As2O3真空碳热还原制备粗金属砷的热力学研究 - 有色金属（冶炼部分）.DOCVIP

As2O3真空碳热还原制备粗金属砷的热力学研究 卢红波 （云南锡业?集团有限责任公司研究设计院，云南个旧 661000） 摘要：采用HSC Chemistry 5.0热力学分析软件研究了As2O3真空碳热还原制备粗金属砷过程的吉布斯自由能与温度的关系，重点研究了挥发过程、碳热还原过程及砷蒸汽冷凝过程。结果表明，常压下As2O3在773 K时以As4O6(g)双原子气态形式挥发，而在100 Pa下挥发只需473 K即可，与实际情况一致；As2O3(g)气体参与碳热还原过程的可能性较小，As2O3(s)粉末、As4O6(g)气体在100 Pa真空压力下参与碳热还原反应温度分别是473~810 K、873 K，该温度均低于常压碳热还原过程所需温度（~1 203 K）；砷蒸汽的冷凝过程是As4(g)蒸汽先凝结成液态砷后，再冷凝成固态粗金属砷。 关键词：三氧化二砷；粗砷；真空；碳热还原；热力学分析 中图分类号：TF131 文献标识码：A 文章编号：1007-7545（2012）10-0000-00 Thermodynamic Analysis on Crude Metal Arsenic Preparation by Arsenic Trioxide Carbothermic Reduction in Vacuum LU Hong-bo (Research and Design Institute of Yunnan Tin Group Company Limited, Gejiu 661000, Yunnan, China) Abstract: Relationships between Gibbs free energy and temperature for crude metal arsenic preparation by As2O3 carbothermic reduction in vacuum were investigated with HSC Chemistry 5.0 thermodynamic analysis software. Volatilization process, carbothermic reduction process and arsenic vapor condensation process were emphatically studied. The results show that As2O3 volatilizes as As4O6(g) diatomic at 773 K under 0.1 MPa and 473 K under 100 Pa, which is highly correspondence with actual situation. There is little possibility for As2O3(g) take part in carbothermic reduction process. The temperature for As2O3(s) and As4O6(g) participate in carbothermic reduction reaction under 100 Pa is 473~810 K and 873 K respectively, which is less than that of 893~1 203 K under 0.1 MPa. The condensation process for arsenic vapor is As4(g) vapor firstly condensated into liquid arsenic, and then into solid arsenic. Key words: arsenic trioxide; crude metal arsenic; vacuum; carbothermic reduction; thermodynamic analysis 根据含砷化合物及单质砷毒性强弱的分析[1]，高纯砷没有毒性，而粗金属砷仅次之。因此，从含砷物料中提取粗金属砷，不仅有利于安全堆存，对粗金属深加工制备高纯砷也有很好的应用前景[2]。 目前，国内粗金属砷的制备普遍采用常压闷罐还原法[3]，但该方法因其生产环境恶劣而被国家严格限制生产。近年来真空冶炼技术得到蓬勃发展，该技术比常压冶炼具备更多的优势[4-5]：低氧环境有利于保证活泼金属的纯度、高真空下较低的初始反应温度可降低冶炼过程能耗、密闭反应环境可防止有毒有害物质对周围环境的危害等。因此，本文从真空碳热还原角度研究As2O3碳热还原制备粗金属砷的热力学。 1 热力学研究方法 采用HSC Chemistry 5.0热力学分析