump feed port. The pH detection cell is installed on the detection cell fixture. The pH electrode is inserted into the pH detection cell. The outside of the pH detection cell is provided with a detection cell feed port and a detection cell discharge port.

[0032] The central common end of the pH feed switching valve is connected to the feed port of the pH peristaltic pump, the discharge port of the peristaltic pump is connected to the feed port of the detection cell, and the peripheral interface of the pH feed switching valve is connected to the water sample treatment reactor, the sample preparation reactor, and the inlet of the water sample column module collection bottle to circulate and monitor the pH value of the water sample.

[0033] The mechanical coordination device includes: a mechanical coordination Z-axis assembly, a mechanical coordination tank chain, and a mechanical coordination Y-axis assembly; the mechanical coordination Z-axis assembly is fixed to the mechanical coordination Y-axis assembly through a Z-axis clamp, and the mechanical coordination tank chain is fixed on the mechanical coordination Z-axis assembly and laid downward to the top of the mechanical coordination Y-axis assembly.

[0034] A method for automatically preparing strontium-90 from a nuclear power plant effluent sample, the method comprising:

[0035] Step 1: Water sample treatment

[0036] Step 1.1, shake the water sample and measure the water sample into the water sample treatment reactor;

[0037] Step 1.2, adjusting the pH value of the water sample in the water sample treatment reactor for the first time, adjusting the pH value of the water sample to 1.0;

[0038] Step 1.3, adding the strontium carrier and the yttrium carrier to the water sample treatment reactor;

[0039] Step 1.4, adjusting the pH value of the water sample in the water sample treatment reactor for the second time to adjust the pH value of the water sample to 8-9;

[0040] Step 1.5, add to the water sample treatment reactor;

[0041] Step 1.6: Heat the water sample treatment reactor in a water bath to condense the precipitate, turn off the heat, and let it stand overnight;

[0042] Step 2: Water sample preparation

[0043] Step 2.1. Open the electric discharge valve of the water sample treatment reactor, use the water sample preparation sand core funnel to directly transfer and filter using negative pressure, add ammonium carbonate solution to the water sample preparation sand core funnel, wash the precipitate, and discard the clear liquid;

[0044] Step 2.2: Add nitric acid to the water sample preparation sand core funnel until the precipitate is completely dissolved. Turn on the negative pressure, wash the filter paper with nitric acid, collect the filtrate into the water sample preparation suction filtration receiving bottle, and wash the water sample preparation sand core funnel with deionized water. Collect the washing liquid into the water sample preparation suction filtration receiving bottle;

[0045] Step 2.3, transfer the water sample to the water sample treatment reactor through the liquid scheduling module, start the water sample treatment mechanical stirring device, continue stirring, adjust the filtrate pH to 1.0, and obtain a sample solution;

[0046] Step 3: Sample preparation

[0047] Step 3.1: When the sample solution passes through the chromatography column, the column liquid sensor is activated and the column passing date, column loading start time, and column passing completion time are recorded;

[0048] Step 3.2, elute the column with nitric acid and discard the washing solution;

[0049] Step 3.3: Desorb yttrium with nitric acid solution, collect the desorbed liquid in a collection bottle in the water sample column module, and transfer it to the sample preparation reactor through the liquid scheduling module;

[0050] Step 3.4: Add saturated oxalic acid to the sample preparation reactor where the analytical solution is collected, start the sample preparation mechanical stirring, and continue stirring;

[0051] Step 3.5, adjusting the pH value of the sample in the sample preparation reactor to pH = 1.5-2.0;

[0052] Step 3.6, heating the sample preparation reactor in a water bath, turning off the heating, and obtaining a sample precipitate;

[0053] Step 4: Dry and weigh

[0054] Step 4.1. Start the mechanical coordination device to transfer the single filter paper separated by the filter paper extraction device to the filter funnel, start the negative pressure filtration, and add oxalic acid solution, deionized water, and anhydrous ethanol to the sample preparation reactor respectively;

[0055] Step 4.2: Start the mechanical coordination device and place the filter paper after sample filtration and precipitation on the filter paper tray of the sample drying and constant weight device. Start the sample drying and constant weight device, set the temperature, and read the balance value at equal intervals. The value error of 20 consecutive readings is less than 0.0005, which is considered constant weight.

[0056] Start the mechanical coordination device to transfer the dried sample containing the filter paper to the sample storage dish of the sample storage device, cover the dust cover of the storage dish, start the sample storage device to eject the sample box, and the automatic sample preparation is completed.

[0057] The beneficial technical effects of the present invention are:

[0058] 1. The present invention has a highly automated sample preparation process, which reduces manual operations and operates in a negative pressure ventilation environment, thus offering high safety. Water sample pretreatment and preparation are automatically performed through the water sample processing module, the water sample preparation module, and the water sample column module. After the water sample is prepared, the sample is finally prepared through the sample preparation module and the drying constant weight module. The reagents required for the experimental process are automatically extracted and added by the liquid dispatch module, and the consumables required for the experimental process are automatically transferred by the mechanical coordination device.

[0059] 2. The present invention has high-precision process control, and uses temperature sensors and pH detection modules to monitor the status of water samples during the water sample preparation process. Photoelectric sensors and proximity sensors are used to perform closed-loop control of equipment operation.

[0060] 3. The present invention realizes the quantitative extraction and mixing of multiple reagents through the water sample peristaltic pump of the liquid scheduling module, the multi-channel liquid scheduling switching valve and the sensor, and then realizes the quantitative and constant-speed addition of reaction reagents. The entire process is transferred in a closed pipeline. Compared with manual addition, the device of the present invention is safer, more accurate and stable.

[0061] 4. The present invention realizes real-time monitoring of the pH value of water samples during the reaction process through the flow detection pool of the independent loop pH detection module, thereby achieving accurate sample preparation. Compared with manual operation, the device of the present invention can realize non-destructive monitoring in a closed loop.

[0062] 5. The present invention realizes column flow rate control through the column peristaltic pump, standard chromatography column and column liquid sensor of the water sample column module, thereby achieving stable column flow of water samples. Compared with manual visual inspection, the device of the present invention uses sensors for greater accuracy.

[0063] 6. The present invention realizes a high degree of integration of drying and weighing through the sample drying constant weight module. After the sample is automatically placed in the work station by the mechanical coordination device, it can be dried and weighed at the same time, and a complete process curve of the sample drying to constant weight is output. Compared with manual repeated use of the oven and then taking it out for weighing, the device of the present invention eliminates the moisture absorption error and the risk of falling during the sample removal process.

