CN-122017264-A - Raman spectrum-based uranium element full-automatic analyzer and analysis method thereof

CN122017264ACN 122017264 ACN122017264 ACN 122017264ACN-122017264-A

Abstract

The application provides a uranium element full-automatic analyzer based on Raman spectrum and an analysis method thereof, wherein the uranium element full-automatic analyzer comprises a sample grade module, a preprocessing module, a titration module, a grabbing mechanical arm and a Raman spectrum detection system; the sample position module comprises a rotary disk, wherein a plurality of sample stations are arranged on the rotary disk, the pretreatment module is provided with a plurality of pretreatment stations, each pretreatment station is provided with five independent liquid adding pipelines, the titration module is provided with a plurality of titration stations, each titration station is provided with two independent titration pipelines, and the Raman spectrum detection system is used for collecting Raman spectrum signals of a solution in a sample bottle in the titration process in real time. The application is based on the specific identification of the characteristic peak of the tetravalent uranium 1150cm ‑1 and the characteristic peak of the hexavalent uranium 860cm ‑1 by a Raman spectrum system, and can judge the reaction process directly through the molecular signal of the uranium element self valence state change, thereby greatly improving the accuracy and reliability of the detection results of different matrixes and uranium samples with different concentrations.

Inventors

Jin Haoshu
CHEN SHIHENG
WANG HAISHENG
LIN YIBO
DING HAIYUN
GUO GUOLONG
LI LIANG

Assignees

核工业北京化工冶金研究院

Dates

Publication Date: 20260512
Application Date: 20260324

Claims (10)

1. A full-automatic uranium element analyzer based on Raman spectrum is characterized by comprising: The sample position module comprises a rotary disk (1), wherein the rotary disk (1) is provided with a plurality of sample stations (11) for placing sample bottles; The pretreatment module is provided with a plurality of pretreatment stations (2), and each pretreatment station (2) is provided with five independent liquid adding pipelines which are respectively used for sequentially adding five reagents of phosphoric acid, pure water, titanium trichloride solution, sodium nitrite solution and urea into a sample bottle at the pretreatment station (2); The titration module is provided with a plurality of titration stations (3), each titration station (3) is provided with two independent titration pipelines, and the two independent titration pipelines are respectively used for sequentially adding two reagents of sodium diphenylamine sulfonate and ammonium vanadate solution into a sample bottle at the titration station (3); a grabbing mechanical arm (4) arranged above the rotating disc (1) and used for grabbing sample bottles in the rotating disc (1) to the pretreatment station (2), grabbing sample bottles at the pretreatment station (2) to the titration station (3) and placing the titrated sample bottles back to the rotating disc (1), and The Raman spectrum detection system (5) is arranged at the titration station (3), the Raman spectrum detection system (5) is used for collecting Raman spectrum signals of the solution in the sample bottle in the titration process in real time, and intelligent judgment of the titration endpoint is realized through Raman spectrum change of uranium valence state in the titration process.
2. A fully automatic uranium analyser based on raman spectroscopy according to claim 1, wherein a magnetic stirrer (6) is provided under each pretreatment station (2) and each titration station (3).
3. A fully automatic uranium analyzer based on raman spectroscopy according to claim 1, wherein a filling arm (21) is provided at each pretreatment station (2), and the ends of five independent filling pipes are provided on the filling arm (21); A titration arm (31) is arranged at each titration station (3), and the tail ends of the two independent titration pipelines are arranged on the titration arms (31); The device comprises a plurality of independent liquid adding pipelines, a plurality of sample bottles and a plurality of titration arms (31), wherein each liquid adding arm (21) and each titration arm (31) are provided with a rotary module below, and the rotary modules are used for driving the liquid adding arms (21) or the titration arms (31) to rotate along a vertical axis so that the tail ends of the five independent liquid adding pipelines or the tail ends of the two independent titration pipelines can be moved to the position above the sample bottles or far away from the position above the sample bottles.
4. The full-automatic uranium analyzer based on raman spectroscopy according to claim 1, wherein the independent titration pipeline for adding ammonium vanadate dropwise is connected with an injection pump, and the other independent titration pipeline and five independent liquid adding pipelines are respectively connected with peristaltic pumps.
5. A uranium element analysis method based on raman spectrum, characterized in that a full-automatic uranium element analyzer based on raman spectrum according to any one of claims 1 to 4 is adopted, comprising the following steps: sequentially placing sample bottles on a rotary disc (1), and grabbing the appointed sample bottles to a pretreatment station (2) through a grabbing mechanical arm (4) to perform pretreatment operation; grabbing the sample bottle after pretreatment to a titration station (3) for titration operation; The Raman spectrum change of uranium valence state in the titration process is monitored in real time through a Raman spectrum detection system (5) by utilizing the position difference of the characteristic Raman peak of the tetravalent uranium at 1150cm -1 and the characteristic Raman peak of the hexavalent uranium at 860cm -1 , so that the intelligent judgment and the result calculation of the titration endpoint are realized.
6. The uranium analysis method based on Raman spectroscopy as claimed in claim 5, wherein the automatic pretreatment step comprises the steps of quantitatively adding 10ml of phosphoric acid, pure water and 3ml of titanium trichloride solution into a sample bottle sequentially through five independent liquid adding pipelines, standing for 2-3 minutes, quantitatively adding 3ml of sodium nitrite solution and 5ml of urea, and standing for 5-10 minutes, wherein the addition amount of the pure water satisfies the total volume of the sample and the pure water being 20ml.
7. A uranium analysis method based on raman spectroscopy according to claim 5, wherein after the pretreatment is completed, 4 drops of sodium diphenylaminesulfonate indicator are added dropwise to the sample bottle after the pretreatment is completed, a raman spectrum signal of the tetravalent uranium solution is collected by a raman spectrum detection system (5), and characteristic peak intensity I 1150 at 1150cm -1 is recorded as raman spectrum baseline data.
8. The uranium analysis method based on Raman spectrum as claimed in claim 7, wherein after the dripping of the sodium diphenylaminesulfonate indicator is completed, 0.05ml of ammonium vanadate standard solution is dripped into the sample bottle each time in the initial stage, when the beginning of attenuation of characteristic peak intensity at 1150cm -1 is detected, the characteristic peak intensity is regulated to be 0.02ml each time, the solution is stirred for 1 second after each dripping to be uniformly mixed, the Raman spectrum detection system (5) collects spectrum data in real time, and the attenuation of tetravalent uranium characteristic peak intensity I 1150 at 1150cm -1 and the increase of hexavalent uranium characteristic peak intensity I 860 at 860cm -1 are monitored.
9. The uranium analysis method based on Raman spectroscopy as claimed in claim 8, wherein the end point is intelligently judged by calculating a ratio R=I 860 /I 1150 of characteristic peak intensity I 860 at the position of hexavalent uranium 860cm -1 to characteristic peak intensity I 1150 at the position of tetravalent uranium 1150cm -1 , judging as a titration end point when the R value is stable by continuous multiple measurement or the characteristic peak at the position of tetravalent uranium 1150cm -1 is basically disappeared, and recording the volume V of the consumed ammonium vanadate standard solution.
10. The uranium analysis method based on raman spectroscopy according to claim 9, wherein the result is calculated as uranium content according to formula c= (v×c 0 )/V 0 , where C 0 is ammonium vanadate standard solution concentration and V 0 is the volume of the sample to be measured.

