锌掺杂型钛系铯离子筛的制备及其吸附性能

doi:10.16085/j.issn.1000-6613.2023-0555

摘要/Abstract

摘要：

钛系离子筛型吸附剂在盐湖卤水提铯、处理放射性核废水等方面具有很好的应用前景。本文基于改进型溶胶-凝胶技术，将微量Zn²⁺掺入Cs₂Ti₆O₁₃的Ti—O晶格中以改善晶胞结构，制备出锌掺杂型钛酸盐前体材料（CZnTO）。前体经过酸处理形成锌掺杂型质子化钛酸盐（HZnTO），通过X射线衍射仪、扫描电子显微镜与能谱仪、傅里叶变换红外光谱、拉曼光谱和X射线光电子能谱等表征手段对制备的HZnTO进行表征，证明微量Zn²⁺的掺入未破坏原有层状结构。通过吸附实验，考察了水相pH、初始Cs⁺浓度、吸附时间和温度等因素对HZnTO吸附行为的影响。研究表明，在288K、pH=11且初始Cs⁺浓度为3000mg/L的最优条件下，吸附2h左右，HZnTO即可达到饱和吸附容量323mg/g。在初始Cs⁺浓度为30mg/L的低浓度溶液下，HZnTO依然能保持80%以上的吸附率。HZnTO对Cs⁺的吸附符合准二级动力学方程和Langmuir吸附等温式，说明Cs⁺在HZnTO上的吸附为化学吸附，以单分子层吸附为主。选择性吸附实验和循环吸附-脱附实验表明，HZnTO对于Cs⁺的选择性远高于其他离子，循环吸附7次后，HZnTO的吸附容量依然能达到初次循环的87.6%，表现出良好的稳定性。

关键词: 铯离子筛, 掺杂, 吸附, 动力学, 热力学

Abstract:

Titanium-based ion sieve adsorbents have good application prospects in the extraction of cesium from salt lake brine and the treatment of radioactive nuclear wastewater. In this paper, based on the improved sol-gel technology, trace Zn²⁺was doped into the Ti—O lattice of Cs₂Ti₆O₁₃ to improve the cell structure, and the zinc doped titanate precursor material (CZnTO) was prepared. The precursor was subjected to acid treatment to form a zinc-doped protonated titanate (HZnTO). The prepared HZnTO was characterized by XRD, SEM, EDS, FTIR, Raman spectroscopy and XPS, which showed that the incorporation of trace amounts of Zn²⁺did not destroy the original layered structure. Through adsorption experiments, the effects of aqueous pH, initial cesium ion concentration, adsorption time and temperature on the adsorption behavior of HZnTO were investigated. The studies found that at 288K, pH=11 and an initial Cs⁺ concentration of 3000mg/L, the adsorption of HZnTO for about 2h could achieve a saturated adsorption capacity of 323mg/g. In a low concentration solution with an initial Cs⁺ concentration of 30mg/L, HZnTO could still maintain an adsorption and removal rate of over 80%. The adsorption of Cs⁺ on HZnTO conformed to the quasi second order kinetic equation and Langmuir adsorption isotherm, indicating that the adsorption of Cs⁺ on HZnTO was chemical adsorption mainly by single molecular layer adsorption. Selective adsorption experiments and cyclic adsorption-desorption experiments showed that the selectivity of HZnTO for Cs⁺was much higher than that of other ions. After 7 cycles of cyclic adsorption, the adsorption capacity of HZnTO could still reach 87.6% of that of the initial cycle, demonstrating a good stability.

Key words: cesium ion sieve, doping, adsorption, kinetics, thermodynamics

中图分类号:

TQ131.1

王德斌, 林梦雨, 杨雪, 董殿权. 锌掺杂型钛系铯离子筛的制备及其吸附性能[J]. 化工进展, 2024, 43(4): 1953-1961.

WANG Debin, LIN Mengyu, YANG Xue, DONG Dianquan. Preparation and adsorption properties of zinc-doped titanium-based cesium ion sieves[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1953-1961.

图/表 19

图1 不同锌掺杂比例下CZnTO-x样品的XRD谱图

图2 不同锌掺杂比例下HZnTO-x样品的XRD谱图

图3 传统方法制备的HTO与使用改进型溶胶-凝胶法制备的HZnTO的SEM图

图4 HZnTO的EDS Mapping图

图5 CZnTO与HZnTO的红外光谱图

图6 CZnTO与HZnTO的拉曼光谱图

图7 CZnTO与HZnTO的XPS能谱图

图8 不同浓度的HCl中Cs+浸出率与时间的关系

图9 不同浓度的HCl中Zn2+与Ti4+的溶损率

图10 pH对吸附性能的影响

图11 初始浓度对吸附性能的影响

图12 HZnTO吸附Cs+的准一级动力学曲线和准二级动力学曲线

表1 准一级、准二级动力学相关参数

溶液浓度 /mg·L^-1	准一级动力学			准二级动力学
溶液浓度 /mg·L^-1	q_m/mg·g^-1	K₁	R²	q_m/mg·g^-1	K₂	R²
3000	274.498	1.172	0.981	280.430	0.01657	0.999

图13 HZnTO对Cs+的吸附等温线

图14 Langmuir吸附模型

图15 Freundlich吸附模型

表2 Langmuir模型和Freundlich模型的相关参数

温度/K	Langmuir模型			Freundlich模型
温度/K	q_m/mg·g^-1	K_L	R²	K_F	1/n	R²
288	344.82	0.0045	0.993	7.26	0.508	0.977
298	295.82	0.0043	0.987	5.43	0.527	0.964
308	266.30	0.0037	0.982	3.32	0.582	0.929

图16 HZnTO的吸附选择性

图17 HZnTO的循环吸附-脱附性能

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