Uranium element full-automatic analyzer based on Raman spectrum and analysis method thereof

Abstract

The invention provides a Raman spectrum-based uranium element full-automatic analyzer and an analysis method thereof. The uranium element full-automatic analyzer comprises a sample position module, a pretreatment module, a titration module, a grabbing mechanical arm and a Raman spectrum detection system, the sample position module comprises a rotating disc, and a plurality of sample stations are arranged on the rotating disc; the pretreatment module is provided with a plurality of pretreatment stations, and each pretreatment station is provided with five independent liquid adding pipelines; the titration module is provided with a plurality of titration stations, and each titration station is provided with two independent titration pipelines; and the Raman spectrum detection system is used for collecting Raman spectrum signals of the solution in the sample bottle in real time in the titration process. Based on specific recognition of a Raman spectrum system on a 1150cm <-1 > characteristic peak of tetravalent uranium and a 860cm <-1 > characteristic peak of hexavalent uranium, the reaction process can be directly judged through molecular signals of valence change of uranium elements, and the accuracy and reliability of detection results of uranium samples with different matrixes and different concentrations are greatly improved.

Description

Technical Field

[0001] This application belongs to the technical field of uranium element analysis, and more specifically, relates to a fully automated uranium element analyzer based on Raman spectroscopy and its analytical method. Background Technology

[0002] Uranium elemental analysis is crucial in uranium mining and metallurgical production in the nuclear industry. Commonly used detection methods include fluorescence and titration. However, existing technologies mainly rely on manual operation, which suffers from low efficiency, large human error, and complex pretreatment.

[0003] Although there are some automated analytical instruments (such as potentiometric titrators), they only automate the detection steps. Sample pretreatment (such as dissolution, acidification, reduction, and degassing) still requires manual intervention, which cannot meet the high-throughput detection requirements of uranium mining and metallurgy. At the same time, for low-concentration uranium samples or complex matrix solutions, whether using fluorescence or titration methods, the human eye or ordinary optical sensors cannot accurately identify the endpoint. Summary of the Invention

[0004] The purpose of this application is to provide a fully automated uranium analyzer and its analysis method based on Raman spectroscopy, so as to solve the technical problems of low sample pretreatment efficiency and the susceptibility to interference and limited accuracy of optical color determination method in complex solution systems in the prior art.

[0005] To achieve the above objectives, firstly, the technical solution adopted in this application is: to provide a fully automated uranium element analyzer based on Raman spectroscopy, comprising: The sample station module includes a rotating disk having multiple sample stations for placing sample vials; The pretreatment module has multiple pretreatment stations, and each pretreatment station is equipped with five independent liquid addition pipelines, which are used to sequentially add five reagents—phosphoric acid, pure water, titanium trichloride solution, sodium nitrite solution, and urea—to the sample bottle at the pretreatment station. The titration module has multiple titration stations, each of which is equipped with two independent burettes, which are used to sequentially add sodium diphenylamine sulfonate and ammonium vanadate solution to the sample bottle at the titration station. A gripping robotic arm, positioned above the rotating disk, is used to grip sample vials from the rotating disk to the pretreatment station, grip sample vials from the pretreatment station to the titration station, and return titrated sample vials to the rotating disk; and A Raman spectroscopy detection system is installed at the titration station. The Raman spectroscopy detection system is used to acquire the Raman spectral signal of the solution in the sample bottle in real time during the titration process. By observing the Raman spectral changes of the valence state of uranium during the titration process, the endpoint of the titration can be intelligently determined.

[0006] In conjunction with the first aspect, in one possible implementation, a magnetic stirrer is provided below each of the pretreatment stations and each of the titration stations.

[0007] In conjunction with the first aspect, in one possible implementation, each of the pretreatment stations is provided with a liquid dispensing arm, and the ends of the five independent liquid dispensing pipelines are all located on the liquid dispensing arm. Each titration station is equipped with a titration arm, and the ends of the two independent titration lines are both located on the titration arm; Each of the liquid addition arms and each of the titration arms is provided with a rotating module below it. The rotating module is used to drive the liquid addition arm or the titration arm to rotate along the vertical axis so that the ends of the five independent liquid addition lines or the ends of the two independent titration lines move to above the sample bottle or away from the sample bottle.

