羟肟酸捕收剂对钛铁矿和钛辉石的浮选效果及作用机理

doi:10.12068/j.issn.1005-3026.2025.20240005

摘要/Abstract

摘要：

通过矿物浮选试验研究了苯甲羟肟酸(BHA)、水杨羟肟酸(SHA)、辛基羟肟酸(OHA)、丁苯羟酸(BFXA)作用下钛铁矿与钛辉石的浮选分离行为.采用接触角、Zeta电位、傅里叶变换红外光谱等测试方法以及密度泛函理论（DFT）分析了4种不同结构羟肟酸在钛铁矿与钛辉石表面的作用机理.结果表明：4种羟肟酸对钛铁矿的浮选分离效果顺序为：BFXA>OHA>SHA>BHA；羟肟酸在钛铁矿表面的吸附作用强于钛辉石，加入羟肟酸显著提高了钛铁矿表面疏水性；羟肟酸捕收剂的反应位点为氧肟基的2个氧原子，相比于其他3种羟肟酸，BFXA的最高占据分子轨道(HOMO)能量最高，具有更强的吸附和捕收能力.

关键词: 钛铁矿, 钛辉石, 羟肟酸捕收剂, 浮选, 机理分析

Abstract:

The flotation separation behaviors of ilmenite and titanaugite with benzohydroxamic acid （BHA）， salicylhydroxamic acid （SHA）， octylhydroxamic acid （OHA） and butoxylate acid （BFXA） were studied by mineral flotation test. The interaction mechanisms of four hydroxamic acids with different structures on ilmenite and titanaugite surfaces were analyzed by these means of contact angle， Zeta potential， Fourier transform infrared spectra and density functional theory （DFT）. The results indicate that the separation effect for ilmenite with four hydroxamic acids is listed in the order： BFXA>OHA>SHA>BHA. The adsorption of hydroxamic acids on the surface of ilmenite is stronger than that of titanaugite， and the hydrophobicity of ilmenite is significantly improved by adding hydroxamic acid. The two oxygen atoms within oxyoxime groups of hydroxamic acid collectors are their reaction sites. Compared with the other three hydroxamic acids， BFXA has the highest HOMO orbital energy and thus exhibits stronger adsorption performance and collection capability.

Key words: ilmenite, titanaugite, hydroxamic acid collector, flotation, mechanism analysis

中图分类号:

TD 923

李倩雯, 孟庆有, 袁致涛, 齐赛男. 羟肟酸捕收剂对钛铁矿和钛辉石的浮选效果及作用机理[J]. 东北大学学报（自然科学版）, 2025, 46(6): 138-146.

Qian-wen LI, Qing-you MENG, Zhi-tao YUAN, Sai-nan QI. Floatation Effect and Mechanism of Hydroxamic Acid Collectors for Ilmenite and Titanaugite[J]. Journal of Northeastern University(Natural Science), 2025, 46(6): 138-146.

图/表 14

表1 钛铁矿和钛辉石单矿物化学多元素分析（质量分数） (ilmenite and titanaugite (mass fraction) %)

Table1 Chemical multi-element analyses of purified

名称	TiO₂	FeO	TF	CaO	SiO₂	Al₂O₃	MgO
钛铁矿	51.20	30.85	32.43	0.45	0.76	1.71	3.65
钛辉石	4.52	9.21	10.45	16.84	41.10	6.21	11.04

图1 钛铁矿和钛辉石单矿物的XRD图谱

Fig.1 XRD pattern of purified ilmenite and titanaugite

图2 浮选试验流程

Fig.2 Flotation test process

图3 优化后的捕收剂分子结构（a）—BHA；（b）—BFXA；（c）—SHA；（d）—OHA.

Fig.3 Optimized molecular structure of the collectors

图4 4种羟肟酸作用下pH对钛铁矿与钛辉石可浮性的影响（a）—BHA为200 mg/L；（b）—BFXA为25 mg/L；（c）—OHA为50 mg/L；（d）—SHA为150 mg/L.

