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钨冶炼除磷渣中浸出钨和钼同步抑制磷溶出研究

Research on simultaneous inhibition of phosphorus leaching with leaching tungsten and molybdenum from phosphorus removal slag in tungsten smelting

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【作者】 曾斌曾祥荣张魁芳王瑞祥

【Author】 ZENG Bin;ZENG Xiangrong;ZHANG Kuifang;WANG Ruixiang;College of Intelligent Manufacturing and Materials Engineering,Gannan University of Science and Technology;Jiangxi Yaosheng Tungsten Industry Co.Ltd.;Key Laboratory of Green Extraction and High Quality Utilization of Regional Characteristic Metal Resources in Ganzhou City,Gannan University of Science and Technology;College of Metallurgical Engineering,Jiangxi University of Science and Technology;

【通讯作者】 张魁芳;

【机构】 赣南科技学院智能制造与材料工程学院江西耀升钨业股份有限公司赣南科技学院赣州市区域特色金属资源绿色提取及高质化利用重点实验室江西理工大学冶金工程学院

【摘要】 钨冶炼过程中会产生大量的除磷渣,除磷渣是重要的钨和钼二次资源,但在浸出钨(WO3)和钼(Mo)的过程中,磷容易同步溶出,严重影响后续的分离和提纯。针对该问题,采用碳酸钠作为浸出剂,加入氧化钙和氯化镁作为抑制磷同步溶出试剂,系统研究了浸出过程中钨、钼、磷的行为。研究结果表明:在浸出剂碳酸钠的质量浓度为160 g/L、抑制剂氧化钙和氯化镁用量均为除磷渣质量的10%、浸出温度为180℃、浸出时间为4 h、液固质量比为4:1、搅拌速度为120 r/min时,在钨冶炼除磷渣中,WO3、Mo浸出率分别达到98.47%、98.66%,在浸出渣中,WO3、Mo质量分数由浸出前的6.92%、9.44%分别降至0.10%、0.12%,而P浸出率仅为0.05%,浸出液中P质量浓度为0.01 g/L,无需进行二次除磷处理,满足后续制备高纯钨和钼产品对杂质P质量分数≤0.000 7%的要求,保留在浸出渣中的P质量分数为8.03%,便于后续回收。利用化学分析法、X衍射(XRD)、能谱(EDS)、荧光光谱法(XRF)等表征浸出前后的除磷渣的物相和元素分布变化,并结合相关反应的热力学数据可知,氧化钙和氯化镁的引入可以维持浸出环境的碱度,防止碳酸根水解,以保证钨和钼高效浸出,同时,氧化钙和氯化镁可与溶出进入浸出液中的磷生成稳定的磷酸钙盐和磷酸镁盐,抑制磷的溶出,实现除磷渣的绿色资源化利用。

【Abstract】 The tungsten smelting process yields substantial quantities of phosphorus removal slag, which is an important secondary resource containing recoverable tungsten and molybdenum. Nevertheless, the hydrometallurgical extraction of tungsten and molybdenum from phosphorus removal slag is frequently accompanied by concomitant dissolution of phosphorus, which seriously affects the subsequent separation and purification. To address these challenges, sodium carbonate was proposed as the leaching agent, while calcium oxide and magnesium chloride were added as reagents to inhibit the simultaneous leaching of phosphorus. The behavior of tungsten, molybdenum, and phosphorus during the leaching process was systematically studied. The results show that at the leaching agent sodium carbonate mass concentration of 160 g/L, inhibitor calcium oxide and magnesium chloride dosage of 10% of the mass of phosphorus removal slag, leaching temperature of 180 ℃, leaching time of 4 h, liquid-solid mass ratio of 4:1, stirring speed of 120 r/min, the leaching rates of WO3 and Mo in tungsten smelting phosphorus removal slag reach 98.47% and 98.66%, respectively. The WO3 and Mo mass fractions in leaching slag decrease from 6.92% and 9.44% leaching to 0.10% and 0.12%, respectively, while the P leaching rate is only 0.05%. And the mass concentration of P in the leaching solution is 0.01 g/L, which does not require secondary phosphorus removal treatment and meets the requirement of impurity P mass fraction ≤0.000 7% for the subsequent preparation of high-purity tungsten and molybdenum products. The mass fraction of P retained in the leaching residue is 8.03%, which is convenient for subsequent recovery. By using chemical analysis, X-ray diffraction(XRD), energy dispersive spectroscopy(EDS), fluorescence spectroscopy(XRF) and other methods to characterize the changes in phase and element distribution in the phosphorus removal slag before and after leaching, combined with thermodynamic data of related reactions, it can be concluded that the introduction of calcium oxide and magnesium chloride can maintain the alkalinity of the leaching environment, prevent carbonate hydrolysis, and ensure efficient leaching of tungsten and molybdenum. At the same time, it can form stable calcium phosphate and magnesium phosphate salts with the phosphorus leaching into the leaching solution, inhibit the leaching of phosphorus, and achieve green resource utilization of phosphorus removal slag.

【基金】 赣鄱英才支持计划青年类创新领军人才资助项目(gpyc20240040);赣鄱俊才支持计划青年科技人才托举资助项目(2025QT15);江西省自然科学基金资助项目(20242BAB25244);江西省重点研发计划项目(20223BBH80012);江西省重点研发计划项目(20244BBG73010);赣州市科技成果熟化与工程化项目(2024SHCC0015)~~
  • 【文献出处】 中南大学学报(自然科学版) ,Journal of Central South University(Science and Technology) , 编辑部邮箱 ,2025年08期
  • 【分类号】X758
  • 【下载频次】9
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