[0008] In conjunction with the first aspect, in one possible implementation, the independent burette for adding ammonium vanadate is connected to an injection pump, and another independent burette and five independent liquid addition lines are each connected to a peristaltic pump.

[0009] Secondly, this application also provides a Raman spectroscopy-based uranium element analysis method, using the aforementioned fully automated Raman spectroscopy-based uranium element analyzer, comprising the following steps: The sample bottles are placed sequentially on the rotating disk, and the designated sample bottles are picked up by the gripping robotic arm and moved to the pre-processing station for pre-processing. After pretreatment, the sample bottle is picked up and placed at the titration station for titration. Using tetravalent uranium at 1150 cm -1 The characteristic Raman peak at 860 cm⁻¹ corresponds to that of hexavalent uranium. -1 The positional differences of characteristic Raman peaks at the titration point are monitored in real time by a Raman spectroscopy detection system to detect changes in the Raman spectrum of the uranium valence state during titration, enabling intelligent determination of the titration endpoint and calculation of the results.

[0010] In conjunction with the second aspect, in one possible implementation, the automatic pretreatment step is as follows: quantitatively add 10 ml of phosphoric acid, pure water, and 3 ml of titanium trichloride solution to the sample vial sequentially through five independent liquid addition lines, let stand for 2-3 minutes, then quantitatively add 3 ml of sodium nitrite solution and 5 ml of urea, and let stand for 5-10 minutes; the amount of pure water added is such that the total volume of the sample and pure water is 20 ml.

[0011] In conjunction with the second aspect, in one possible implementation, after pretreatment, four drops of sodium diphenylamine sulfonate indicator are added to the pretreated sample vial. The Raman spectral signal of the tetravalent uranium solution is acquired using a Raman spectroscopy detection system, and recorded at 1150 cm⁻¹. -1 Characteristic peak intensity I at the location 1150 , as the baseline data for Raman spectroscopy.

[0012] In conjunction with the second aspect, in one possible implementation, after the sodium diphenylamine sulfonate indicator has been completely added, 0.05 ml of ammonium vanadate standard solution is initially added to the sample vial each time. When 1150 cm⁻¹ is detected... -1 When the intensity of the characteristic peak begins to decay, adjust the dosage to 0.02 ml per drop; stir for 1 second after each drop to ensure the solution is thoroughly mixed; the Raman spectroscopy detection system acquires spectral data in real time, monitoring at 1150 cm⁻¹. -1 The characteristic peak intensity of tetravalent uranium I 1150 attenuation and 860cm -1 The characteristic peak intensity of hexavalent uranium I 860 Growth.

[0013] In conjunction with the second aspect, in one possible implementation, the endpoint intelligent determination is: calculating hexavalent uranium 860cm⁻¹ -1 Characteristic peak intensity I 860 With tetravalent uranium-1150cm -1 Characteristic peak intensity I 1150 The ratio R=I 860 / I 1150 When the R value stabilizes after multiple consecutive measurements, or when tetravalent uranium at 1150 cm⁻¹... -1 When the characteristic peak at the point basically disappears, it is determined to be the titration endpoint, and the volume V of ammonium vanadate standard solution consumed is recorded.

[0014] In conjunction with the second aspect, in one possible implementation, the result is calculated as follows: the uranium content is calculated according to the formula C=(V×C0) / V0, where C0 is the concentration of the ammonium vanadate standard solution and V0 is the volume of the sample to be tested.

[0015] The advantages of the fully automated uranium analyzer based on Raman spectroscopy provided in this application are as follows: Compared with the prior art, this application completely replaces the traditional manual sample transfer and sequential addition of multiple reagents by using a rotating disk multi-station sample position module in conjunction with a gripping robotic arm for automatic flow, and precise reagent addition by using five independent liquid addition lines in the pretreatment module and two independent titration lines in the titration module. Multiple samples can be processed in parallel in a single batch, which can fully adapt to the high-throughput sample detection needs in uranium mining and metallurgical production scenarios.

