Ca<sup>2+</sup>影响辛基异羟肟酸浮选独居石的FTIR、XPS研究

doi:10.3964/j.issn.1000-0593(2024)10-2959-09

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摘要：独居石浮选体系中往往有方解石、萤石、白云石等大量的伴生矿，而这些伴生矿在独居石矿中会解离出大量的Ca²⁺，而Ca²⁺往往会影响矿浆浮选环境。为此，通过Ca²⁺的溶液化学计算、独居石浮选试验，以及浮选条件下作用的独居石表面红外光谱分析（FTIR）和X射线光电子能谱（XPS），分析研究Ca²⁺的影响。Ca²⁺的溶液化学计算显示，在水溶液中，随着pH值的升高，Ca²⁺分别以离子态、羟基络合物和氢氧化合物的形式存在，当pH值在7~8之间，优势组分为Ca²⁺和Ca(OH)⁺。独居石浮选结果表明，不添加Ca²⁺时，捕收剂OHA不能充分的浮选独居石，回收率为75.37%；而在pH为8±0.5，加入3×10^-4 mol·L^-1的Ca²⁺剂量，可显著的提高OHA对独居石的浮选性能，回收率达到96.48%。由溶液化学计算可知，Ca(OH)⁺是活化独居石的优势组分；Ca²⁺剂量大于3×10^-4 mol·L^-1时浮选回收率下降幅度较大，说明Ca²⁺剂量的进一步增加，反而抑制独居石浮选，只有一定剂量的Ca²⁺有效的促进独居石浮选，这可能归因于Ca²⁺剂量消耗了OHA的浓度，进而影响独居石的浮选。红外光谱分析表明，在Ca²⁺的作用下，光谱中出现两个关键性的新峰，其一为1 454 cm^-1处的N—O—H弯曲振动峰，其二为880 cm^-1处的O—N拉伸振动峰，而在2 974和2 928 cm^-1的有机峰—CH₃和—CH₂—峰明显增强，这些基团的出现表明发生了化学吸附且吸附强度大于纯独居石吸附OHA的效果。XPS分析表明，仅使用OHA吸附独居石，独居石表面的N元素相对含量较低，为0.61%，而Ca²⁺处理后的独居石，OHA吸附独居石时，独居石表面的N元素相对含量较高，达到2.36，由此可以得出，Ca²⁺会促进OHA吸附到独居石表面。从分峰拟合中可以看出，添加Ca²⁺在独居石的解理面上氧原子与Ca(OH)⁺反应形成O—Ca—OH基团，可以作为吸附OHA的新吸附位点，同时独居石的铈原子与OHA上的两个氧原子形成五元螯合物也作吸附位点，得出独居石表面可以有两个吸附位点，独居石表面的Ca和Ce原子的活性位点都能吸附OHA，有利于OHA在独居石表面吸附，形成更均匀更致密的OHA疏水吸附层，这就是Ca²⁺在OHA浮选独居石的性能得到改善的原因。这项研究有助于丰富矿浆中金属离子的活化理论，也证实了有效的矿物浮选分离不仅仅依赖于捕收剂-矿物相互作用的强度，而在很大程度上依赖于浮选溶液的化学性质。利用或者控制表面反应是开发一种更高效、更经济的浮选工艺的主要技术手段。