[0064] 7. The present invention is equipped with special software to realize intelligent control, support full process visualization, experimental process customization, experimental result output, equipment status display, automatic stop and alarm when the operation process is abnormal. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 This is a schematic diagram of the overall structure of a strontium-90 automatic sample preparation device for nuclear power plant effluent samples provided by the present invention;

[0066] Figure 2 This is a front view of a strontium-90 automatic sample preparation device for nuclear power plant effluent samples provided by the present invention;

[0067] Figure 3 This is an isometric view of an automatic sample preparation device for strontium-90 of nuclear power plant effluent samples provided by the present invention;

[0068] Figure 4 A top view of a strontium-90 automatic sample preparation device for nuclear power plant effluent samples provided by the present invention;

[0069] Figure 5 This is a schematic diagram of the column frame structure of the device in the present invention;

[0070] Figure 6 Schematic diagram of the water sample processing module structure in the device of the present invention;

[0071] Figure 7 Schematic diagram of the water sample preparation module structure in the device of the present invention;

[0072] Figure 8 This is a front view of the water sample column module in the device of the present invention;

[0073] Figure 9 This is a three-dimensional diagram of the water sample column module in the device of the present invention;

[0074] Figure 10 This is an exploded view of the water sample column module in the device of the present invention;

[0075] Figure 11 Schematic diagram of the structure of the sample preparation module-L reactor in the device of the present invention;

[0076] Figure 12 Schematic diagram of the structure of the sample preparation module-R filter in the device of the present invention;

[0077] Figure 13 This is a structural diagram of the sample drying constant weight module and the sample drying constant weight device in the device of the present invention;

[0078] Figure 14 This is a schematic diagram of the structure of the sample drying constant weight module-sample storage device in the device of the present invention;

[0079] Figure 15 This is a schematic diagram of the structure of the sample drying constant weight module-filter paper extraction device in the device of the present invention;

[0080] Figure 16 Schematic diagram of the structure of the liquid scheduling module in the device of the present invention;

[0081] Figure 17 Schematic diagram of the pH detection module structure in the device of the present invention;

[0082] Figure 18 Schematic diagram of the structure of the mechanical coordination device in the device of the present invention;

[0083] Figure 19 This is a process flow chart of the preparation method in an embodiment of the present invention;

[0084] Figure 20 A schematic diagram of the pipeline connection of the device of the present invention;

[0085] Figure 21 This is a sample drying time-gram weight curve of the sample drying constant weight module in the device of the present invention. DETAILED DESCRIPTION

[0086] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0087] like Figure 1-4 As shown, the present invention provides an automatic sample preparation device for strontium-90 of nuclear power plant effluent samples, including: a water sample processing module 1, a water sample preparation module 2, a water sample column module 3 (or called a chromatographic column array), a sample preparation module 4, a sample drying and constant weight module 5, a liquid scheduling module 6, a pH detection module 7, a mechanical coordination device 8, a central control box 9 and an equipment column frame 10.

[0088] like Figure 5 As shown, the equipment column frame 10 includes: a mechanical stirring support plate 101, a mechanical stirring support member 102, a reactor support plate 103, an equipment structure support plate 104, an equipment structure support member 105, a reactor support member 106, and a fastener 107.

[0089] The mechanical stirring support plate 101, the mechanical stirring support member 102, the reactor support plate 103, and the equipment structure support plate 104 are installed in sequence from top to bottom; a reactor support member 106 is provided between the mechanical stirring support plate 101 and the mechanical stirring support member 102, and a reactor support member 106 is provided between the mechanical stirring support member 102 and the reactor support plate 103; an equipment structure support member 105 is provided between the reactor support plate 103 and the equipment structure support plate 104; the top or bottom ends of the equipment structure support member 105 and the reactor support member 106 and the adjacent components are fixedly connected by fasteners 107 respectively.

[0090] The water sample processing module 1, the water sample preparation module 2, and the water sample column module 3 are installed from top to bottom on the mechanical stirring support 102, the reactor support plate 103, and the equipment structure support plate 104; the sample preparation module 4, the sample drying constant weight module 5, and the mechanical coordination device 8 are installed from left to right on the reactor support plate 103; the pH detection module 7 and the liquid scheduling module 6 are installed from left to right on the equipment structure support plate 104.

[0091] like Figure 2 、 3 As shown in Figure 6, the water sample processing module 1 includes: a water sample processing reactor 11, a water sample processing mechanical stirring device 12, an electric discharge valve 13 for the water sample processing reactor, a water sample processing filtration pump 18, and a water sample processing high and low temperature circulation pump 19.

[0092] In one embodiment, the water sample processing reactor 11 may be 500 mL or 1000 mL.

[0093] A water sample treatment mechanical stirring device 12 is installed on the top of the water sample treatment reactor 11, and a water sample treatment reactor electric discharge valve 13 is installed at the bottom of the water sample treatment reactor 11. A water sample treatment filtration pump 18 and a water sample treatment high and low temperature circulation pump 19 are respectively connected to the water sample treatment reactor 11.

[0094] The water sample processing reactor 11 includes: a water sample processing reactor lock cover 111, a water sample processing reactor cover 112, a water sample inlet 1121, a reagent inlet 1122, a pH extraction port 1123, a pH return port 1124, a reactor jacket inlet and outlet 113, a reactor outlet 114, and a PTFE gasket 116.

[0095] The water sample processing mechanical stirring device 12 includes a polytetrafluoroethylene stirring paddle 121 .

[0096] The electric discharge valve 13 of the water sample treatment reactor includes: a polytetrafluoroethylene discharge valve 131 and a discharge valve locking pin 1311.

[0097] The liquid scheduling module 6 allows the water sample to enter the reactor 11 from the water sample inlet 1121 for treatment, and can perform strontium-90 enrichment and precipitation treatment on 1-3 500mL water samples.

[0098] like Figure 2 、 3 As shown in Figure 7, the water sample preparation module 2 includes: a water sample preparation sand core funnel 21, a water sample preparation suction filtration receiving bottle 22, and a glass bottle receiving rack A108. The water sample preparation sand core funnel 21 is installed on the glass bottle receiving rack A108, and the water sample preparation suction filtration receiving bottle 22 is connected to the bottom of the water sample preparation sand core funnel 21.

[0099] The water sample preparation sand core funnel 21 includes: a sand core reactor cover 211 , a sand core reactor feed port 212 , and a suction filter nozzle 213 .

[0100] The water sample preparation filtration receiving bottle 22 includes: a filtration receiving bottle feed port 221 and a filtration receiving bottle discharge port 222 .

[0101] The water sample preparation module 2 can perform solid-liquid separation on the strontium-90 precipitate produced by water sample treatment to obtain a strontium-90 nitric acid solution, thereby reducing the total amount of liquid that passes through the column later.

[0102] like Figure 8 、 9 As shown in Figure 10, the water sample column module 3 includes: a glass bottle receiving rack B3136, a column peristaltic pump 32, a column liquid sensor 33, a column switching valve 34, a chromatography column, a collecting bottle, a chromatography column base 38, a chromatography column turntable 381, a pipeline fixing clamp 391, a liquid storage bottle, and a water sample column module housing 39.