[0016] The seven independent pipelines of the pretreatment module and titration module can precisely control the order and amount of adding various reagents such as phosphoric acid, titanium trichloride, and sodium nitrite, avoiding problems such as incorrect reagent addition, dosage deviation, and inconsistent operation sequence during manual liquid addition, thus providing a stable foundation for the accuracy of subsequent titration detection.

[0017] Unlike traditional methods that rely on human visual observation of color changes or ordinary optical sensors to determine the endpoint, this method uses Raman spectroscopy to analyze tetravalent uranium-1150 cm⁻¹. -1 Characteristic peaks, hexavalent uranium 860 cm⁻¹ -1 The specific identification of characteristic peaks allows for direct determination of the reaction process through molecular signals of uranium element valence state changes, unaffected by interference factors such as complex matrix solution color and turbidity. It can also achieve accurate endpoint identification for low-concentration uranium samples, significantly improving the accuracy and reliability of detection results for uranium samples with different matrices and concentrations.

[0018] The beneficial effects of the Raman spectroscopy-based uranium elemental analysis method provided in this application are as follows: Compared with existing technologies, this application has clearly defined quantitative parameters controlling all operational steps, from sample placement and automated transfer via robotic arm to quantitative dispensing of pretreatment reagents and gradient addition during titration, significantly improving the consistency and traceability of the detection results. The endpoint is determined by the ratio of the characteristic peak intensities of hexavalent uranium to tetravalent uranium. Compared to identifying the intensity of a single characteristic peak, this effectively offsets signal interference caused by factors such as laser power fluctuations and sample vial position deviations during Raman spectroscopy detection, thus doubly improving the anti-interference capability and sensitivity of endpoint determination. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 A front view of a fully automated uranium analyzer based on Raman spectroscopy provided for the first embodiment of this application; Figure 2 A top view of a fully automated uranium analyzer based on Raman spectroscopy provided for the first embodiment of this application; Figure 3 Official drawings of the Raman spectroscopy detection system and magnetic stirrer provided in the first embodiment of this application; Figure 4 Raman spectral characteristics of tetravalent and hexavalent uranium provided for the second embodiment of this application.

[0021] The labels for the attached figures are as follows: 1. Rotary disk; 11. Sample station; 2. Pre-treatment station; 21. Liquid dispensing arm; 3. Titration station; 31. Titration arm; 4. Grasping robotic arm; 5. Raman spectroscopy detection system; 51. Laser source; 52. Raman spectrometer; 6. Magnetic stirrer. Detailed Implementation

[0022] To make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the described embodiments are only a part of the embodiments of this application, not all of them. The specific embodiments described herein are only used to explain this application and are not intended to limit this application. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0023] It should be further noted that the accompanying drawings and embodiments of this application mainly describe the concept of this application. Based on this concept, some specific forms and arrangements of connection relationships, positional relationships, power mechanisms, power supply systems and control systems may not be fully described. However, under the premise that those skilled in the art understand the concept of this application, they can implement the above-mentioned specific forms and arrangements in a well-known manner.

[0024] When a component is referred to as being "fixed to" or "set on" another component, it can be directly on or indirectly on that other component. When a component is referred to as being "connected to" another component, it can be directly connected to or indirectly connected to that other component.

[0025] The directional terms "inner" and "outer" refer to the inner and outer contours of each component itself. The terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application.

[0026] For ease of description, spatial relative terms such as "above," "over," "on the upper surface of," "above," etc., are used herein to describe the spatial positional relationship of a device or feature as shown in the figures to other devices or features. It should be understood that spatial relative terms are intended to encompass different orientations in use or operation beyond the orientation of the device as described in the figures. For example, if the device in the figures were inverted, a device described as "above" or "above" other devices or structures would subsequently be positioned as "below" or "under" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below." The device may also be positioned in other different ways, and the spatial relative descriptions used herein will be interpreted accordingly.

[0027] In the description of this application, "multiple" means two or more, and "several" means one or more, unless otherwise expressly and specifically defined.

[0028] This application describes a fully automated uranium analyzer based on Raman spectroscopy and its analytical method.

[0029] like Figure 1 , Figure 2 and Figure 3 As shown, the first embodiment of this application provides a fully automated uranium element analyzer based on Raman spectroscopy, including a sample position module, a pretreatment module, a titration module, a gripping robotic arm 4, and a Raman spectroscopy detection system 5.

