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用于回收U(VI)的新型螯合亚氨基磷烷衍生物(磷腈)的合成。

Synthesis of a New Chelating Iminophosphorane Derivative (Phosphazene) for U(VI) Recovery.

作者信息

Atia Bahig M, Sakr Ahmed K, Gado Mohamed A, El-Gendy Hassan S, Abdelazeem Nagwa M, El-Sheikh Enass M, Hanfi Mohamed Y, Sayyed M I, Al-Otaibi Jamelah S, Cheira Mohamed F

机构信息

Nuclear Materials Authority, P.O. Box 530, El Maadi, Cairo, Egypt.

National Research Center (NRC), 33 El-Buhoth Street, Dokki, Cairo 12622, Egypt.

出版信息

Polymers (Basel). 2022 Apr 21;14(9):1687. doi: 10.3390/polym14091687.

Abstract

A new synthetic chelating N-hydroxy-N-trioctyl iminophosphorane (HTIP) was prepared through the reaction of trioctylphosphine oxide (TOPO) with N-hydroxylamine hydrochloride in the presence of a Lewis acid (AlCl). Specifications for the HTIP chelating ligand were successfully determined using many analytical techniques, C-NMR, H-NMR, FTIR, EDX, and GC-MS analyses, which assured a reasonable synthesis of the HTIP ligand. The ability of HTIP to retain U(VI) ions was investigated. The optimum experimental factors, pH value, experimental time, initial U(VI) ion concentration, HTIP dosage, ambient temperature, and eluents, were attained with solvent extraction techniques. The utmost retention capacity of HTIP/CHCl was 247.5 mg/g; it was achieved at pH = 3.0, 25 °C, with 30 min of shaking and 0.99 × 10 mol/L. From the stoichiometric calculations, approximately 1.5 hydrogen atoms are released during the extraction at pH 3.0, and 4.0 moles of HTIP ligand were responsible for chelation of one mole of uranyl ions. According to kinetic studies, the pseudo-first order model accurately predicted the kinetics of U(VI) extraction by HTIP ligand with a retention power of 245.47 mg/g. The thermodynamic parameters Δ°, Δ°, and Δ° were also calculated; the extraction process was predicted as an exothermic, spontaneous, and advantageous extraction at low temperatures. As the temperature increased, the value of ∆° increased. The elution of uranium ions from the loaded HTIP/CHCl was achieved using 2.0 mol of HSO with a 99.0% efficiency rate. Finally, the extended variables were used to obtain a uranium concentrate (NaUO, Y.C) with a uranium grade of 69.93% and purity of 93.24%.

摘要

通过三辛基氧化膦(TOPO)与盐酸羟胺在路易斯酸(AlCl)存在下反应制备了一种新型合成螯合N-羟基-N-三辛基亚氨基膦烷(HTIP)。使用多种分析技术,即碳核磁共振(C-NMR)、氢核磁共振(H-NMR)、傅里叶变换红外光谱(FTIR)、能谱分析(EDX)和气相色谱-质谱联用(GC-MS)分析,成功确定了HTIP螯合配体的规格,这确保了HTIP配体的合理合成。研究了HTIP保留U(VI)离子的能力。采用溶剂萃取技术获得了最佳实验因素,即pH值、实验时间、初始U(VI)离子浓度、HTIP用量、环境温度和洗脱剂。HTIP/CHCl的最大保留容量为247.5 mg/g;在pH = 3.0、25℃、振荡30分钟且初始U(VI)离子浓度为0.99×10⁻³mol/L的条件下实现。通过化学计量计算,在pH 3.0的萃取过程中大约释放1.5个氢原子,且4.0摩尔的HTIP配体负责螯合一摩尔的铀酰离子。根据动力学研究,伪一级模型准确预测了HTIP配体萃取U(VI)的动力学,保留能力为245.47 mg/g。还计算了热力学参数ΔG°、ΔH°和ΔS°;预测萃取过程是放热的、自发的,且在低温下是有利的萃取过程。随着温度升高,∆G°值增大。使用2.0摩尔的H₂SO₄以99.0%的洗脱效率实现了从负载的HTIP/CHCl中洗脱铀离子。最后,使用扩展变量获得了铀品位为69.93%、纯度为93.24%的铀精矿(Na₂UO₄·Y₂O₃·C)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92e6/9099652/7be72a6bb55e/polymers-14-01687-g011.jpg

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