[0103] The chromatography column and peristaltic pump 32 are mounted outside the water sample column module housing 39, with the column peristaltic pump 32 connected to the chromatography column. A column switching valve 34 is mounted inside the water sample column module housing 39 and connected to the chromatography column. Liquid sensors 33 are mounted at the top and bottom of the water sample column module housing 39, respectively, to monitor the sample's column flow time and determine if the sample volume is abnormal. A chromatography column base 38 is mounted at the bottom of the water sample column module housing 39 via a chromatography column turntable 381. Collection bottles and liquid storage bottles are mounted outside the water sample column module housing 39 via a glass bottle holder B3136, each connected to the chromatography column.

[0104] The chromatography column includes: a chromatography column body 351 , a chromatography column sleeve 352 , a chromatography column fixing frame 3521 , and a chromatography column bracket 3522 .

[0105] The collecting bottle includes: a collecting bottle inlet 361 , a collecting bottle cleaning port 362 , and a collecting bottle liquid outlet 363 .

[0106] The liquid storage bottle includes: a liquid storage bottle feed port 311 , a liquid storage bottle cleaning port 312 , and a liquid storage bottle discharge port 313 .

[0107] The peristaltic pump 32 includes a peristaltic pump feed port 321 and a peristaltic pump discharge port 322 .

[0108] The water sample column module 3 can separate and purify the water sample to obtain strontium-90 and yttrium-90 analytical solutions.

[0109] like Figure 2 、 3 As shown in Figures 11 and 12, the sample preparation module 4 includes: a sample preparation reactor 41, an electric discharge valve 43 for the sample preparation reactor, a sample preparation mechanical stirrer 42, a filter press component, a filter component, a sample preparation suction filtration receiving bottle 47, and a sample preparation suction filtration pump 48.

[0110] The upper and lower ends of the sample preparation reactor 41 are respectively connected to the sample preparation mechanical stirrer 42 and the sample preparation reactor electric discharge valve 43. The sample preparation reactor electric discharge valve 43 is connected to the filter press component, the filter component, and the sample preparation filtration receiving bottle 47 in sequence through pipelines. The sample preparation filtration pump 48 is connected to the filter press component, the filter component, and the sample preparation filtration receiving bottle 47 in sequence through pipelines.

[0111] like Figure 11 The sample preparation module-L reactor in the device of the present invention, Figure 12 The sample preparation module-R filter in the device of the present invention is installed on the sample preparation module-R filter, and the sample preparation module-L reactor is connected with a closed pipeline.

[0112] The sample preparation reactor 41 includes: a sample preparation reactor locking cover 411 , a sample preparation reactor cover 412 , a pH return port 4124 , a reactor jacket inlet and outlet 413 , and a reactor outlet 414 .

[0113] In one embodiment, the sample preparation reactor 41 may be 100 mL.

[0114] The sample preparation mechanical stirring 42 includes a small stirring paddle 421 .

[0115] The electric discharge valve 43 of the reactor includes: a polytetrafluoroethylene discharge valve 431 and a discharge valve locking pin 4311 .

[0116] The filter press assembly includes: a filter press motor 441, a filter press screw guide rail 442, a filter press motor screw 443, a filter press slide 444, a slide bracket 445, a sample preparation filter inlet 4454, a filter upper pressure valve fixing part 432, a filter upper pressure valve 433, a filter upper pressure fixing platform 4451, a spring 4452, and a spring pressure-bearing part 4453.

[0117] The filter press slide 444 is slidably connected to the filter press screw guide rail 442. The filter press motor 441 is connected to the filter press motor screw 443, which is in transmission connection with the filter press slide 444. The filter press upper fixed platform 4451 is connected to the filter press slide 444 via a slide bracket 445. The filter press motor 441 drives the filter press motor screw 443, which in turn drives the filter press slide 444 to move up and down along the filter press screw guide rail 442, thereby compressing the filter paper. The filter press upper pressure valve fixing member 432 is fixedly connected to the upper side of the filter press upper fixed platform 4451 via fasteners 107. The filter press upper pressure valve 433 and the spring pressure member 4453 are connected from top to bottom to the lower side of the filter press upper fixed platform 4451 via fasteners 107. The spring 4452 is located on the outside of the filter press upper pressure valve 433. The filter pressure valve fixing part 432 and the filter pressure valve 433 are provided with a through sample preparation filter inlet 4454 .

[0118] The filtration assembly includes a filter funnel 461, a funnel holder 462, and a filter nozzle 463. The funnel holder 462 is mounted on the glass bottle receiving frame A108, and the filter funnel 461 is mounted on the funnel holder 462. The filter nozzle 463 is connected to the bottom of the filter funnel 461, and the filter nozzle 463 is connected to the sample preparation filter receiving bottle 47.

[0119] The sample preparation filtration receiving bottle 47 includes: a filtration receiving bottle outlet 471 .

[0120] In cooperation with the mechanical coordination device 8, the sample preparation module 4 can prepare a solid-liquid mixture containing an oxalic acid (Y2(C2O4)3·9H2O) sample by reacting the yttrium-90 analytical solution, and perform filter paper filling and solid-liquid separation operations.

[0121] like Figure 2 As shown, the sample drying and constant weight module 5 includes: a sample drying and constant weight device 51 , a sample storage device 52 , and a filter paper extraction device 53 .

[0122] like Figure 13 As shown, the sample drying constant weight device 51 includes: an electronic balance 511, an electronic balance fixing part 5111, a filter paper tray 5112, an electronic balance level calibrator 5117, a drying feed inlet 51211, a drying feed inlet valve 51212, an inlet valve motor 51213, a valve opening sensor 5122, a valve opening sensor port 51221, a valve closing slave sensor 5123, a valve closing slave sensor port 51231, a temperature sensor 51241, an infrared heating tube 51242, a drying component housing fixing part 51291, and a drying component housing 51292.

[0123] The electronic balance fixing part 5111 and the electronic balance level calibrator 5117 are installed at the bottom of the electronic balance 511. The filter paper tray 5112 is installed at the top center of the electronic balance 511. The drying component housing 51292 is fixedly installed on the electronic balance 511 through the drying component housing fixing part 51291. The imported valve motor 51213, the temperature sensor 51241 and the infrared heating tube 51242 are fixedly installed inside the drying component housing 51292. An open valve sensor 5122 and a closed valve slave sensor 5123 are fixed to the top of 1292, and a drying feed port 51211, an open valve sensor port 51221, and a closed valve slave sensor port 51231 are provided on the top of the drying component housing 51292. The drying feed port 51211 is used to install the filter paper tray 5112, and the open valve sensor port 51221 and the closed valve slave sensor port 51231 are used to install the open valve sensor 5122 and the closed valve slave sensor 5123 to detect the status of the switch valve.

[0124] like Figure 14 As shown, the sample storage device 52 includes: a sample storage dish limiting column 5009, a sample storage dish 5211, a storage dish dust cover 5212, a storage motor 5221, a storage slide 5222, a storage bracket fixing part 5223, a storage screw 5224, a screw motor housing 5229, a storage rack 523, and a storage sliding tank chain 5282.