[0030] The sample station module includes a horizontally arranged rotating disk 1, which has multiple sample stations 11 for placing sample bottles. In this embodiment, there are no fewer than 20 sample stations 11. The bottom of the rotating disk 1 can be driven to rotate by a rotary cylinder or a motor.

[0031] The pretreatment module has multiple pretreatment stations 2, specifically five pretreatment stations 2 in this embodiment. Each pretreatment station 2 is equipped with five independent liquid addition pipelines, which are used to sequentially add five reagents—phosphoric acid, pure water, titanium trichloride solution, sodium nitrite solution, and urea—to the sample vials at the pretreatment station 2.

[0032] The titration module has multiple titration stations 3, specifically five titration stations 3 in this embodiment. Each titration station 3 is equipped with two independent burettes, which are used to sequentially add sodium diphenylamine sulfonate solution and ammonium vanadate solution to the sample vial at the titration station 3, respectively.

[0033] The gripping robotic arm 4 is positioned above the rotary table 1 and has the ability to move in three-dimensional directions (XYZ). It is used to grip sample bottles in the rotary table 1 to the pretreatment station 2, grip sample bottles at the pretreatment station 2 to the titration station 3, and return the titrated sample bottles to the rotary table 1.

[0034] The Raman spectroscopy detection system 5 is set at the titration station 3. The Raman spectroscopy detection system 5 is used to acquire the Raman spectral signal of the solution in the sample bottle in real time during the titration process. By observing the Raman spectral changes of the valence state of uranium during the titration process, the endpoint of the titration can be intelligently determined.

[0035] The Raman spectroscopy detection system 5 includes a laser source 51 and a Raman spectrometer 52. The laser source 51 and the Raman spectrometer 52 are located on opposite sides of the sample bottle at the titration station 3, and the Raman spectrometer 52 is connected to the computer system.

[0036] refer to Figure 4 The horizontal coordinate of the icon (Wavenumber, cm) -1 Raman shift wavenumber reflects the frequency difference of molecular vibration / rotation, covering a range of 200-1400 cm⁻¹. -1 The vertical axis (Intensity, au) represents the Raman scattering signal intensity (in arbitrary units), and the peak height represents the signal strength of the corresponding vibrational mode. The curve as a whole represents the baseline of the Raman spectrum (the intensity gradually decreases with increasing wavenumber) and the characteristic peaks; baseline fluctuations are normal spectral noise.

[0037] Hexavalent uranium (UO2) 2+ ): at approximately 860cm -1 There is a distinct characteristic peak at this location, corresponding to uranyl ions (UO2). 2+ The symmetrical stretching vibration of uranium is the hallmark Raman signal of hexavalent uranium.

[0038] Tetravalent uranium (U) 4+ ): at approximately 1150cm -1 There is a sharp characteristic peak at 445 cm⁻¹. -1 There are also characteristic peaks nearby (the trend can be seen on the left side of the figure), which is the characteristic Raman signal of tetravalent uranium.

[0039] The principle of Raman spectroscopy identification is as follows: Hexavalent uranium [U(VI)]: in the form of uranyl ions (UO2) 2+ It exists in the form of ) and its symmetric stretching vibration produces a strong characteristic peak in the Raman spectrum, located at 860 cm⁻¹. -1 nearby.

[0040] Tetravalent uranium [U(IV)]: does not form a uranyl ion structure; its characteristic peak is located at 445 cm⁻¹. -1 and 1150cm -1The location of the peak is completely different from that of hexavalent uranium in the vicinity.

[0041] By monitoring the rise and fall of characteristic peaks in real time, the titration reaction process can be accurately tracked, avoiding interference from optical color determination.

[0042] This embodiment provides a fully automated uranium analyzer based on Raman spectroscopy. Through the automatic transfer of the rotating disk type 1 multi-station sample position module in conjunction with the gripping robotic arm 4, and the precise addition of reagents through five independent liquid addition pipelines in the pretreatment module and two independent titration pipelines in the titration module, it completely replaces the traditional manual operations such as sample transfer and sequential addition of multiple reagents. Multiple samples can be processed in parallel in a single batch, which can fully adapt to the high-throughput sample detection needs in uranium mining and metallurgical production scenarios.

