1 热力学数据的选取 - 有色金属科学与工程.doc

湿法分解钨酸钴的热力学分析 易 军1*，曹才放2 （1. 广东翔鹭钨业股份有限公司，广东 潮州 515633； 2. 江西理工大学冶金与化学工程学院，江西 赣州 341000） 摘 要：采用空气(或氧气)氧化法处理WC-Co硬质合金废料时，钴和钨将形成难溶于水的化合物钨酸钴．针对湿法分解钨酸钴的问题，分别对Co-W-H2O体系和Co-W-C-H2O体系进行了热力学分析，获得了一系列平衡关系图．，钨酸钴在中性溶液中可稳定存在，采用酸分解或碱分解的方式，均可使钨酸钴分解，并实现钨和钴的分离．碳酸盐分解钨酸钴的热力学趋势较大，分解反应可在较低的碳酸盐过量系数下完成．此外，溶液pH值对碳酸盐分解钨酸钴具有较大的影响． 关键词：硬质合金；钨酸钴；热力学；分解 中图分类号：TF111.31 文献标识码：A Thermodynamic analysis on hydrometallurgical decomposition of cobalt tungstate YI Jun1, CAO Cai-fang2 (1. Guangdong Xianglu Tungsten Co. Ltd., Chaozhou 515633, China; 2. School of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China) Abstract: When treating scraps of WC-Co hard metal with oxygen or air, cobalt tungstate which is insoluble in water would form in the oxidation products. In order to investigate issues related to hydrometallurgical decomposition of cobalt tungstate, thermodynamic equilibriums of Co-W-H2O system and Co-W-C-H2O system were studied respectively and a series of equilibrium diagrams were obtained. The results show that cobalt tungstate is relatively stable in neutral solution. Furthermore, cobalt tungstate can be decomposed by acid or alkali under certain conditions and thus tungsten and cobalt can be separated at the same time. In addition, the decomposition reaction of cobalt tungstate with carbonate can be accomplished at lower excess coefficient of carbonate due to its strong thermodynamic tendency. And, pH value has a remarkable effect on the reaction. Key words: hard metal; cobalt tungstate; thermodynamics; decomposition 0 引 言 硬质合金是钨的主要应用领域，每年约50%~60%的钨用于制造碳化钨基硬质合金[1]．我国是钨的生产和消费大国，随着装备制造、矿山采掘、交通隧道等行业的快速发展，废旧硬质合金日益增多，合理利用此类二次资源对钨行业的可持续发展具有重要意义[2?4]．目前，废旧硬质合金再生利用的技术手段较多[5?7]，按照钨资源回用方式的不同，大体可分为两类：一类是采用锌熔法、酸溶法、选择性电溶法等手段将黏结相钴脱除，得到的碳化钨粉返回用于制造新的硬质合金．这类方法具有工艺流程短、试剂和能源消耗低等优点，但返回的碳化钨粉能否满足高性能硬质合金的需要，碳化钨粉循环使用的限度和回用机制等系列问题仍需深入研究．另一类方法则采用硝石氧化法、硫酸钠熔炼法、空气（氧气）氧化法等手段将碳化钨彻底分解，进而采用湿法冶金流程得到纯的仲钨酸铵．其中，硝石氧化法能使钨转变为可溶水的钨酸钠，有利于后续钨的浸出，但该工艺释放的氮氧化合物容易造成环境污染；硫酸钠