Kroll法制备海绵锆的热力学和动力学  

Thermodynamics and Kinetics of Preparing Sponge Zirconium by Kroll Method

作　　者：王俊博 陈健 杨占鑫 尹桂丽[3] 李青春[3] 齐国超[3] 吴琼[3] WANG Jun-bo;CHEN jian;YANG Zhan-xin;YIN Gui-li;LI Qing-chun;Qi Guo-chao;Wu Qiong(Baotai Huashen Titanium Industry Co.,Ltd.,Jinzhou 121001,China;Baoji Titanium Industry Co.,Ltd,Baoji 721014,China;School of Materials Science and Engineering,Liaoning University of Technology,Jinzhou 121001,China)

机构地区：[1]宝钛华神钛业有限公司,辽宁锦州121001 [2]宝鸡钛业股份有限公司,陕西宝鸡721014 [3]辽宁工业大学材料科学与工程学院,辽宁锦州121001

出　　处：《辽宁工业大学学报(自然科学版)》2024年第6期380-387,共8页Journal of Liaoning University of Technology(Natural Science Edition)

基　　金：辽宁省“揭榜挂帅”科技计划项目(2023JH1/10400055);锦州市“春芽计划”重点科技攻关项目(JZ2023A013)。

摘　　要：为进一步优化镁热还原法(Kroll法)制备海绵锆的工艺,通过计算Mg还原ZrCl_(4)过程的吉布斯自由能变化和还原速率,分析还原剂Mg量、升华温度及氩气分压对还原过程的影响,同时研究海绵锆成品的结构成分、杂质分布和硬度变化。结果表明:升华炉温度控制在792℃,并保证还原剂Mg过量时,可减少进入还原炉的金属氯化物杂质种类;当氩气pAr平均占比为0.25时,相应还原反应速率为17.9 kg·h^(-1),产生的黑粉最少;海绵锆成品中Cl、Fe、Mg、O杂质元素在海绵锆中呈局部聚集状态,且Cl、Mg元素的聚集部位与O元素的聚集部位相对应;样品的最高硬度值为112 HB。In this paper,in order to further optimize the process of preparing sponge zirconium by magnesium thermal reduction method(Kroll method),the effects of reducing agent Mg content,sublimation temperature and argon partial pressure on the reduction process are analyzed by calculating the Gibbs free energy change and reduction rate of ZrCl_(4) reduced by Mg,and the structural composition,impurity distribution and hardness changes of sponge zirconium products were studied.The results show that controlling the temperature of the sublimation furnace at 792℃and ensuring an excess of reducing agent Mg can reduce the types of metal chloride impurities entering the reduction furnace.The least amount of black powder can be produced when the average proportion of pAr is 0.25 and the corresponding reduction reaction rate is 17.9 kg·h^(-1).Cl,Fe,Mg and O impurity elements exhibit local aggregation in sponge zirconium.The aggregation sites of Cl and Mg elements correspond to the aggregation site of O elements.In addition,the highest hardness value of the sample is 112 HB.

关 键 词：ZrCl_(4) 海绵锆 Kroll法 热力学 动力学 

分 类 号：TF841.4[冶金工程—有色金属冶金]