[0125] The sample storage dish limiting column 5009 is fixed on the storage rack 523, and the storage rack 523 is placed with a replaceable consumable sample storage dish 5211 and a storage dish dust cover 5212; the storage motor 5221, the storage screw rod 5224, and the storage slide 5222 are installed on the inner side of the screw motor housing 5229, and the storage sliding tank chain 5282 is installed above the screw motor housing 5229. An opening is provided above the screw motor housing 5229 in a direction parallel to the storage screw rod 5224, and the bracket fixing member 5223 is installed in the opening. The storage rack 523 is arranged above the storage sliding tank chain 5282; the storage rack 523 is fixed above the storage slide 5222 by the storage bracket fixing member 5223, the storage motor 5221 is connected to the storage screw rod 5224, and the storage screw rod 5224 is transmission-connected to the storage slide 5222. The storage motor 5221 drives the storage screw 5224 to rotate. The rotation of the storage screw 5224 drives the storage slide 5222 to move axially along the storage screw 5224. The movement of the storage slide 5222 drives the storage rack 523 and the storage sliding tank chain 5282 to move, thereby realizing the movement of the sample storage dish 5211.

[0126] like Figure 15As shown, the filter paper extraction device 53 includes: a filter paper dust cover fastener 5322, a filter paper dust cover 5323, a filter paper conveyor belt 5324, a filter paper rack 5325, a filter paper box 5326, a filter paper outlet 533, a sample storage dish cover rack 534, a sample storage dish limiting column 5009, a main transmission roller 535, a forward transmission motor 5361, a forward transmission wheel 53611, a reverse transmission motor 5362, a reverse transmission wheel 53621, a conveyor belt main motor 5363, a filter paper extraction device fixing part 537, and a filter paper extraction device dust cover 539.

[0127] The forward transmission motor 5361 and the reverse transmission motor 5362 are installed in the filter paper box 5326, and the conveyor belt main motor 5363 is installed on the side of the filter paper extraction device fixing part 537 outside the filter paper box 5326; the conveyor belt main motor 5363, the forward transmission motor 5361, and the reverse transmission motor 5362 are respectively connected to the main transmission roller 535, the forward transmission wheel 53611, and the reverse transmission wheel 53621, and the filter paper conveyor belt 5324 connects the main transmission roller 535 and the forward transmission wheel 53611; the filter paper extraction device dust cover 539 and the filter paper dust cover 5323 are fixed to the roller side of the filter paper extraction device fixing part 537 through the filter paper box 5326 and the filter paper dust cover fastener 5322 and the filter paper rack 5325; the sample storage dish cover rack 534 and the sample storage dish limiting column 5009 are installed from bottom to top on the top of the filter paper extraction device dust cover 539.

[0128] More than two sheets of filter paper are neatly stacked in the filter paper box 5326. After the filter paper extraction device 53 is started, its conveyor belt main motor 5363 drives the main transmission roller 535 and drives the forward transmission wheel 53611 through the filter paper conveyor belt 5324. At this time, the filter paper conveyor belt 5324 uses friction to apply a thrust to the filter paper at the bottom layer to move toward the filter paper outlet 533. At this time, the reverse transmission motor 5362 drives the reverse transmission wheel 53621 to reversely rub the filter paper at the top layer. An adaptive gap is provided between the reverse transmission wheel 53621 and the filter paper conveyor belt 5324. At this time, the bottom filter paper will pass through the gap to reach the filter paper outlet 533, completing the single sheet of filter paper extraction.

[0129] In cooperation with the mechanical coordination device 8, the sample drying constant weight module 5 completes operations such as single sheet extraction of filter paper, weighing, filter paper drying, sample drying, sample weighing, and sample storage.

[0130] like Figure 2 、 16 As shown, the liquid scheduling module 6 includes: a liquid scheduling syringe 61, a liquid scheduling switching valve 62, and a water sample peristaltic pump 63.

[0131] The liquid scheduling syringe 61 corresponds to the liquid scheduling switching valve 62 up and down, the discharge port of the liquid scheduling syringe 61 is connected to the central common port of the liquid scheduling switching valve 62 through a closed pipeline, the outer ring output port of the liquid scheduling switching valve 62 is connected to the water sample treatment reactor 11 and the water sample preparation sand core funnel 21 using a closed pipeline, and the water sample peristaltic pump 63 is connected to the water sample treatment reactor 11 of the water sample treatment module 1, the water sample preparation sand core funnel 21 of the water sample preparation module 2, the chromatography column of the water sample column module 3, and the sample preparation reactor 41 of the sample preparation module 4 for adding water samples.

[0132] The liquid dispatching syringe 61 includes: a syringe pump slide 6111, a syringe pump fixture 6112, a 10mL syringe push rod 61211, a 10mL syringe barrel 61212, a syringe fixing part 61221, a 25mL syringe push rod 61222, a 25mL syringe barrel 61223, and a syringe discharge port 61224.

[0133] The syringe plunger is inserted into the syringe barrel, which constrains the plunger's freedom of movement, limiting its up-and-down motion to automatic liquid extraction and injection. A syringe fixture 61221 is located at the top of the plunger, while a syringe discharge port 61224 is located at the bottom of the barrel. The syringe plunger includes a 10mL syringe plunger 61211 and a 25mL syringe plunger 61222, while the syringe barrel includes a 10mL syringe barrel 61212 and a 25mL syringe barrel 61223.

[0134] The 10mL syringe push rod 61211 and the 25mL syringe push rod 61222 are fixedly installed under the syringe pump slide 6111 through the syringe fixing part 61221, and the 10mL syringe barrel 61212 and the 25mL syringe barrel 61223 are installed under the syringe pump fixture 6112.

[0135] The liquid dispatch switching valve 62 is a 12-channel switching valve.

[0136] The water sample peristaltic pump 63 includes: a water sample peristaltic pump outlet 6311 and a water sample peristaltic pump inlet 6312 .

[0137] The liquid dispatch module 6 is used for liquid dispatch during processes such as water sample treatment, water sample preparation, and sample preparation. The water sample peristaltic pump 63 is responsible for pumping in the water sample. After the liquid dispatch syringes 61 are connected to the liquid dispatch switching valve 62, since there are five sets of liquid dispatch syringes 61 and the liquid dispatch switching valve 62 is a 12-channel switching valve, this means that a single set can provide 11 types of reagents for a total of 55 reagents. The remaining five channels are connected to the reagent inlets of each reactor (water sample treatment reactor 11, water sample preparation sand core funnel 21, chromatography column, sample preparation reactor 41) to perform reagent addition during processes such as water sample treatment, water sample preparation, water sample column flow, and sample preparation.

[0138] like Figure 2 、 17 As shown, the pH detection module 7 includes: a pH standby pump 71, a pH standby pump outlet 711, a pH standby pump inlet 712, a pH peristaltic pump 72, a peristaltic pump outlet 721, a pH peristaltic pump inlet 722, a pH electrode 73, a pH detection cell 74, a detection cell inlet 741, a detection cell outlet 742, a detection cell clamp 743, a pH feed switching valve 75, a pH discharge switching valve 76, and a pH detection module housing 77.