Fig.4 Effect of pH on the floatability of ilmenite and titanaugite under the action of four types of hydroxamic acids

图5 4种羟肟酸用量对钛铁矿与钛辉石可浮性的影响（a）—pH=8；（b）—pH=8；（c）—pH=9；（d）—pH=6.

Fig.5 Effect of the dosage of four hydroxamic acids on the floatability of ilmenite and titanaugite

图6 4种不同羟肟酸作用下混合矿的浮选分离效果

Fig.6 Effect of different hydroxamic acid on flotation separation effect of mixed ore

图7 不同羟肟酸对钛铁矿与钛辉石表面接触角的影响

Fig.7 Effect of different hydroxamic acids on surface contact angls of ilmenite and titanaugite

图8 羟肟酸作用前后pH对钛铁矿与钛辉石动电位的影响（a）—钛铁矿；（b）—钛辉石.

Fig.8 Effect of pH on Zeta potential of ilmenite and titanaugite before and after hydroxamic acid action

图9 不同结构羟肟酸的红外光谱

Fig.9 Infrared spectra of hydroxamic acids with different structures

图10 羟肟酸作用前后钛铁矿的红外光谱图（a）—钛铁矿+BHA；（b）—钛铁矿+BFXA；（c）—钛铁矿+OHA；（d）—钛铁矿+SHA.

Fig.10 Infrared spectra of ilmenite before and after hydroxamic acid action

图11 羟肟酸作用前后钛辉石的红外光谱图（a）—钛辉石+BHA；（b）—钛辉石+BFXA；（c）—钛辉石+OHA；（d）—钛辉石+SHA.

Fig.11 Infrared spectra of titanaugite before and after hydroxamic acid action

图12 羟肟酸分子静电势图

Fig 12 Molecular electrostatic potential diagram of hydroxamic acids

表2 4种羟肟酸的分子轨道能量参数

Table 2 Molecular orbital energy parameters of four hydroxamic acids

羟肟酸	E_HOMO/eV	E_LUMO/eV	∆E/eV
BHA	-5.598 6	-2.227 2	-3.371 4
BFXA	-5.217 5	-1.177 5	-4.040 0
OHA	-5.554 1	-0.912 1	-4.642 0
SHA	-5.748 8	-2.440 6	-3.308 2

