摘要
粉煤灰盐酸法制备氧化铝是具有重要工业应用潜力的工艺之一,研究粉煤灰酸浸液的离子结构对于该工艺中的除铁工序具有重要意义。将热力学计算法、量子化学计算方法和Raman光谱法相结合,研究了在pH分别为1.0、1.5、2.0条件下,粉煤灰盐酸浸出液中AlCl_(3)-FeCl_(3)-FeCl_(2)-HCl-H_(2)O体系的离子结构。结果表明:在pH=1.0时,体系中Fe和Al配合离子主要以[FeCl]^(+)、[FeCl_(2)]^(+)、[AlCl]^(2+)等形式存在;在pH升至1.5和2.0时,体系中[FeCl]^(+)、[FeCl_(2)]^(+)、[AlCl]^(2+)向水解产物[FeOH]^(+)、[FeOH]^(2+)、[AlOH]^(2+)等羟基配体转变;波函数分析结果表明,在低pH下,由于氯离子因浓度较高而占据优势,使得氯化物配合物更稳定;随pH升高,氢氧根离子浓度升高,同时高配位羟基配合物因具备更高的金属-氧键级与更低的吉布斯自由能,其形成过程变得更加容易。
Preparation of alumina from fly ash by hydrochloric acid method is one of the processes with significant industrial application potential.Therefore,studying the ionic structure in acid leaching solution of fly ash is of great significance for iron removal process in the method.The ionic structure of the AlCl_(3)-FeCl_(3)-FeCl_(2)-HCl-H_(2)O system in hydrochloric acid leaching solution of fly ash at pH values of 1.0,1.5,and 2.0 was investigated by combining thermodynamic calculation,quantum chemical calculation,and Raman spectroscopy.The results show that at pH=1.0,the main forms of Fe and Al complex ions in the system are[FeCl]^(+),[FeCl_(2)]^(+)and[AlCl]^(2+);when the pH rises to 1.5 and 2.0,[FeCl]^(+),[FeCl_(2)]^(+)and[AlCl]^(2+)transform into hydrolysis products such as[FeOH]^(+),[FeOH]^(2+)and[AlOH]^(2+)with hydroxyl ligands.The wave function analysis results indicate that at low pH,due to the high concentration of chloride ions,the chloride complexes are more stable.As the pH increases,the concentration of hydroxide ions increases,and the formation of high-coordination hydroxyl complexes becomes easier due to their higher metal-oxygen bond order and lower Gibbs free energy.
作者
张晗阳
胡宪伟
康红光
郭瑞东
Muhammad Murtadho
严枫云
杨酉坚
王耀武
王兆文
ZHANG Hanyang;HU Xianwei;KANG Hongguang;GUO Ruidong;MUHAMMAD Murtadho;YAN Fengyun;YANG Youjian;WANG Yaowu;WANG Zhaowen(School of Metallurgy,Northeastern University,Shenyang 110819,China;Key Laboratory of Ecological Metallurgy of Multimetallic Mineral Resources,Ministry of Education,Shenyang 110819,China)
出处
《湿法冶金》
北大核心
2025年第4期440-447,共8页
Hydrometallurgy of China
基金
国家自然科学基金资助项目(52341402)
教育部中央高校基本科研业务费资助项目(N2225045)。
关键词
氧化铝
粉煤灰
配合离子
拉曼光谱
量子化学计算
alumina
fly ash
complex ion
Raman spectroscopy
quantum chemical calculations
作者简介
第一作者:张晗阳(1998—),男,硕士研究生,主要研究方向为水溶液电化学。;通信作者:胡宪伟(1981—),男,博士,教授,主要研究方向为铝电解。E-mail:huxw@smm.neu.edu.cn。