[0139] The pH detection module housing 77 is equipped with a pH standby pump 71, a pH peristaltic pump 72, a pH feed switching valve 75, a pH discharge switching valve 76, and a detection cell clamp 743. The pH standby pump 71 is provided with a pH standby pump discharge port 711 and a pH standby pump feed port 712. The pH peristaltic pump 72 is provided with a peristaltic pump discharge port 721 and a pH peristaltic pump feed port 722. The pH detection cell 74 is installed on the detection cell clamp 743. The pH electrode 73 is inserted into the pH detection cell 74. The outside of the pH detection cell 74 is provided with a detection cell feed port 741 and a detection cell discharge port 742.

[0140] The central common end of the pH feed switching valve 75 is connected to the pH peristaltic pump feed port 722, the peristaltic pump discharge port 721 is connected to the detection pool feed port 741, and the peripheral interface of the pH feed switching valve 75 is connected to the water sample treatment reactor 11, the sample preparation reactor 41, and the water sample column module 3 collection bottle inlet 361 for cyclic monitoring of the water sample pH value.

[0141] like Figure 2 、 18 As shown, the mechanical coordination device 8 includes: a mechanical coordination Z-axis component 81, a mechanical coordination tank chain 82, and a mechanical coordination Y-axis component 83.

[0142] The mechanical coordination Z-axis assembly 81 includes: a Z-axis motor 811 , a Z-axis housing 812 , a Z-axis slide 813 , a slide fixture 814 , a pneumatic interface 815 , and a suction cup 816 .

[0143] The mechanical coordination Y-axis assembly 83 includes: a Y-axis motor 831 , a Y-axis housing 832 , a Y-axis slide 833 , and a Z-axis fixture 834 .

[0144] The mechanical coordination Z-axis assembly 81 is fixed to the mechanical coordination Y-axis assembly 83 via the Z-axis fixture 834. The mechanical coordination tank chain 82 is fixed to the mechanical coordination Z-axis assembly 81 and laid down above the mechanical coordination Y-axis assembly 83. A negative pressure air source is connected to the pneumatic interface 815, and the suction cup 816 is attached to the filter paper to achieve negative pressure suction and transfer of the filter paper.

[0145] The mechanical coordination device 8 is used for coordinated operations of filter paper transfer during sample preparation and sample transfer during sample drying and constant weight.

[0146] The central control box 9, which serves as an equipment power control, data center, and industrial control collection, is respectively connected to the water sample processing module 1, the water sample preparation module 2, the water sample column module 3, the sample preparation module 4, the sample drying and constant weight module 5, the liquid scheduling module 6, the pH detection module 7, and the mechanical coordination device 8, and is used to control the water sample processing module 1, the water sample preparation module 2, the water sample column module 3, the sample preparation module 4, the sample drying and constant weight module 5, the liquid scheduling module 6, the pH detection module 7, and the mechanical coordination device 8.

[0147] The sample preparation method using the device provided by the present invention specifically includes the following steps:

[0148] Step 1: Water sample treatment

[0149] Step 1.1, shake the liquid effluent sample (ZLD) of the nuclear power plant nuclear island evenly, and measure 500 mL of the water sample into the water sample treatment reactor 11;

[0150] Start the water sample peristaltic pump 63 in the liquid scheduling module, set the flow rate to 100 mL / min, and shake the ZLD water sample;

[0151] 500 mL of ZLD water sample a1 was measured and put into the water sample treatment reactor 11 (1000 mL beaker), and the water sample treatment mechanical stirring device 12 was turned on and the speed was set to 200 rpm for continuous stirring.

[0152] Step 1.2: Adjust the pH value of the water sample in the water sample treatment reactor 11 for the first time: start the pH detection cell 74 and use 6M nitric acid at a flow rate of 0.5-1 mL / min to adjust the pH value of the water sample to 1.0.

[0153] Step 1.3: Add 2 mL of strontium carrier and 1 mL of yttrium carrier to the water sample treatment reactor 11.

[0154] Step 1.4, second adjustment of the pH value of the water sample in the water sample treatment reactor 11: start the pH detection cell 74, and use ammonia water at a flow rate of 0.5-1 mL / min to adjust the pH value of the water sample to 8-9.

[0155] Step 1.5: Add 4 g of ammonium carbonate to the water sample treatment reactor 11 and wait for 3 minutes.

[0156] Step 1.6: Heat the water sample treatment reactor in a water bath at 11 to 115°C, wait for 30 minutes to allow the precipitate to condense, turn off the heat, and let it stand overnight.

[0157] Step 2: Water sample preparation

[0158] Step 2.1. Open the electric discharge valve 13 of the water sample treatment reactor, use the water sample preparation sand core funnel 21 to directly transfer and filter using negative pressure, add 1% (m / m) ammonium carbonate solution to the water sample preparation sand core funnel 21, wait for 2 minutes, wash the precipitate, and discard the clear liquid.

[0159] Step 2.2. Add 30 mL of 6 M nitric acid to the water sample preparation sand core funnel 21, wait for 2 minutes until the precipitate is completely dissolved, turn on the negative pressure, wash the filter paper with 10 mL of 0.5 M nitric acid, collect the filtrate into the water sample preparation suction filtration receiving bottle 22, and wash the water sample preparation sand core funnel 21 with 10 mL of deionized water, and collect the washing liquid into the water sample preparation suction filtration receiving bottle 22.

[0160] Step 2.3: Transfer the water sample to the water sample treatment reactor 11 through the liquid scheduling module 6, start the water sample treatment mechanical stirring device 12, set the speed to 200 rpm for continuous stirring, and adjust the pH of the filtrate to 1.0 with ammonia water to obtain a sample solution.

[0161] Step 3: Sample preparation

[0162] Step 3.1: The sample solution passes through the HDEHP-KeL-F column. The column liquid sensor 33 is activated, the flow rate is controlled at 2 mL / min, and the column is waited for 30 minutes. The column date, column loading start time, and column completion time are recorded.

[0163] Step 3.2: Elute the column with 40 mL of 1.5 M nitric acid at a flow rate of 2 mL / min, wait 23 min, and discard the washing solution.

[0164] Step 3.3: Desorb yttrium with 30 mL of 6 M nitric acid solution at a flow rate of approximately 1 mL / min. Collect the desorbed liquid in a collection bottle in the water sample column module 3 and transfer it to the sample preparation reactor 41 via the liquid dispatch module 6.

[0165] Step 3.4: Add 5 mL of saturated oxalic acid to the sample preparation reaction kettle 41 where the analytical solution is collected, start the sample preparation mechanical stirrer 42, set the speed to 200 rpm and continue stirring.

[0166] Step 3.5: Start the pH detection cell 74 and adjust the pH to 1.5-2.0 with ammonia water at a flow rate of 0.5-1 mL / min.

[0167] Step 3.6: Heat the sample preparation reactor 41 in a water bath at 115° C. for 30 min, turn off the heating, and wait for 90 min to obtain sample precipitation.

[0168] Step 4: Dry and weigh.