参考文献 23

[1]	Meng Q Y， Yuan Z T， Yu L， et al. Study on the activation mechanism of lead ions in the flotation of ilmenite using benzyl hydroxamic acid as collector ［J］. Journal of Industrial and Engineering Chemistry， 2018， 62： 209-216.
[2]	Liu H， Zhao W Q， Zhai J H， et al. Activation mechanism of lead （II） to ilmenite flotation using salicylhydroxamic acid as collector［J］. Minerals， 2020， 10（6）： 10060567.
[3]	Miao Y C， Wen S M， Feng Q C， et al. Enhanced adsorption of salicylhydroxamic acid on ilmenite surfaces modified by Fenton and its effect on floatability［J］. Colloids and Surfaces A： Physicochemical and Engineering Aspects， 2021， 626： 127057.
[4]	Zhai J H， Chen P， Sun W， et al. A review of mineral processing of ilmenite by flotation［J］. Minerals Engineering， 2020， 157： 106558.
[5]	Yang Y H， Xu L H， Liu Y C， et al. Flotation separation of ilmenite from titanaugite using mixed collectors［J］. Separation Science and Technology， 2016， 51（11）： 1840-1846.
[6]	Meng Q Y， Du Y S， Yuan Z T， et al. Study on the mineral characteristics and separation performances of a low-TiO₂ ilmenite［J］. Minerals Engineering， 2022， 179： 107458.
[7]	Xiao W， Shao Y H， Yu J Y， et al. Adsorption differences and mechanism of Pb-BHA and Al-BHA in the flotation separation of ilmenite and titanaugite［J］. Minerals Engineering， 2023， 197： 108072.
[8]	Cai J Z， Deng J S， Wang L， et al. Reagent types and action mechanisms in ilmenite flotation： a review［J］. International Journal of Minerals， Metallurgy and Materials， 2022， 29（9）： 1656-1669.
[9]	程奇，钟宏，王帅，等.长碳链烷基羟肟酸对钛铁矿的浮选性能与机理研究［J］.应用化工，2016，45（8）：1407-1411.
	Cheng Qi， Zhong Hong， Wang Shuai， et al. Flotation performance and adsorption mechanism of long-chain alkyl hydroxamic acid to ilmenite ［J］. Applied Chemical Industry，2016，45（8）：1407-1411.
[10]	Xu H F， Zhong H， Tang Q， et al. A novel collector 2-ethyl-2-hexenoic hydroxamic acid： flotation performance and adsorption mechanism to ilmenite［J］. Applied Surface Science， 2015， 353： 882-889.
[11]	董宏军，陈正学.水杨羟肟酸浮选细粒钛铁矿的研究［J］.矿冶工程，1991，11（1）：19-22.
	Dong Hong-jun， Chen Zheng-xue. A study on flotation of fine ilmenite with salicylhydroxamic acid ［J］. Mining and Metallurgical Engineering，1991，11（1）：19-22.
[12]	Zhao G， Zhou X T， Li F X， et al. Flotation performance of anisic hydroxamic acid as new collector for tungsten and tin minerals［J］. Journal of Central South University， 2022， 29（11）： 3645-3655.
[13]	Li Y Q， Liu Y C， Chen J H， et al. Structure-activity of chelating collectors for flotation： a DFT study［J］. Minerals Engineering， 2020， 146： 106133.
[14]	Zhao G， Liu S， Qi J， et al. The structure-property relationship of p-alkoxyl benzohydroxamic acids towards wolframite flotation： theoretical and experimental investigations［J］. Journal of Molecular Liquids， 2023， 381： 121659.
[15]	黄建平，钟宏，邱显杨，等.环己甲基羟肟酸对黑钨矿的浮选行为与吸附机理［J］.中国有色金属学报，2013，23（7）：2033-2039.
	Huang Jian-ping， Zhong Hong， Qiu Xian-yang，et al. Flotation behavior and adsorption mechanism of cyclohexyl hydroxamic acid to wolfrienite ［J］. The Chinese Journal of Nonferrous Metals，2013，23（7）：2033-2039.
[16]	Fang S， Xu L H， Wu H Q， et al. Comparative studies of flotation and adsorption of Pb （II）/benzohydroxamic acid collector complexes on ilmenite and titanaugite［J］. Powder Technology， 2019， 345： 35-42.
[17]	Yao X， Yu X Y， Wang L P， et al. Preparation of cinnamic hydroxamic acid collector and study on flotation characteristics and mechanism of scheelite［J］. International Journal of Mining Science and Technology， 2023，33（6）：773-781.
[18]	Yu L， Xu X Y， Yuan Z T， et al. Effect of lead ions on the selective flotation of ilmenite against titanaugite using octyl hydroxamic acid as collector［J］. Applied Surface Science， 2022， 603： 154458.
[19]	Wang X F， Wang Y J， Wen S M， et al. Flotation behavior and adsorption mechanism of salicylhydroxamic acid in artificial mineral anosovite［J］. Journal of Central South University， 2019， 26（4）： 806-812.
[20]	Lu Y X， Wang S， Cao Z F， et al. Structure-activity relationships of oxime compounds as flotation collectors by DFT calculations［J］. Transactions of Nonferrous Metals Society of China， 2022， 32（12）： 4076-4087.
[21]	Wang Z J， Xu L H， Wu H Q， et al. Adsorption of octanohydroxamic acid at fluorite surface in presence of calcite species［J］. Transactions of Nonferrous Metals Society of China， 2021， 31（12）： 3891-3904.
[22]	Xu Y L， Huang K H， Li H Q， et al. Adsorption mechanism of styryl phosphonate ester as collector in ilmenite flotation［J］. Transactions of Nonferrous Metals Society of China， 2022， 32： 4088-4098.
[23]	Zhao G， Zhong H， Qiu X Y， et al. The DFT study of cyclohexyl hydroxamic acid as a collector in scheelite flotation［J］. Minerals Engineering， 2013， 49： 54-60.