二丁基(2-(羟基氨基)-2-氧乙基)膦酸酯的制备及在锡石浮选中的吸附机理  

Preparation of a novel surfactant dibutyl(2-(hydroxyamino)-2-oxoethyl)phosphonate and its adsorption mechanism in cassiterite flotation

作　　者：肖静晶 吴经芝 刘思思 涂佳 刘汝宽 李昌珠 赵刚 XIAO Jing-jing;WU Jing-zhi;LIU Si-si;TU Jia;LIU Ru-kuan;LI Chang-zhu;ZHAO Gang(State Key Laboratory of Utilization of Woody Oil Resource,Hunan Academy of Forestry,Changsha 410004,China;School of Chemistry and Chemical Engineering,University of South China,Hengyang 421001,China;School of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China)

机构地区：[1]State Key Laboratory of Utilization of Woody Oil Resource,Hunan Academy of Forestry,Changsha 410004,China [2]School of Chemistry and Chemical Engineering,University of South China,Hengyang 421001,China [3]School of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China

出　　处：《Journal of Central South University》2023年第5期1569-1580,共12页中南大学学报（英文版）

基　　金：Project(22108114)supported by the National Natural Science Foundation of China。

摘　　要：设计并合成了一种新型表面活性剂二丁基(2-(羟基氨基)-2-氧乙基)膦酸酯(DBPHA)作为锡石浮选捕收剂。单矿物浮选实验结果表明,在pH~9.00、捕收剂初始浓度8×10^(-5)mol/L的条件下,以DBPHA为捕收剂的锡石浮选回收率可达90%左右,而以苯甲羟肟酸(BHA)为捕收剂的浮选回收率仅为22%。通过zeta电位、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)测量和密度泛函理论计算研究了DBPHA在锡石表面的吸附机理。DBPHA处理过的锡石颗粒zeta电位变化表明DBPHA化学吸附到锡石表面,而添加BHA几乎没有改变锡石的zeta电位。密度泛函理论预测DBPHA具有两个反应中心活性位点,即异羟肟酸基和磷酰基,而BHA只有一个异羟肟酸基活性位点。FTIR和高分辨XPS表明,DBPHA在锡石上的化学吸附产生了DBPHA-Sn表面物质,其中异羟肟酸基(—C(=O)—NHOH)和磷酰基(P=O)基团与表面Sn原子键合,使得DBPHA的疏水基团朝向溶液中,粘附气泡。因此,实现了锡石的有效富集。A novel surfactant dibutyl(2-(hydroxyamino)-2-oxoethyl)phosphonate(DBPHA)was designed and synthesized as a cassiterite flotation collector.Micro-flotation experiment results indicated that under the condition of pH~9.00,collector initial concentration 8×10^(-5) mol/L,the flotation recovery of cassiterite reached about 90%using DBPHA as collector,while only 22%using BHA as collector.The adsorption mechanism of DBPHA on the cassiterite surface was investigated by zeta potential,Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy measurements and density functional theory calculations.The changes in the zeta potential for the DBPHA-treated cassiterite particles demonstrated that DBPHA chemisorbed onto the cassiterite surface,while the addition of benzohydroxamic acid(BHA)barely changed the zeta potential of cassiterite.Density functional theory predicted that DBPHA possessed two active sites of the reaction center,namely,hydroxamate and phosphoryl groups,while BHA only had one hydroxamate group.Fourier transform infrared spectroscopy and high-resolution X-ray photoelectron spectroscopy spectra revealed that the chemisorption of DBPHA on cassiterite produced DBPHA-Sn surface species,where both hydroxamate(—C(=O)—NHOH)and phosphoryl(P=O)groups bonded with surface Sn atoms,causing the hydrophobic groups of DBPHA to orient towards the solutions for attaching bubbles.Therefore,an effective enrichment of cassiterite was achieved.

关 键 词：二丁基(2-(羟基氨基)-2-氧乙基)膦酸酯 羟肟酸 锡石 浮选 吸附机理 

分 类 号：TD952[矿业工程—选矿] TD923.13