[0169] Step 4.1. Start the mechanical coordination device 8 to transfer the single filter paper separated by the filter paper extraction device 53 to the filter funnel 461, start the negative pressure filtration, and simultaneously add 10 mL of 0.5% oxalic acid solution to the sample preparation reactor 41, wait for 2 minutes, add 10 mL of deionized water, wait for 2 minutes, add 10 mL of anhydrous ethanol and wait for 2 minutes.

[0170] Step 4.2: Start the mechanical coordination device 8 and place the filter paper after sample filtration and precipitation on the filter paper tray 5112 of the sample drying and constant weight device 51. Start the sample drying and constant weight device 51, set the temperature to 45℃-50℃, read the balance value every 1 minute, and read the value for 20 consecutive times if the error is less than 0.0005, which is considered to be constant weight.

[0171] Whether the sample is completely dried and the drying process monitoring are important indicators for judging whether the experimental results are valid. The device of the present invention adds a visual chart to the experimental results, such as Figure 21 As shown, the stable state of the sample and the equipment is intuitively represented.

[0172] Start the mechanical coordination device 8 to transfer the dried sample containing the filter paper to the sample storage dish 5211 of the sample storage device 52, cover the storage dish dust cover 5212, start the sample storage device 52 to pop out the sample box (including the sample storage dish 5211 and the storage dish dust cover 5212), and the automatic sample preparation is completed.

[0173] Example

[0174] The sample preparation is carried out using the device provided by the present invention. The specific steps of sample preparation are as follows: Figure 19 As shown in FIG, yttrium oxalate samples were automatically prepared by strontium-90. The test data of strontium-90 sample preparation are shown in Table 1.

[0175] Table 1 Strontium-90 sample preparation test data

[0176]

[0177] The data in Table 1 shows that the device successfully prepared 0.0533g of yttrium oxalate sample in the preparation of sample 20240804-TSET-001. The entire process was automated, requiring no human intervention.

[0178] In this embodiment, the configuration table of various raw materials and reagents between devices is shown in Table 2.

[0179] Table 2 Raw materials and reagent configuration

[0180]

[0181]

[0182] The present invention has been described in detail above with reference to the accompanying drawings and embodiments. However, the present invention is not limited to the above embodiments. Various modifications can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention. Any content not described in detail in the present invention may be adapted from existing technologies.

Claims

1. A nuclear power plant effluent sample strontium-90 automatic sample preparation device, characterized in that: The device comprises: A water sample processing module (1) is used for enriching and precipitating strontium-90 in water samples; The water sample preparation module (2) is used to perform solid-liquid separation on the strontium-90 precipitate produced by water sample treatment to obtain a strontium-90 nitric acid solution, thereby reducing the total amount of liquid that passes through the column later; The water sample column module (3) is used to separate and purify the water sample to obtain strontium-90 and yttrium-90 analytical solutions; A sample preparation module (4) is used to prepare a solid-liquid mixture of the sample after the yttrium-90 analytical solution reaction and perform solid-liquid separation; A sample drying and constant weight module (5) is used for extracting a single piece of filter paper, weighing it, drying the filter paper, drying the sample, weighing the sample, and storing the sample; Liquid scheduling module (6), used for liquid scheduling in water sample treatment, water sample preparation, water sample column flow, and sample preparation processes; pH detection module (7), used for water sample treatment, water sample preparation and pH monitoring during sample preparation; A mechanical coordination device (8) is used for coordinated operations of filter paper transfer during sample preparation and sample transfer during sample drying and constant weight; A central control box (9) is used to control the water sample processing module (1), the water sample preparation module (2), the water sample column module (3), the sample preparation module (4), the sample drying and constant weight module (5), the liquid scheduling module (6), the pH detection module (7), and the mechanical coordination device (8); The equipment column frame (10) is used to install a water sample processing module (1), a water sample preparation module (2), a water sample column module (3), a sample preparation module (4), a sample drying and constant weight module (5), a liquid scheduling module (6), a pH detection module (7), a mechanical coordination device (8) and a central control box (9).

2. The automatic sample preparation device for strontium-90 of nuclear power plant effluent samples according to claim 1, characterized in that: The water sample treatment module (1) comprises: a water sample treatment reactor (11), a water sample treatment mechanical stirring device (12), an electric discharge valve (13) for the water sample treatment reactor, a water sample treatment suction filter pump (18), and a water sample treatment high and low temperature circulation pump (19); the water sample treatment mechanical stirring device (12) is installed on the top of the water sample treatment reactor (11), the water sample treatment reactor electric discharge valve (13) is installed on the bottom of the water sample treatment reactor (11), and the water sample treatment suction filter pump (18) and the water sample treatment high and low temperature circulation pump (19) are respectively connected to the water sample treatment reactor (11).

3. The automatic sample preparation device for strontium-90 of nuclear power plant effluent samples according to claim 1, characterized in that: The water sample preparation module (2) comprises: a water sample preparation sand core funnel (21), a water sample preparation suction filtration receiving bottle (22), and a glass bottle receiving frame A (108); the water sample preparation sand core funnel (21) is installed on the glass bottle receiving frame A (108), and the water sample preparation suction filtration receiving bottle (22) is connected to the bottom of the water sample preparation sand core funnel (21).

4. The automatic sample preparation device for strontium-90 of nuclear power plant effluent samples according to claim 1, characterized in that: The water sample column module (3) comprises: a glass bottle receiving frame B (3136), a column peristaltic pump (32), a column liquid sensor (33), a column switching valve (34), a chromatographic column, a collecting bottle, a chromatographic column base (38), a chromatographic column turntable (381), a pipeline fixing clamp (391), a liquid storage bottle, and a water sample column module housing (39); the chromatographic column and the column peristaltic pump (32) are installed on the outside of the water sample column module housing (39), and the column peristaltic pump (32) is connected to the chromatographic column; the column switching valve (34) is connected to the chromatographic column; the chromatographic column and the column peristaltic pump (32) are ... The valve (34) is installed in the water sample column module housing (39), and the column switching valve (34) is connected to the chromatographic column; the top and bottom ends of the outer side of the water sample column module housing (39) are respectively installed with a column liquid sensor (33); the bottom of the water sample column module housing (39) is installed with a chromatographic column base (38) through a chromatographic column turntable (381); the collecting bottle and the liquid storage bottle are installed on the outer side of the water sample column module housing (39) through a glass bottle receiving frame B (3136), and the collecting bottle and the liquid storage bottle are respectively connected to the chromatographic column.