关键词：独居石；浮选；辛基异羟肟酸；钙离子；红外光谱；分峰拟合

Abstract：The monazite flotation system often has many associated minerals such as calcite, fluorite, and dolomite. These associated minerals will dissociate a large amount of Ca²⁺ in the monazite ore, and Ca²⁺ often affects the pulp flotation environment. In this paper, the surface properties of monazite were studied by FTIR and XPS when Ca²⁺ affected the flotation of monazite by octyl hydroxamic acid. The research method is mainly through the solution chemical calculation of Ca²⁺, the flotation test of monazite, and the surface infrared spectroscopy ( FTIR ) and X-ray photoelectron spectroscopy ( XPS ) of monazite under flotation conditions. The solution chemical calculation of Ca²⁺ shows that an aqueous solution with increased pH value, Ca²⁺ exists in an ionic state, hydroxyl complex, and hydroxide compound, respectively. At the same time, the dominant components are Ca²⁺ and Ca(OH)⁺ at pH between 7 and 8. The results of monazite flotation showed that OHA could not fully float monazite without adding Ca²⁺, and the recovery rate was 75.37%. When the pH is (8±0.5), and the dosage of Ca Ca²⁺ is 3×10^-4 mol·L^-1, the flotation performance of OHA on monazite can be significantly improved, and the recovery rate reaches 96.48%. According to the solution chemistry calculation, Ca(OH)⁺ is the dominant component of activated monazite. When the Ca²⁺ dose is greater than 3×10^-4 mol·L^-1, the flotation recovery rate decreases greatly, indicating that the further increase of Ca²⁺ dose inhibits the flotation of monazite. Only a certain dose of Ca²⁺ effectively promotes the flotation of monazite, which may be attributed to the consumption of OHA concentration by Ca²⁺ dose, which in turn affects the flotation of monazite. Infrared spectroscopy analysis showed that under the action of Ca²⁺, two key new peaks appeared in the spectrum, one was the N—O—H bending vibration peak at 1 454 cm^-1, the other was the O—N stretching vibration peak at 880 cm^-1, and the organic peaks at 2 974 and 2 928 cm^-1. The —CH₃ and —CH₂— peaks were significantly enhanced, and these groups appeared to indicate that chemical adsorption occurred and the adsorption intensity was greater than that of pure monazite adsorption of OHA. XPS analysis showed that the relative content of N element on the surface of monazite was 0.61 % when only OHA was used to adsorb monazite. In comparison, the relative content of N element on the surface of monazite was 2.36% when OHA was used to adsorb monazite after Ca²⁺ treatment. It can be concluded that Ca²⁺ will promote the adsorption of OHA on the surface of monazite. It can be seen from the peak fitting that the addition of Ca²⁺ reacts with Ca(OH)⁺ to form O—Ca—OH groups on the cleavage surface of monazite to form O—Ca—OH groups, which can be used as a new adsorption site for adsorbing OHA. At the same time, the cerium atom of monazite and the two oxygen atoms on OHA form a five-membered chelate, which also acts as an adsorption site. It is concluded that there can be two adsorption sites on the surface of monazite. The active sites of Ca and Ce atoms on the surface of monazite can adsorb OHA, which is beneficial to the adsorption of OHA on the surface of monazite and forms a more uniform and dense OHA hydrophobic adsorption layer. This is why the performance of Ca²⁺ in OHA flotation of monazite is improved. This study helps to enrich the activation theory of metal ions in pulp and also confirms that effective mineral flotation separation depends not only on the strength of collector-mineral interaction but also on the chemical properties of the flotation solution to a large extent. Utilizing or controlling the surface reaction should be the main goal of developing a more efficient and economical flotation process.

Key words：Monazite; Flotation; Octyl hydroxamic acid; Calcium ion; Infrared spectrum; Peak fitting

收稿日期: 2023-07-14 修订日期: 2023-12-04

中图分类号:

TQ174

基金资助: 国家自然科学基金项目(52264033，51964038)，科技部国家重点研发计划课题(2020YFC1909101)，内蒙古自治区科技计划项目(2021GG0438)，内蒙古自然科学基金项目（2020MS05048）资助

通讯作者: 杨占峰，李解 E-mail: yjslijie@126.com；yang_zhanfeng@163.com

作者简介: 刘荣祥, 1991年生, 内蒙古科技大学矿业与煤炭学院博士研究生 e-mail: 2842014603@qq.com

引用本文:

刘荣祥，杨占峰，李解，曹钊，李强，李计川. Ca²⁺影响辛基异羟肟酸浮选独居石的FTIR、XPS研究[J]. 光谱学与光谱分析, 2024, 44(10): 2959-2967.
LIU Rong-xiang, YANG Zhan-feng, LI Jie, CAO Zhao, LI Qiang, LI Ji-chuan. FTIR and XPS Studies on the Effect of Ca²⁺ on the Fotation of Monazite by Octyl Hydroxamic Acid. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2024, 44(10): 2959-2967.

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