工程科学学报，第37卷，第8期：994999,2015年8月 Chinese Journal of Engineering,Vol.37,No.8:994-999,August 2015 DOI:10.13374/j.issn2095-9389.2015.08.004:http://journals.ustb.edu.cn 红土镍矿非自由水脱除热分析动力学 刘梅”，吕学伟)@，白晨光”，邓青宇”，宋晶晶2 1)重庆大学材料科学与工程学院，重庆4000442)重庆市计量质量检测研究院，重庆401121 ☒通信作者，E-mail:lvxuewei@163.com 摘要在升温速率分别为10、15、20和25℃·min的条件下，利用差示扫描量热仪对红土镍矿广非自由水脱除过程进行了测 试.针对测试数据，分别采用Fynn-Wall-Ozawa(FWO)法、胡荣祖-高红旭-张海(HuGZ)法、Boswell法、Starink法、Friedman- Reich-Levi(Friedman)法等不同的转化率法计算其活化能，利用Malek法计算指前因子(A)以及确定机理函数，最后利用所 得的动力学公式推导出等温下反应进度与时间的关系并对不同温度下的能耗进行分析比较.红土镍矿非自由水脱除过程的 平均活化能为181.50k·mol1:指前因子lnA为21.95min:机理函数符合Z-L-T方程，即脱除过程为三维扩散控制机制； 干燥温度越高所需的平均功率越小 关键词红土镍矿：脱水：热分析：动力学：活化能 分类号TF815 Thermal analysis kinetics of non-free water removal in nickel laterite LIU Mei,LO Xue-wei,BAI Chen-guang,DENG Qing-yu,SONG Jing-jing? 1)College of Materials Science and Engineering,Chongqing University,Chongqing 400044,China 2)Chongqing Academy of Metrology and Quality Inspection,Chongging 401121,China Corresponding author,E-mail:Ivxuewei@163.com ABSTRACT Differential scanning calorimetric (DSC)data during non-free water removal in nickel laterite were determined with a NETZSCH STA 449C thermal analyzer.Experiments were carried out at four heating rates of 10,15,20 and 25 C.min-.According to these DSC curves at different heating rates,the activation energies were calculated by five different calculation methods of conversion rate,namely the Flynn-Wall-Ozawa (FWO),Hu-Gao-Zhang (HuGZ),Boswell,Starink,and Friedman-Reich-Levi (Friedman) methods.The pre-exponential factor (A)and the most probable mechanism function were determined by the Malek method,then the relationship between reaction degree and time under an isothermal condition was derived and the energy consumptions at different temperatures were analyzed and compared.The average activation energy of non-free water removal in nickel laterite is 181.50 k]. mol-.The average InA is 21.95 min-.The most probable mechanism function fits the Zhuralev-Lesokin-Tempelman (Z-T) equation well.The non-free water removal is controlled by three-dimensional diffusion.The average power decreases with increasing temperature. KEY WORDS nickel laterite;dewatering:thermal analysis;kinetics:activation energy 随着全球硫化镍资源的减少和不锈钢生产的需 近的热带国家，集中分布在环太平洋的热带和亚热带 求，红土镍矿被大量的应用到镍铁生产中.红土镍矿 地区四.红土镍矿含水量较大，一般含有20%~30% 是含橄榄岩在热带或亚热带地区经过大规模长期风化 左右的自由水和10%~20%左右的非自由水（包括结 淋滤变质而来的习.世界上红土镍矿分布在赤道附 晶水及羟基).水的大量存在将会对红土镍矿的开采 收稿日期：20140105 基金项目：国家自然科学基金资助项目(51234010)工程科学学报，第 37 卷，第 8 期: 994--999，2015 年 8 月 Chinese Journal of Engineering，Vol． 37，No． 8: 994--999，August 2015 DOI: 10． 13374 /j． issn2095--9389． 2015． 08． 004; http: / /journals． ustb． edu． cn 红土镍矿非自由水脱除热分析动力学 刘 梅1) ，吕学伟1) ，白晨光1) ，邓青宇1) ，宋晶晶2) 1) 重庆大学材料科学与工程学院，重庆 400044 2) 重庆市计量质量检测研究院，重庆 401121  通信作者，E-mail: lvxuewei@ 163． com 摘 要 在升温速率分别为 10、15、20 和 25℃·min － 1的条件下，利用差示扫描量热仪对红土镍矿非自由水脱除过程进行了测 试． 针对测试数据，分别采用 Flynn--Wall--Ozawa ( FWO) 法、胡荣祖--高红旭--张海( HuGZ) 法、Boswell 法、Starink 法、Friedman-- Ｒeich--Levi ( Friedman) 法等不同的转化率法计算其活化能，利用 Malek 法计算指前因子( A) 以及确定机理函数，最后利用所 得的动力学公式推导出等温下反应进度与时间的关系并对不同温度下的能耗进行分析比较． 红土镍矿非自由水脱除过程的 平均活化能为 181. 50 kJ·mol － 1 ; 指前因子 lnA 为 21. 95 min － 1 ; 机理函数符合 Z--L--T 方程，即脱除过程为三维扩散控制机制; 干燥温度越高所需的平均功率越小． 关键词 红土镍矿; 脱水; 热分析; 动力学; 活化能 分类号 TF815 Thermal analysis kinetics of non-free water removal in nickel laterite LIU Mei1) ，L Xue-wei1)  ，BAI Chen-guang1) ，DENG Qing-yu1) ，SONG Jing-jing2) 1) College of Materials Science and Engineering，Chongqing University，Chongqing 400044，China 2) Chongqing Academy of Metrology and Quality Inspection，Chongqing 401121，China  Corresponding author，E-mail: lvxuewei@ 163． com ABSTＲACT Differential scanning calorimetric ( DSC) data during non-free water removal in nickel laterite were determined with a NETZSCH STA 449C thermal analyzer． Experiments were carried out at four heating rates of 10，15，20 and 25 ℃·min － 1 ． According to these DSC curves at different heating rates，the activation energies were calculated by five different calculation methods of conversion rate，namely the Flynn--Wall--Ozawa ( FWO) ，Hu--Gao--Zhang ( HuGZ) ，Boswell，Starink，and Friedman--Ｒeich--Levi ( Friedman) methods． The pre-exponential factor ( A) and the most probable mechanism function were determined by the Malek method，then the relationship between reaction degree and time under an isothermal condition was derived and the energy consumptions at different temperatures were analyzed and compared． The average activation energy of non-free water removal in nickel laterite is 181. 50 kJ· mol － 1 ． The average lnA is 21. 95 min － 1 ． The most probable mechanism function fits the Zhuralev--Lesokin--Tempelman ( Z-L-T) equation well． The non-free water removal is controlled by three-dimensional diffusion． The average power decreases with increasing temperature． KEY WOＲDS nickel laterite; dewatering; thermal analysis; kinetics; activation energy 收稿日期: 2014--01--05 基金项目: 国家自然科学基金资助项目( 51234010) 随着全球硫化镍资源的减少和不锈钢生产的需 求，红土镍矿被大量的应用到镍铁生产中． 红土镍矿 是含橄榄岩在热带或亚热带地区经过大规模长期风化 淋滤变质而来的［1--3］． 世界上红土镍矿分布在赤道附 近的热带国家，集中分布在环太平洋的热带和亚热带 地区［4］． 红土镍矿含水量较大，一般含有 20% ～ 30% 左右的自由水和 10% ～ 20% 左右的非自由水( 包括结 晶水及羟基) ． 水的大量存在将会对红土镍矿的开采