5. The automatic sample preparation device for strontium-90 of nuclear power plant effluent samples according to claim 1, characterized in that: The sample preparation module (4) comprises: a sample preparation reactor (41), an electric discharge valve (43) for the sample preparation reactor, a sample preparation mechanical stirrer (42), a filter press component, a filter component, a sample preparation suction filtration receiving bottle (47), and a sample preparation suction filtration pump (48); the upper and lower ends of the sample preparation reactor (41) are respectively connected to the sample preparation mechanical stirrer (42) and the electric discharge valve (43) for the sample preparation reactor, the electric discharge valve (43) for the sample preparation reactor is sequentially connected to the filter press component, the filter component, and the sample preparation suction filtration receiving bottle (47) through pipelines, and the sample preparation suction filtration pump (48) is sequentially connected to the filter press component, the filter component, and the sample preparation suction filtration receiving bottle (47) through pipelines; The filter press assembly comprises: a filter press motor (441), a filter press screw guide rail (442), a filter press motor screw rod (443), a filter press slide (444), a slide bracket (445), a sample preparation filter inlet (4454), a filter upper pressure valve fixing member (432), a filter upper pressure valve (433), a filter upper pressure fixing platform (4451), a spring (4452), and a spring pressure member (4453); the filter press slide (444) is slidably connected to the filter press screw guide rail (442), the filter press motor (441) is connected to the filter press motor screw rod (443), the filter press motor screw rod (443) is transmission-connected to the filter press slide (444), and the filter upper pressure fixing platform (4451) is connected to the filter press through the slide bracket (445). The filter press motor (441) drives the filter press motor screw rod (443), thereby driving the filter press slide (444) to move up and down along the filter press screw rod guide rail (442) to press the filter paper; the filter upper pressure valve fixing member (432) is fixedly connected to the upper side of the filter upper pressure fixing platform (4451) through the fastener (107); the filter upper pressure valve (433) and the spring pressure member (4453) are connected to the lower side of the filter upper pressure fixing platform (4451) from top to bottom through the fastener (107); the spring (4452) is arranged on the outside of the filter upper pressure valve (433); the filter upper pressure valve fixing member (432) and the filter upper pressure valve (433) are provided with a through sample preparation filter inlet (4454); The filtering component comprises: a filtering funnel (461), a funnel support (462), and a filtering nozzle (463); the funnel support (462) is installed on a glass bottle receiving frame A (108), the filtering funnel (461) is installed on the funnel support (462), the filtering nozzle (463) is connected below the filtering funnel (461), and the filtering nozzle (463) is connected below the sample preparation filtering receiving bottle (47).

6. The automatic sample preparation device for strontium-90 of nuclear power plant effluent samples according to claim 1, characterized in that: The sample drying constant weight module (5) comprises: a sample drying constant weight device (51), a sample storage device (52), and a filter paper extraction device (53); The sample drying constant weight device (51) comprises: an electronic balance (511), an electronic balance fixing part (5111), a filter paper tray (5112), an electronic balance horizontal calibrator (5117), a drying feed port (51211), a drying feed port valve (51212), an inlet valve motor (51213), a valve opening sensor (5122), a valve opening sensor port (51221), a valve closing slave sensor (5123), a valve closing slave sensor port (51231), a temperature sensor (51241), an infrared heating tube (51242), a drying component housing fixing part (51291), and a drying component housing (51292); the electronic balance fixing part (5111) and the electronic balance horizontal calibrator (5117) are installed at the bottom of the electronic balance (5111), a filter paper tray (5112) is installed at the top center of the electronic balance (5111), and the drying component housing (51292) is installed at the bottom of the electronic balance (5111). The housing (51292) is fixedly mounted on the electronic balance (511) through the drying component housing fixing member (51291); an inlet valve motor (51213), a temperature sensor (51241), and an infrared heating tube (51242) are fixedly mounted on the inner side of the drying component housing (51292); an opening valve sensor (5122) and a closing valve slave sensor (5123) are fixed on the top of the drying component housing (51292); a drying feed port (51211), an opening valve sensor port (51221), and a closing valve slave sensor port (51231) are provided on the top of the drying component housing (51292); the drying feed port (51211) is used to mount a filter paper tray (5112); the opening valve sensor port (51221) and the closing valve slave sensor port (51231) are used to mount the opening valve sensor (5122) and the closing valve slave sensor (5123) to detect the state of the switch valve; The sample storage device (52) comprises: a sample storage dish limiting column (5009), a sample storage dish (5211), a storage dish dust cover (5212), a storage motor (5221), a storage slide (5222), a storage bracket fixing member (5223), a storage screw (5224), a screw motor housing (5229), a storage rack (523), and a storage slide tank chain (5282); the sample storage dish limiting column (5009) is fixed on the storage rack (523), and a replaceable consumable sample storage dish (5211) and a storage dish dust cover (5212) are placed on the storage rack (523); the storage motor (5221), the storage screw (5224), and the storage slide (5222) are installed on the inner side of the screw motor housing (5229), and the storage slide tank chain (5282) is installed on the screw motor housing (5229). The screw motor housing (5229) is provided with an opening in a direction parallel to the storage screw (5224), the bracket fixing member (5223) is installed in the opening, and the storage rack (523) is provided above the storage sliding tank chain (5282); the storage rack (523) is fixed above the storage slide (5222) through the storage bracket fixing member (5223), the storage motor (5221) is connected to the storage screw (5224), and the storage screw (5224) is transmission-connected to the storage slide (5222); the storage motor (5221) drives the storage screw (5224) to rotate, the rotation of the storage screw (5224) drives the storage slide (5222) to move, and the movement of the storage slide (5222) drives the storage rack (523) to move on the storage sliding tank chain (5282), thereby realizing the movement of the sample storage dish (5211); The filter paper extraction device (53) comprises: a filter paper dust cover fastener (5322), a filter paper dust cover (5323), a filter paper conveyor belt (5324), a filter paper rack (5325), a filter paper box (5326), a filter paper outlet (533), a sample storage dish cover rack (534), a sample storage dish limiting column (5009), a main transmission roller (535), a forward transmission motor (5361), a forward transmission wheel (53611), a reverse transmission motor (5362), a reverse transmission wheel (53621), a conveyor belt main motor (5363), a filter paper extraction device fixing member (537), and a filter paper extraction device dust cover (539); the forward transmission motor (5361) and the reverse transmission motor (5362) are installed in the filter paper box (5326), and the conveyor belt main motor (5363) is installed in the filter paper box ( 5326) on one side of the outer filter paper extraction device fixing part (537); the conveyor belt main motor (5363), the forward transmission motor (5361), and the reverse transmission motor (5362) are respectively connected to the main transmission roller (535), the forward transmission wheel (53611), and the reverse transmission wheel (53621); the filter paper conveyor belt (5324) connects the main transmission roller (535) and the forward transmission wheel (53611); the filter paper extraction device dust cover (539) and the filter paper dust cover (5323) are fixed to the roller side of the filter paper extraction device fixing part (537) through the filter paper box (5326) and the filter paper dust cover fastener (5322), and the filter paper rack (5325); the sample storage dish cover rack (534) and the sample storage dish limiting column (5009) are installed from bottom to top on the top of the filter paper extraction device dust cover (539).

