EVALUATION OF INTERFACIAL REACTIONS IN SOLVENT EXTRACTION PROCESSES

溶剂萃取过程中界面反应的评估

• 批准号: 61470034
• 负责人: WATARAI Hitoshi
• 金额: $ 3.65万
• 依托单位: AKITA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61470034/
• 关键词: Solvent extraction; Chelate extraction; Ion-association extraction; Extraction rate; Interfacial adsorption; Interfacial reaction; Complex formation; 撹拌効果; 協同抽出; 錯生成速度; 液液界面における錯形成反応

INTERFACIAL REACTIONS IN SOLVENT EXTRACTION SYSTEMS WERE EXTENSIVELY INVESTIGATED BY MEANS OF THE HIGH-SPEED STIRRING METHOD AND OTHER TECHNIQUES. THE FOLLOWING RESULTS WERE OBTAINED.1. INTERFACIAL PHENOMENA IN CHELATE EXTRACTIONS (1) THE INTERFACIAL ADSORPTIVITY OF -HYDROXY OXIMES WAS STUDIED UNDER VARIOUS CONDITIONS AND THE ADSORPTION MECHANISM WAS CLARIFIED. THE EXTRACTION RATES OF NICKEL (II) WITH SME529 OR LIX65N IN HEPTANE WERE STUDIED AND THE RATE-CONTROLLING STEP WAS CONCLUDED TO BE THE FORMATION OF 1:1 COMPLEX AT INTERFACE, SINCE THE EXTRACTION RATE WAS PROPORTIONAL TO NICKEL(II) CONCENTRATION, HYDROGEN ION CONCENTRATION, AND THE INTERFACIAL CONCENTRATION OF THE EXTRACTANAT. THE KINETIC EFFECTS OF THE EXTRACTANTS AND ORGANIC SOLVENTS WERE ALSO EXPLAINED ACCORDING TO THE INTERFACIAL MECHANISM. (2) -DIKETONES ADSORBED AT HEPTANE/WATER INTERFACE ONLY IN THE FORMS OF THE ENCLATE IONS. THE PH DEPENDENCE OF THE INTERFACIAL ADSORPTIVITY WAS EXPLAINED BY THE EFFECTS OF PH ON THE DISSOCIATION EQUILIBRIA AND THE DISTRIBUTION RATIO. A CORRELATION BETWEEN THE ADSORPTION CONSTANTS AND THE DISTRIBUTION CONSTANTS WAS FOUND OUT.2. INTERFACIAL PHENOMENA IN ION-ASSOCIATION EXTRACTIONS (1) THE EFFECTS OF SUBSTITUENTS, ORGANIC SOLVENTS AND COUNTER ANIONS ON THE INTERFACIAL ADSORPTIVITY OF TRIS(1,10-PHENANTHROLINE)IRON(II) COMPLEX WERE ELUCIDATED. THE ADSORPTIVITY OF THE COMPLEX INCREASED IN THE LIGAND OF SMALLER DISTRIBUTION CONSTANT AND IN THE COUNTER ANION OF LARGER HYDRATION ENERGY. (2) THE ION-ASSOCIATION EXTRACTION RATES OF IRON(II)-1,10-PHENANTHROLINES COMPLEX WERE STUDIED AND THE RATE CONTROLLING STEP WAS CONCLUDED TO BE THE 1:1 COMPLEX FORMATION FROM THE FIRST-ORDER DEPENDENCES OF THE RATE ON THE IRON(II) AND THE LIGAND CONCENTRATIONS. THE CONTRIBUTION OF THE INTERFACIAL REACTION WAS HIGHER IN THE LIGAND OF LARGER DISTRIBUTION CONSTANT. THE ADSORPTION OF THE ION-PAIRS DEPRESSED APPARENTLY THE OBSERVED EXTRACTION RATES.

采用高速搅拌法等技术对溶剂萃取体系中的界面反应进行了广泛的研究。得到以下结果： 1．螯合物萃取中的界面现象 (1)研究了不同条件下α-羟基肟的界面吸附性能，阐明了吸附机理。研究了 SME529 或 LIX65N 在庚烷中对镍 (II) 的萃取率，由于萃取率与镍 (II) 浓度、氢气成正比，因此速率控制步骤被认为是在界面处形成 1:1 络合物离子提取物的浓度和界面浓度。还根据界面机制解释了提取剂和有机溶剂的动力学效应。 (2) -二酮仅以 ENCLATE 离子的形式吸附在庚烷/水界面上。通过PH值对解离平衡和分布比的影响来解释界面吸附力的PH值依赖性。发现了吸附常数与分布常数之间的相关性。 2．离子缔合萃取中的界面现象(1)阐明了取代基、有机溶剂和抗衡阴离子对三(1,10-菲咯啉)铁(II)络合物界面吸附性的影响。配体分布常数较小、水化能较大的反阴离子时，络合物的吸附力增强。 (2)研究了铁(II)-1,10-菲咯啉络合物的离子缔合萃取率，根据速率对铁的一阶依赖性，得出速率控制步骤为1:1络合物形成(II) 和配体浓度。配体分布常数越大，界面反应的贡献越大。离子对的吸附明显降低了观察到的萃取率。

项目成果

H. Watarai: "Interfacial adsorption of iron(II)-4,7-diphenyl-1,10-phenanthroline complex in ion-association extraction systems" Bull. Soc. Chem. Jpn.

H. Watarai：“离子缔合萃取系统中铁(II)-4,7-二苯基-1,10-菲咯啉复合物的界面吸附”Bull。

H. Watarai: "Interfacial adsorption of beca-diketones in vigorously stirred heptane/aqueous phase systems" Solv. Extr. Ion Exch.

H. Watarai：“β-二酮在剧烈搅拌的庚烷/水相系统中的界面吸附”Solv。

H. Watarai: "Interfacial phenomena in the extraction kinetics of nickel(II) with 2'-hydroxy-5'-nonylacetophenone oxime" Bull. Chem. Soc. Jpn.59. 3469-3473 (1986)

H. Watarai：“镍 (II) 与 2-羟基-5-壬基苯乙酮肟萃取动力学中的界面现象”Bull。

H.Watarai: Anal.Chem.

H.Watarai：《肛门化学》。

Hitoshi Wataroi: Bull.Chem.Soc.Jpn.59. 3469-3473 (1986)

渡井仁：Bull.Chem.Soc.Jpn.59。