腔增强拉曼光谱法快速定量分析地浸溶液中的酸根离子

doi:10.3964/j.issn.1000-0593(2025)06-1744-08

摘要
参考文献
相关文章 (15)

全文: PDF (6379 KB)
输出: BibTeX | EndNote (RIS)

摘要：为解决铀矿地浸溶液中离子快速定量分析难题，设计一套带自动进样排废装置的腔增强拉曼光谱仪，分别检测SO^2-₄、NO^-₃、CO^2-₃、HCO^-₃的标准溶液，建立SO^2-₄、NO^-₃、CO^2-₃、HCO^-₃的标准定量分析模型，实现对我国某铀矿地浸溶液中的SO^2-₄、NO^-₃、CO^2-₃、HCO^-₃进行快速定量分析。相对于其他类型的增强腔，近共心腔有更好的性价比和结构简洁性；近共心腔通过增加入射激光的反射次数以达到增强拉曼散射信号的目的。实验所用近共心腔增强拉曼散射信号的光谱仪能将单光束入射激光的拉曼散射信号增强23.77倍。为避免人工操作的繁琐性和带入实验误差，为腔增强拉曼光谱仪专门设计了一套自动进样排废装置，该装置能够实现选择进样、进样液位监测、空气清洗及自动排废等功能；自动进样排废装置的配备有助于腔增强拉曼光谱仪在在线检测领域的功能拓展。相比于传统定量分析方法（滴定法），腔增强拉曼光谱法具有高灵敏度、操作简便、无需试剂前处理、无损检测、快速检测、可同时检测多种分子和离子等优势，为化学分析等领域提供了一种新颖且高效的分析手段。实验结果表明，该技术对SO^2-₄、NO^-₃、CO^2-₃、HCO^-₃的检测限分别为50、50、17、30 mg·L^-1，建立的标准定量分析模型的相关系数（R²）均超过0.999，有优异的分析性能和线性响应能力。用模型对两个矿区的实际地浸样品溶液分别进行五组检测，得出酸法地浸溶液中包含SO^2-₄和NO^-₃，五组检测离子浓度平均值分别为10 743.10和1 253.52 mg·L^-1，RSD分别为0.39%和1.39%；中性地浸溶液中包含SO^2-₄、CO^2-₃和HCO^-₃，五组检测离子浓度平均值分别为1 400.87、98.31和550.04 mg·L^-1，RSD分别为1.42%、2.13%、1.69%。腔增强拉曼光谱法的比对实验结果误差远比滴定法的小，进一步表明腔增强拉曼光谱法在准确、高效的定量分析溶液中离子方面有着极大的应用价值。

关键词：腔增强拉曼光谱；自动进样排废装置；地浸溶液；标准定量分析模型

Abstract：A cavity-enhanced Raman spectrometer equipped with an automatic sampling and waste disposal device was designed to address the challenge of rapid quantitative analysis of ions in uranium ore in situ leaching solutions. Standard solutions of SO^2-₄, NO^-₃, CO^2-₃, and HCO^-₃ were tested to establish standard quantitative analysis models for these anions. This enables rapid quantitative analysis of these ions in in-situ leaching solutions from a uranium mine in China. Compared to other enhancement cavities, near-concentric cavities offer better cost-effectiveness and structural simplicity, enhancing Raman scattering signals by increasing the number of reflections of the incident laser light. The near-concentric cavity used in this experiment enhanced the Raman scattering signal by 23.77 times for single-beam incident laser light. To avoid the cumbersome nature of manual operations and the introduction of experimental errors, a dedicated automatic sampling and waste disposal device was designed for the cavity-enhanced Raman spectrometer, capable of functions such as selective sampling, sampling liquid level monitoring, air purging, and automatic waste disposal. The inclusion of the automatic sampling and waste disposal device aids in expanding the functionality of the cavity-enhanced Raman spectrometer in online detection. Compared to traditional quantitative analysis methods (such as titration), cavity-enhanced Raman spectroscopy offers advantages such as high sensitivity, ease of operation, no need for reagent pretreatment, non-destructive detection, rapid detection, and the ability to detect multiple molecules and ions simultaneously, providing a novel and efficient analytical tool for fields such as chemical analysis. Experimental results show that the detection limits of this technique for SO^2-₄, NO^-₃, CO^2-₃, and HCO^-₃ are 50, 50, 17, and 30 mg·L^-1, respectively, with correlation coefficients (R²) of the established standard quantitative analysis models exceeding 0.999, demonstrating excellent analytical performance and linear response capabilities. Five sets of tests were conducted on actual in-situ leaching sample solutions from two mining areas using the models, revealing that the acid leaching solution contained SO^2-₄ and NO^-₃, with average ion concentrations of 10 743.10 and 1 253.52 mg·L^-1, respectively, and relative standard deviations (RSD) of 0.39% and 1.39%, respectively. In contrast, the neutral leaching solution contained SO^2-₄, CO^2-₃, and HCO^-₃, with average ion concentrations of 1 400.87, 98.31, and 550.04 mg·L^-1, respectively, and RSD of 1.42%, 2.13%, and 1.69%, respectively. The comparison of experimental results using cavity-enhanced Raman spectroscopy showed much smaller errors than those using titration, further demonstrating the great application value of cavity-enhanced Raman spectroscopy in accurate and efficient quantitative analysis of ions in solutions.

Key words：Cavity-Enhanced Raman spectrometry; Automatic sampling and waste disposal device; In-situ leaching solution; Standard quantitative analysis model

收稿日期: 2024-06-27 修订日期: 2024-11-08

中图分类号:

TP216

基金资助: 国家自然科学基金项目(51205005)资助

通讯作者: 罗成奎，陈士恒 E-mail: 2217046383@qq.com; 89387815@qq.com

作者简介: 李文，1975年生，北方工业大学机电工程研究所副教授 e-mail: lw@ncut.edu.cn

引用本文:

李文，罗成奎，陈士恒，靳昊澍，李杰，李迤博. 腔增强拉曼光谱法快速定量分析地浸溶液中的酸根离子[J]. 光谱学与光谱分析, 2025, 45(06): 1744-1751.
LI Wen, LUO Cheng-kui, CHEN Shi-heng, JIN Hao-shu, LI Jie, LI Yi-bo. Rapid Quantitative Analysis of Acidic Ions in In-Situ Leaching Solution Using Cavity-Enhanced Raman Spectrometry. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(06): 1744-1751.

链接本文:

https://www.gpxygpfx.com/CN/10.3964/j.issn.1000-0593(2025)06-1744-08 或 https://www.gpxygpfx.com/CN/Y2025/V45/I06/1744