[0043] The seven independent pipelines of the pretreatment module and titration module can precisely control the order and amount of adding various reagents such as phosphoric acid, titanium trichloride, and sodium nitrite, avoiding problems such as incorrect reagent addition, dosage deviation, and inconsistent operation sequence during manual liquid addition, thus providing a stable foundation for the accuracy of subsequent titration detection.

[0044] Unlike traditional methods that rely on human visual observation of color changes or ordinary optical sensors to determine the endpoint, this method uses Raman spectroscopy to analyze tetravalent uranium-1150 cm⁻¹. -1 Characteristic peaks, hexavalent uranium 860 cm⁻¹ -1 The specific identification of characteristic peaks allows for direct determination of the reaction process through molecular signals of uranium element valence state changes, unaffected by interference factors such as complex matrix solution color and turbidity. It can also achieve accurate endpoint identification for low-concentration uranium samples, significantly improving the accuracy and reliability of detection results for uranium samples with different matrices and concentrations.

[0045] like Figures 2 to 3 As shown, this application provides a further specific implementation method based on the first implementation method as follows: A magnetic stirrer 6 is installed below each pretreatment station 2 and each titration station 3.

[0046] A magnetic stir bar is placed inside the sample vial and activated during sample pretreatment and titration. The magnetic stir bar stirs the solution, ensuring uniform mixing of reagents and effectively removing air bubbles from the solution, thus preventing air bubbles from interfering with the acquisition of Raman spectral signals.

[0047] In addition, automated magnetic stirring replaces manual shaking, further reducing human intervention and making the reaction conditions for pretreatment and titration more stable and controllable. The repeatability of testing different batches of samples is greatly improved, solving the problem of fluctuations in test results caused by inconsistent manual shaking strength and frequency.

[0048] like Figures 1 to 2As shown, this application provides a further specific implementation method based on the first implementation method as follows: Each pretreatment station is equipped with a liquid addition arm 21 at two locations, and the ends of the five independent liquid addition pipelines are all located on the liquid addition arm 21. Each titration station is equipped with a titration arm 31 at 3 locations, and the ends of the two independent titration lines are located on the titration arm 31. Each dispensing arm 21 and each titration arm 31 is provided with a rotating module below it. The rotating module is used to drive the dispensing arm 21 or the titration arm 31 to rotate along the vertical axis so that the end of the five independent dispensing lines or the end of the two independent titration lines moves to above the sample bottle or away from the sample bottle.

[0049] In this embodiment, the rotating module can be driven by a rotary cylinder or a motor to rotate the corresponding liquid addition arm 21 or titration arm 31.

[0050] When the gripping robotic arm 4 grips or places sample vials at the pretreatment station 2 or titration station 3, the rotating module drives the corresponding liquid addition arm 21 or titration arm 31 to rotate to one side in advance to avoid interference with the gripping robotic arm 4. After the gripping or placement is completed, the rotating module drives the corresponding liquid addition arm 21 or titration arm 31 to reset so that subsequent reagent titration can be performed.

[0051] Based on the first embodiment, this application provides another specific embodiment as follows: An independent burette for adding ammonium vanadate is connected to a syringe pump, and another independent burette and five independent liquid addition lines are each connected to a peristaltic pump.

[0052] Each reagent is delivered by an independent pump to avoid cross-contamination. The pump used to deliver the ammonium vanadate standard solution is a high-precision syringe pump, which can achieve precise micro-drops of 0.02 ml to ensure titration accuracy. The pumps for the other six reagents are peristaltic pumps, which can meet the quantitative requirements of pretreatment and indicator addition. The five liquid addition arms 21 of the pretreatment module and the two titration arms 31 of the titration module all adopt an independent liquid addition tube design, and each pipeline is isolated from each other to further eliminate the risk of cross-contamination of reagents.