Description

Raman spectrum-based uranium element full-automatic analyzer and analysis method thereof Technical Field The application belongs to the technical field of uranium element analysis, and particularly relates to a full-automatic uranium element analyzer based on Raman spectrum and an analysis method thereof. Background Uranium element analysis is crucial in uranium mining and metallurgy production in the nuclear industry, and common detection methods include a fluorescence method, a titration method and the like, but the prior art mainly relies on manual operation, and has the problems of low efficiency, large human error, complex pretreatment and the like. Although some automatic analysis instruments (such as potentiometric titrators) exist, automation of detection steps is realized, manual intervention is still needed for sample pretreatment (such as dissolution, acidification, reduction, bubble removal and the like), the high-flux detection requirement of uranium mining and metallurgy cannot be met, and meanwhile, for low-concentration uranium samples or complex matrix solutions, whether a fluorescence method or a titration method, a human eye or a common optical sensor is difficult to accurately identify an endpoint. Disclosure of Invention The application aims to provide a full-automatic uranium element analyzer based on Raman spectrum and an analysis method thereof, which are used for solving the technical problems that in the prior art, the sample pretreatment efficiency is low, and an optical color judgment method is easy to be interfered in a complex solution system and has limited accuracy. In order to achieve the above purpose, the technical scheme adopted by the application is that the application provides a uranium element full-automatic analyzer based on Raman spectrum, which comprises the following steps: the sample position module comprises a rotary disk, wherein the rotary disk is provided with a plurality of sample stations for placing sample bottles; The pretreatment module is provided with a plurality of pretreatment stations, and each pretreatment station is provided with five independent liquid adding pipelines which are respectively used for sequentially adding five reagents of phosphoric acid, pure water, titanium trichloride solution, sodium nitrite solution and urea into a sample bottle at the pretreatment station; The titration module is provided with a plurality of titration stations, each titration station is provided with two independent titration pipelines, and the titration stations are respectively used for sequentially adding two reagents of sodium diphenylamine sulfonate and ammonium vanadate solution into a sample bottle at the titration station; A grabbing mechanical arm arranged above the rotating disk and used for grabbing sample bottles in the rotating disk to the pretreatment station, grabbing sample bottles at the pretreatment station to the titration station and placing the titrated sample bottles back to the rotating disk, and The Raman spectrum detection system is arranged at the titration station and is used for collecting Raman spectrum signals of the solution in the sample bottle in the titration process in real time, and the intelligent judgment of the titration endpoint is realized through Raman spectrum change of uranium valence state in the titration process. With reference to the first aspect, in a possible implementation manner, a magnetic stirrer is disposed below each pretreatment station and each titration station. With reference to the first aspect, in a possible implementation manner, a liquid adding arm is disposed at each pretreatment station, and the ends of the five independent liquid adding pipelines are disposed on the liquid adding arms; a titration arm is arranged at each titration station, and the tail ends of the two independent titration pipelines are arranged on the titration arms; the automatic titration device comprises a plurality of titration arms, a plurality of independent liquid adding pipelines, a plurality of sample bottles, a plurality of titration arms, a plurality of rotation modules, a plurality of liquid adding modules, a plurality of sample bottles and a plurality of sample bottles, wherein each liquid adding arm and each titration arm are arranged below the corresponding rotation module, and the rotation modules are used for driving the liquid adding arms or the titration arms to rotate along a vertical axis so that the tail ends of the five independent liquid adding pipelines or the tail ends of the two independent titration pipelines move to the top of the sample bottles or are far away from the top of the sample bottles. With reference to the first aspect, in one possible implementation manner, the independent titration pipeline for dripping ammonium vanadate is connected with a syringe pump, and the other independent titration pipeline and the five independent liquid adding pipelines are respectively connected with peris