N-烷酰基卤代苯基羟胺的设计、合成及对稀土矿物的浮选特性  

Design,Synthesis and Flotation Characteristics of N-acyl Halogenated Phenylhydroxylamine for Rare Earth Minerals

作　　者：卢宇熙 黄磊 刘兴华[1] 刘旭[1] 陈雯[1] LU Yuxi;HUANG Lei;LIU Xi nghua;LIU Xu;CHEN Wen(Changsha Research Institute of Mining and Metallurgy Co.,Ltd.,Changsha 410012,China;College of Chemistry and Chemi cal Engineering of Central South University,Changsha 410083,China)

机构地区：[1]长沙矿冶研究院有限责任公司,长沙410012 [2]中南大学化学化工学院,长沙410083

出　　处：《有色金属(选矿部分)》2025年第2期146-156,共11页Nonferrous Metals(Mineral Processing Section)

基　　金：国家重点研发计划项目(2020YFC1909103)。

摘　　要：稀土是极其重要的战略资源,稀土和含钙矿物的高效浮选分离是稀土浮选领域的一大难题。在N-烷酰基苯基羟胺的基础上,通过苯环对位卤代,设计并合成了新型捕收剂N-正丁酰基对氯苯基羟胺(NPCl-4)和N-正丁酰基对氟苯基羟胺(NPF-4),将其应用于稀土浮选。密度泛函理论(DFT)计算说明卤素在苯环的对位取代,增加了药剂的负电中心,强化了主要作用基团上关键含氧位点的空间位阻效应,提升了药剂的给电子能力和疏水性能。在卤素取代后,降低的pKa及作用基团二面角有利于与矿物表面金属位点进行高效的靶向螯合作用。浮选试验结果表明,NPCl-4和NPF-4均对于氟碳铈矿具有较强的浮选性能,明显优于相应的N-正丁酰基苯基羟胺(NP-4)。同时Cl较大的半径带来的空间位阻会阻碍NPCl-4在萤石表面的吸附,而F与萤石表面Ca位点更强的作用有利于NPF-4在萤石表面的密集吸附,导致NPCl-4在氟碳铈矿与萤石的分选中具有更好的选择性,有望成为稀土矿物的新型高效捕收剂。Rare earth is a critical strategic resource,and the efficient flotation separation of rare earth and calcium-containing minerals is a significant challenge in the field of rare earth flotation.This study involved the design and synthesis of novel collectors,namely N-butyryl-p-chlorophenylhydroxylamine(NPCl-4)and N-butyryl-p-fluorophenylhydroxylamine(NPF-4),based on N-alkanoylphenylhydroxylamine by para-halogenation of the benzene ring,which were applied to rare earth flotation.The results of density functional theory(DFT)calculations showed that the para-substitution of halogens on the benzene ring increased the negative charge center,enhanced the steric hindrance effect of key oxygen-containing sites on the main functional groups,and improved the electron-donating ability and hydrophobic properties of the agent.After halogen substitution,the reduced pKa and the dihedral angle of the action group were beneficial to the efficient targeted chelation with the metal sites on the mineral surface.The results of the flotation experiment showed that both NPCl-4 and NPF-4 exhibited strong flotation performance for bastnaesite,which was significantly better than the corresponding the N-butyrylphenylhydroxylamine(NP-4).Concurrently,the steric hindrance caused by the larger radius of Cl will impede the adsorption of NPCl-4 on the fluorite surface,while the stronger interaction between F and Ca sites on the fluorite surface will facilitate the dense adsorption of NPF-4 on the fluorite surface,resulting in NPCl-4 has better selectivity in the separation of bastnaesite and fluorite,and is expected to become a new type of efficient collector for rare earth minerals.

关 键 词：N-烷酰基卤代苯基羟胺 氟碳铈矿 萤石 浮选 捕收剂 

分 类 号：TD923[矿业工程—选矿]