[0053] Based on the same inventive concept, the second embodiment of this application provides a uranium element analysis method based on Raman spectroscopy, using the aforementioned fully automated uranium element analyzer based on Raman spectroscopy, including the following steps: The sample bottles are placed sequentially on the rotating disk 1, and the designated sample bottles are picked up by the gripping robotic arm 4 and placed at the pre-processing station 2 for pre-processing. After pretreatment, the sample bottle is picked up and placed at titration station 3 for titration. Using tetravalent uranium at 1150 cm -1The characteristic Raman peak at 860 cm⁻¹ corresponds to that of hexavalent uranium. -1 The positional differences of characteristic Raman peaks at the titration point are monitored in real time by the Raman spectroscopy detection system 5 to detect changes in the Raman spectrum of the uranium valence state during the titration process, thereby enabling intelligent determination of the titration endpoint and calculation of the results.

[0054] This embodiment provides a Raman spectroscopy-based uranium elemental analysis method. From sample placement and automated transfer via robotic arm to quantitative dispensing of pretreatment reagents and gradient addition during titration, all operational steps are controlled by clearly defined quantitative parameters, significantly improving the consistency and traceability of the detection results. The endpoint is determined by the ratio of the characteristic peak intensities of hexavalent uranium to tetravalent uranium. Compared to identifying the intensity of a single characteristic peak, this method effectively counteracts signal interference caused by factors such as laser power fluctuations and sample vial position deviations during Raman spectroscopy detection, thus doubly improving the anti-interference capability and sensitivity of endpoint determination.

[0055] Based on the second embodiment, this application provides a further specific embodiment as follows: The automated pretreatment process is as follows: 10 ml of phosphoric acid, pure water, and 3 ml of titanium trichloride solution are sequentially added to the sample vials via five independent addition lines. After standing for 2-3 minutes, 3 ml of sodium nitrite solution and 5 ml of urea are added quantitatively. Simultaneously, the magnetic stirrer 6 is activated to continuously stir and remove air bubbles from the solution. After the bubbles have completely disappeared, the vials are allowed to stand for 5-10 minutes. The amount of pure water added ensures a total volume of 20 ml for both the sample and pure water. This pretreatment process can be performed on five samples simultaneously, improving overall detection efficiency.

[0056] Based on the second embodiment, this application provides a further specific embodiment as follows: After pretreatment, 4 drops of sodium diphenylamine sulfonate indicator were added to the pretreated sample vial. The Raman spectral signal of the tetravalent uranium solution was acquired using the Raman spectroscopy detection system 5, and recorded at 1150 cm⁻¹. -1 Characteristic peak intensity I at the location 1150 As the baseline data for Raman spectroscopy, this intensity value will be used as the baseline data for comparing spectral changes during subsequent titration, providing a benchmark reference for endpoint determination.

[0057] Based on the second embodiment, this application provides a further specific embodiment as follows: After the sodium diphenylamine sulfonate indicator has been added, initially add 0.05 ml of ammonium vanadate standard solution to the sample vial each time. When 1150 cm⁻¹ is detected... -1 When the intensity of the characteristic peak begins to decay, adjust the dosage to 0.02 ml per drop; stir for 1 second after each drop to ensure the solution is thoroughly mixed; the Raman spectroscopy detection system 5 acquires spectral data in real time, monitoring at 1150 cm⁻¹. -1 The characteristic peak intensity of tetravalent uranium I 1150attenuation and 860cm -1 The characteristic peak intensity of hexavalent uranium I 860 Growth.

[0058] In the initial stage of titration, a relatively large volume of 0.05 ml is added each time, which can quickly advance the titration reaction process, significantly shorten the titration time, improve the overall detection efficiency, and avoid the problem of excessively long detection cycles caused by adding small volumes throughout the process. When the intensity of the characteristic peak of tetravalent uranium begins to decay, the volume is immediately adjusted to 0.02 ml each time, which achieves fine titration near the endpoint, accurately controls the amount of ammonium vanadate added, and avoids the problem of over-titration leading to an over-calculated uranium content.

[0059] The design of stirring for 1 second after each drop ensures that the added ammonium vanadate solution is quickly and evenly mixed with the sample solution, allowing the titration reaction to reach equilibrium rapidly. This guarantees that the spectral signal acquired by the Raman spectrometer 52 can accurately reflect the current uranium valence state change in the solution, avoiding spectral signal distortion caused by local unbalanced reactions. It provides continuous and reliable spectral data support for intelligent endpoint determination.