7. The automatic sample preparation device for strontium-90 of nuclear power plant effluent samples according to claim 1, characterized in that: The liquid dispatching module (6) comprises: a liquid dispatching syringe (61), a liquid dispatching switching valve (62), and a water sample peristaltic pump (63); the liquid dispatching syringe (61) corresponds to the liquid dispatching switching valve (62) in upper and lower positions; the discharge port of the liquid dispatching syringe (61) is connected to the central common port of the liquid dispatching switching valve (62) via a sealed pipeline; the outer ring output port of the liquid dispatching switching valve (62) is connected to the water sample treatment reactor (11) and the water sample preparation sand core funnel (21) via a sealed pipeline; the water sample peristaltic pump (63) is connected to the water sample treatment reactor (11) of the water sample treatment module (1), the water sample preparation sand core funnel (21) of the water sample preparation module (2), the chromatographic column of the water sample column module (3), and the sample preparation reactor (41) of the sample preparation module (4) for adding water samples; The liquid dispatching syringe (61) comprises: a syringe pump slide (6111), a syringe pump fixture (6112), a syringe push rod, a syringe barrel, a syringe fixing part (61221), and a syringe discharge port (61224); the syringe push rod is inserted into the syringe barrel, and the syringe push rod's freedom is constrained by the syringe barrel so that the syringe push rod can only move up and down, automatically extracting and injecting liquid; the syringe push rod is provided with a syringe fixing part (61221) at the top, and the syringe barrel is provided with the syringe discharge port (61224) at the bottom; the syringe push rod is fixedly mounted below the syringe pump slide (6111) through the syringe fixing part (61221), and the syringe barrel is mounted below the syringe pump fixture (6112).

8. The automatic sample preparation device for strontium-90 of nuclear power plant effluent samples according to claim 1, characterized in that: The pH detection module (7) comprises: a pH standby pump (71), a pH standby pump discharge port (711), a pH standby pump feed port (712), a pH peristaltic pump (72), a peristaltic pump discharge port (721), a pH peristaltic pump feed port (722), a pH electrode (73), a pH detection cell (74), a detection cell feed port (741), a detection cell discharge port (742), a detection cell fixture (743), a pH feed switching valve (75), a pH discharge switching valve (76), and a pH detection module housing (77); A pH standby pump (71), a pH peristaltic pump (72), a pH feed switching valve (75), a pH discharge switching valve (76), and a detection cell fixture (743) are installed on the pH detection module housing (77); a pH standby pump discharge port (711) and a pH standby pump feed port (712) are provided on the pH standby pump (71); a peristaltic pump discharge port (721) and a pH peristaltic pump feed port (722) are provided on the pH peristaltic pump (72); a pH detection cell (74) is installed on the detection cell fixture (743); a pH electrode (73) is inserted into the pH detection cell (74); and a detection cell feed port (741) and a detection cell discharge port (742) are provided outside the pH detection cell (74); The central common end of the pH feed switching valve (75) is connected to the pH peristaltic pump feed port (722), the peristaltic pump discharge port (721) is connected to the detection cell feed port (741), and the peripheral interface of the pH feed switching valve (75) is connected to the water sample treatment reactor (11), the sample preparation reactor (41), and the water sample column module (3) collection bottle inlet (361) to perform cyclic monitoring of the water sample pH value.

9. The automatic sample preparation device for strontium-90 of nuclear power plant effluent samples according to claim 1, characterized in that: The mechanical coordination device (8) includes: a mechanical coordination Z-axis component (81), a mechanical coordination tank chain (82), and a mechanical coordination Y-axis component (83); the mechanical coordination Z-axis component (81) is fixed to the mechanical coordination Y-axis component (83) through a Z-axis clamp (834), and the mechanical coordination tank chain (82) is fixed on the mechanical coordination Z-axis component (81) and laid downward to the top of the mechanical coordination Y-axis component (83).

10. A method for automatically preparing strontium-90 from nuclear power plant effluent samples, characterized in that: The method comprises: Step 1: Water sample treatment Step 1.1, shake the water sample and measure the water sample into the water sample treatment reactor (11); Step 1.2, adjusting the pH value of the water sample in the water sample treatment reactor (11) for the first time, adjusting the pH value of the water sample to 1.0; Step 1.3, adding a strontium carrier and a yttrium carrier into the water sample treatment reactor (11); Step 1.4, adjusting the pH value of the water sample in the water sample treatment reactor (11) for the second time, adjusting the pH value of the water sample to 8-9; Step 1.5, add to the water sample treatment reactor (11); Step 1.6, heating the water sample treatment reactor (11) in a water bath to condense the precipitate, turning off the heating, and letting it stand overnight; Step 2: Water sample preparation Step 2.1, open the electric discharge valve (13) of the water sample treatment reactor, use the water sample preparation sand core funnel (21) to directly transfer and filter using negative pressure, add ammonium carbonate solution to the water sample preparation sand core funnel (21), wash the precipitate, and discard the clear liquid; Step 2.2, add nitric acid to the water sample preparation sand core funnel (21) until the precipitate is completely dissolved, turn on the negative pressure, wash the filter paper with nitric acid, collect the filtrate into the water sample preparation suction filtration receiving bottle (22), and wash the water sample preparation sand core funnel (21) with deionized water, and collect the washing liquid into the water sample preparation suction filtration receiving bottle (22); Step 2.3, transfer the water sample to the water sample treatment reactor (11) through the liquid scheduling module (6), start the water sample treatment mechanical stirring device (12), continue stirring, adjust the filtrate pH to 1.0, and obtain a sample solution; Step 3: Sample preparation Step 3.1, the sample solution passes through the chromatography column, the column liquid sensor (33) is activated, and the column passing date, column loading start time, and column passing completion time are recorded; Step 3.2, elute the column with nitric acid and discard the washing solution; Step 3.3, desorbing yttrium with nitric acid solution, collecting the desorbed liquid in a collection bottle in the water sample column module (3), and transferring it to the sample preparation reactor (41) through the liquid scheduling module (6); Step 3.4, add saturated oxalic acid to the sample preparation reaction kettle (41) for collecting the analytical solution, start the sample preparation mechanical stirring (42), and continue stirring; Step 3.5, adjusting the pH value of the sample in the sample preparation reaction vessel (41) to pH = 1.5-2.0; Step 3.6, heating the sample preparation reactor (41) in a water bath, turning off the heating, and obtaining a sample precipitate; Step 4: Dry and weigh Step 4.1, start the mechanical coordination device (8) to transfer the single filter paper separated by the filter paper extraction device (53) to the filter funnel (461), start the negative pressure filtration, and add oxalic acid solution, deionized water, and anhydrous ethanol to the sample preparation reactor (41) respectively; Step 4.2, start the mechanical coordination device (8) and place the filter paper after the sample is filtered and precipitated on the filter paper tray (5112) of the sample drying and constant weight device (51), start the sample drying and constant weight device (51), set the temperature, read the balance value at equal intervals, and read the value for 20 consecutive times with an error of less than 0.0005 as constant weight; The mechanical coordination device (8) is started to transfer the dried sample containing the filter paper to the sample storage dish (5211) of the sample storage device (52), and the dust cover (5212) of the storage dish is covered. The sample storage device (52) is started to eject the sample box, and the automatic sample preparation is completed.

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