[0060] Based on the second embodiment, this application provides a further specific embodiment as follows: The endpoint intelligent judgment is: calculate hexavalent uranium 860cm -1 Characteristic peak intensity I 860 With tetravalent uranium-1150cm -1 Characteristic peak intensity I 1150 The ratio R=I 860 / I 1150 When the R value stabilizes after multiple consecutive measurements, or when tetravalent uranium at 1150 cm⁻¹... -1 When the characteristic peak at the point basically disappears, it is determined to be the titration endpoint, and the volume V of ammonium vanadate standard solution consumed is recorded.

[0061] By setting a criterion that the R value tends to stabilize after multiple consecutive measurements, misjudgments caused by random errors in a single spectral measurement are avoided, ensuring the reliability of the endpoint determination and making the determination result more consistent with the actual endpoint state of the titration reaction. At the same time, the near disappearance of the characteristic peak of tetravalent uranium is used as an auxiliary criterion, forming a dual determination system of stable ratio and disappearance of characteristic peak. This further avoids the problem of misjudgment caused by small fluctuations in the ratio due to the complexity of the solution matrix, making the endpoint determination more rigorous and accurate.

[0062] Automated intelligent judgment replaces manual visual observation, completely eliminating the subjective error of human judgment, ensuring that the endpoint judgment criteria are consistent for different operators and different batches of samples, and greatly improving the repeatability and comparability of test results.

[0063] Based on the second embodiment, this application provides a further specific embodiment as follows: The result is calculated as follows: the uranium content is calculated by computer system according to the formula C=(V×C0) / V0, where C0 is the concentration of ammonium vanadate standard solution and V0 is the volume of the sample to be tested.

[0064] The computer system automatically calculates the uranium content according to the formula. By utilizing the instrument's precise data processing capabilities, arithmetic errors caused by addition, subtraction, multiplication, and division during manual calculation are completely avoided, ensuring the accuracy of the results and significantly improving calculation efficiency. The test results are automatically saved to the database, avoiding omissions and errors when manually recording data, and achieving complete retention of test data.

[0065] The above are merely preferred embodiments of this application and are not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

[0066] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments according to this application. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0067] Unless otherwise specifically stated, the relative arrangement, numerical expressions, and values ​​of the components and steps described in these embodiments do not limit the scope of this application. It should also be understood that, for ease of description, the dimensions of the various parts shown in the drawings are not drawn to actual scale. Techniques, methods, and devices known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques, methods, and devices should be considered part of the specification. In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values. It should be noted that similar reference numerals and letters in the following drawings denote similar items; therefore, once an item is defined in one drawing, it need not be further discussed in subsequent drawings.

Claims

1. A fully automated uranium analyzer based on Raman spectroscopy, characterized in that, include: The sample station module includes a rotating disk (1) having multiple sample stations (11) for placing sample vials. The pretreatment module has multiple pretreatment stations (2), and each pretreatment station (2) is equipped with five independent liquid addition pipelines, which are used to add phosphoric acid, pure water, titanium trichloride solution, sodium nitrite solution and urea to the sample bottle at the pretreatment station (2) in sequence. The titration module has multiple titration stations (3), and each titration station (3) is equipped with two independent titration lines, which are used to add sodium diphenylamine sulfonate and ammonium vanadate solution to the sample bottle at the titration station (3) in sequence. A gripping robotic arm (4), positioned above the rotating disk (1), is used to grip sample vials from the rotating disk (1) to the pretreatment station (2), grip sample vials from the pretreatment station (2) to the titration station (3), and return titrated sample vials to the rotating disk (1); and The Raman spectroscopy detection system (5) is set at the titration station (3). The Raman spectroscopy detection system (5) is used to collect the Raman spectral signal of the solution in the sample bottle in real time during the titration process. The intelligent determination of the titration endpoint is achieved by the Raman spectral change of the valence state of uranium during the titration process.

2. The fully automated uranium analyzer based on Raman spectroscopy as described in claim 1, characterized in that, A magnetic stirrer (6) is provided below each of the pretreatment stations (2) and each of the titration stations (3).

3. The fully automated uranium analyzer based on Raman spectroscopy as described in claim 1, characterized in that, Each of the pretreatment stations (2) is equipped with a liquid addition arm (21), and the ends of the five independent liquid addition pipelines are all located on the liquid addition arm (21); Each titration station (3) is provided with a titration arm (31), and the ends of the two independent titration lines are provided on the titration arm (31); Each of the liquid addition arms (21) and each of the titration arms (31) is provided with a rotating module below it. The rotating module is used to drive the liquid addition arm (21) or the titration arm (31) to rotate along the vertical axis so that the ends of the five independent liquid addition lines or the ends of the two independent titration lines move to above the sample bottle or away from above the sample bottle.

4. The fully automated uranium analyzer based on Raman spectroscopy as described in claim 1, characterized in that, The independent burette for adding ammonium vanadate is connected to an injection pump, and another independent burette and five independent liquid addition lines are each connected to a peristaltic pump.

5. A method for uranium elemental analysis based on Raman spectroscopy, characterized in that, The fully automated uranium analyzer based on Raman spectroscopy as described in any one of claims 1-4 includes the following steps: The sample bottles are placed on the rotating disk (1) in sequence, and the designated sample bottles are picked up by the gripping robotic arm (4) and placed at the pre-processing station (2) for pre-processing. After pretreatment, the sample bottle is picked up and placed at the titration station (3) for titration. Using tetravalent uranium at 1150 cm -1 The characteristic Raman peak at 860 cm⁻¹ corresponds to that of hexavalent uranium. -1 The positional differences of the characteristic Raman peaks at the titration point are monitored in real time by the Raman spectroscopy detection system (5) to detect the Raman spectral changes of the uranium valence state during the titration process, thereby realizing intelligent judgment of the titration endpoint and calculation of the results.

6. The Raman spectroscopy-based uranium elemental analysis method as described in claim 5, characterized in that, The automatic pretreatment step is as follows: 10 ml of phosphoric acid, pure water, and 3 ml of titanium trichloride solution are added to the sample bottle sequentially through five independent liquid addition lines. After standing for 2-3 minutes, 3 ml of sodium nitrite solution and 5 ml of urea are added quantitatively, and the bottle is left to stand for 5-10 minutes. The amount of pure water added is such that the total volume of the sample and pure water is 20 ml.

7. The Raman spectroscopy-based uranium elemental analysis method as described in claim 5, characterized in that, After pretreatment, add 4 drops of sodium diphenylamine sulfonate indicator to the pretreated sample vial. Collect the Raman spectral signal of the tetravalent uranium solution using the Raman spectroscopy detection system (5) and record the signal at 1150 cm⁻¹. -1 Characteristic peak intensity I at the location 1150 , as the baseline data for Raman spectroscopy.

8. The Raman spectroscopy-based uranium elemental analysis method as described in claim 7, characterized in that, After the sodium diphenylamine sulfonate indicator has been added, initially add 0.05 ml of ammonium vanadate standard solution to the sample vial each time. When 1150 cm⁻¹ is detected... -1 When the intensity of the characteristic peak begins to decay, adjust the dosage to 0.02 ml per drop; stir for 1 second after each drop to ensure the solution is mixed evenly; the Raman spectroscopy detection system (5) collects spectral data in real time and monitors 1150 cm⁻¹. -1 The characteristic peak intensity of tetravalent uranium I 1150 attenuation and 860cm -1 The characteristic peak intensity of hexavalent uranium I 860 Growth.

9. The Raman spectroscopy-based uranium elemental analysis method as described in claim 8, characterized in that, The endpoint intelligent judgment is: calculate hexavalent uranium 860cm⁻¹ -1 Characteristic peak intensity I 860 With tetravalent uranium-1150cm -1 Characteristic peak intensity I 1150 The ratio R=I 860 / I 1150 When the R value stabilizes after multiple consecutive measurements, or when tetravalent uranium at 1150 cm⁻¹... -1 When the characteristic peak at the point basically disappears, it is determined to be the titration endpoint, and the volume V of ammonium vanadate standard solution consumed is recorded.

10. The Raman spectroscopy-based uranium elemental analysis method as described in claim 9, characterized in that, The result is calculated as follows: the uranium content is calculated according to the formula C=(V×C0) / V0, where C0 is the concentration of the ammonium vanadate standard solution and V0 is the volume of the sample to be tested.

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